151 Pages
English

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 [Elektronische Ressource] / presented by: Muhammad Lukman

-

Gain access to the library to view online
Learn more

Description

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, IndonesiaA dissertation submitted for the degree of - Doktor der Naturwissenschaften - (Dr. rer. nat.) at the Faculty of Biology/Chemistry the University of Bremen, GermanyPresented 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 Referees : 1. Professor Dr. Wolfgang Balzer 2. Professor Dr. Wolfram Thiemann Examiners : 1. Professor Dr. Gerhard Kattner Professor Dr. Venugopalan Ittekkot Date of Colloquium: 29 March 2010ACKNOWLEDGMENTS 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.

Subjects

Informations

Published by
Published 01 January 2010
Reads 137
Language English
Document size 4 MB

lycyclic Aromatic Hydrocarbons Distribution and Sources of Po

in Sediments, Suspended Particulate Matter and Waters from

d Coastal Area of Sumatra, the Siak River System, Estuary an

Indonesia

itted for the degree of A dissertation subm- Doktor der Naturwissenschaften - (Dr. rer. nat.) the University ofat the Faculty of Biology/Che Bremen, Germmanyistry

Presented by:

man Muhammad Luk

Bremen, 2010

ycyclic Aromatic Hydrocarbons in Distribution and Sources of PolSediments, Suspended Particulate Matter and Waters from the Siak River System, Estuary and Coastal Area of Sumatra, Indonesia

A dissertatioat the Faculty of Biology/Chemn submistry, the University of Bremitted for the degree of Doktor der Naturwissenschaftenen, Germany (Dr. rer. nat.)

: yPresented b

ad LukmMuhamman

Referees 2.

iners Exam 2.

:

:

:Date of Colloquium

lfgang Balzer o1. Professor Dr. WProfessor Dr. Wolfram Thiemann

1. Professor Dr. Gerhard Kattner Professor Ittekkot Venugopalan Dr.

29 March 2010

ACKNOWLEDGMENTS

First of all, I would like to express my sincerely and great gratitude to Prof. Dr. Wolfgang
me of Bremen) for his remarkable role in pouring , UniversityBalzer (FB 2, Marine Chemistrywith 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
SPICE Cluster 3.1. (Science for the Protection of Indonesian Coastal group as well as to join theEcosystem) 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.
Gerhard Kattner and Prof. Dr. Venugopalan ItteI would like to thank Prof. Dr. Wolframkkot as the examiners, and Thiemann as the second referee, Prof. Dr. all the colleagues
and those previous colleagues in the marine chemistry working group, University of Bremen:
o Daberkow, , Tim Becker, Olaf Wilhelmüßler, Dr. Wolfgang Barkmann, ImmoDr. Uwe SchXiaoliang Tang, Jun Fu, Björn 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
proving the English. and critics, as well as to Nathan Giles for imAlso, 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
t. enof better environmthose who are fond

Kurzfassung

Die vorliegende Arbeit untersucht Ursprung und Verteilung von Polycyclischen Aromatischen
Kohlenwasserstoffen (PAKs) als Indikator für anthropogene Verschmutzung in den Küsten- und
Flussregionen der Insel Sumatra in Indonesien. Im Vordergrund steht dabei die Analyse der 16 PAK-
Prioritätsverbindungen, von denen Referenzmaterial gemäß der USA-EPA priority pollutants Liste
vorliegt. Untersucht wurden Proben in der Lösung und von Oberflächensedimenten und
Schwebstoffen (SPM) des Siak-Flusses, seiner Flussmündung und des Riau Küstenbereichs in
tra.amSu DiChromae Quantifitographen (RP-C18-HPLC) zierung der PAKs wurde untmit UV- und Fler Einsatz eiuoreszenz-Detektines Hochloneist durchgefungs-Flührtüssi. Digkeits-e
Analysenmethode beinhaltete eine Reihe von Probenahmetechniken für die individuellen Phasen
(Sediment, SPM, Lösung), Probenaufbereitung, Extraktion, Aufarbeitung und HPLC-Quantifizierung.
Die Unt(Sand) 2 mm – 63 μmersuchung der PAKs im und Feinf Sedraktioniment (Schl konzenick) < 63 trieμrte sich aum. Dife zweiSchwebst Größenkloffe wurassen: Grobfden über 0,7 μraktion m
Glasfaserfilter (GF/F) herausgefiltert. Die PAKs der Lösung wurden dann mittels eines Octadecyl
Festphasen Extraktionssystems (SPE) extrahiert. Die Qualitätskontrolle beinhaltete den Gebrauch von
Blindwerten und Ersatzstandards, um Genauigkeit und Effizienz der Analyse und die
Reproduzierbarkeit der Ergebnisse zu gewährleisten. Die Aufteilung in die verschiedenen
Stoffquellen der PAK-Verbindungen wurde unter Einbeziehung bekannter Indexe der
Molekulargewichte und spezifischen Isomer-Verhältnissen ausgeführt.
Die Untersuchungen ergaben, dass sowohl der Flusslauf als auch Flussmündung und Küstenbereich
des Siak-Flusses erheblich mit PAKs belastet sind. Die Untersuchungsergebnisse weisen auf kräftige
pyrogene Stoffquellen hin, insbesondere auf die Verbrennung von Biomasse und Erdöl. Sie können
daher als Nachweis für großräumiges, länger anhaltendes und intensives Verbrennen
landwirtschaftlicher Nutzflächen im Zusammenhang mit kräftigen Wald- und Torf-Feuern, die über
die letzten Jahrzehnte stattfanden, angesehen werden. In diesen von Buschfeuern heimgesuchten
Gegenden bilden die PAK-Verteilungen zwischen Grob- und Feinfraktion an der Küste und in der
Flussmündung ein deutliches Muster, das von den Verteilungen üblicher Küstenbereiche deutlich
der Siabweicht.ak-Küste Ein Verglmiteich den Küstder PAK-Verenbereichen von Wteilungen iennc den beihang und Wden Größenfanquan iraktin Conhinen ina deutet den Sedim daraufen hitenn,
dass die PAKs der Küstengewässer um Sumatra hauptsächlich mit den hohen kohleartigen
Materialien wie Ruß und verbranntem Torf assoziiert sind. Wie die Untersuchungen zeigen, können
auch andere relevante Stoffquellen wie andauernde Erdölverschmutzung in den Gewässern um die
Städte, in den industriellen Vororten von Perawang, der Ölstadt Dumai und der Erdölraffinerien im
Gebiet der Flussmündung für 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.
) V Kapitel Ianuskript – I,PAKs im Sediment (MDie PAK-Gehalte (Summe der 16 Standard-Verbindungen) in der Sedimentfraktion aller beprobten
Gebiete bewegen sich zwischen 0,13 und 5,47 μg/g Trockengewicht (TG). In der Grobfraktion (Sand)
wurden mit Werten zwischen 0,16 bis 5,47 μg/g TG (median m = 0,84) weitaus höhere
Konzentrationen gefunden (etwa um einen Faktor 2) als in der Feinfraktion (Schlick) mit Werten
zwischen 0,13 und 1,31 μg/g TG (m = 0,52). In der Grobfraktion ist die Anreicherung unerwartet, da
diese in der Regel wegen der größeren Oberfläche pro Masseneinheit in der Feinfraktion zu erwarten
ist. Ein ähnliches Muster wurde für das organische Material beobachtet. So variiert der Anteil des
organischen Kohlenstoffs an der Gesamtmasse der Grobfraktion zwischen 0,01% und 24%, während

lisich der Anteil inearer Zusammenhang zwin der Feinfraktion zwischen PAK und organiscschen 0,34% und 3,7% bewegthem Kohlenstoff. Ebenf nur in der Grobfalls war eiraktin nahezuon zu
erkennen. Aus diesen Untersuchungsergebnissen kann geschlossen werden, dass eine bestimmte Sorte
organischen Materials für die Affinität zwischen Kohlenstoff und PAKs verantwortlich ist, nämlich
vaskuläre Pflanzenreste, Torf und Ruß, wie auch in ähnlichen Untersuchungen festgestellt wurde.
Entlang des Flusslaufes in Richtung Flussmündung konnte kein klares Muster in den PAK-Gehalten
festgestellt werden, auffallend sind nur die Anreicherungen in den urbanen und industriellen
pyGebietrogene Spen. Die weiturenstoffgehenquellen schd hohen Molließen, inekulsbesondere aufargewicht die und die Verbe Molerennung von kularverhältBiomnisse asse und Erdöllassen au. f
Die PAK-Gehalte gelangen daher über den Land- und Luftweg in die Gewässer.
– II, Kapitel V) (Manuskript stoffenPAKs in der Lösung und in den SchwebDie gemessenen PAK-Gehalte in der Lösung bewegen sich zwischen 0,13 und 5,14 μg/L im
FlKüstusslaufenberei, zwich. In Richtschen 0,32 und 0,62 ung Küste niμg/mmt dL inie demmi ttlÄstere Konzentuar und zwiration umschen 0,12 und einen Fakt0,13 or 3 ab. Diμg/L ime
höchsten PAK-Gehalte wurden an der Einmündung des Mandau Flusses in den Siak Fluss gemessen.
Die PAKs wurden durch 2-, 3- und 4-Ring-Aromate dominiert. Die PAK-Gehalte in den
Schwebstoffen variieren zwischen 1,48 bis 59.1 μg/g im Flusslauf, zwischen 0,16 und 7,67 μg/g in
der Flussmündung und zwischen 0,33 und 10,2 μg/g in der Küstenregion. Auf das Volumen bezogen
bewegen sich die PAK-Gehalte im SPM jeweils zwischen 0,06 und 0,69 μg/L, 0,03 und 0,29 μg/L
und zwiwas auf eine schen 0,01 Ablagerung imund 0,15 μg/ SedimL. Dient und/e PAK-Gehaloder Verdünnung te nehmen immit AllgeSeewasser zumeinen inrückzuf Richtühren istung Küst. Eie ab, ne
Anreicherung mit PAKs findet sowohl in der Trockenzeit als auch in der Regenzeit statt, die durch
lassen sich dadurch die verschiedenenfalls n gekennzeichnet sind. Ebenverschiedene Ring-GrößeTransportwege der PAKs erschließen. Die Anreicherungen der PAKs in der Regenzeit können durch
eiwahrscheine Zunahnlich durch dime des Oberflächenabe Atmofsphäre stlusses entstattfindet. ehen, während in der Trockenzeit die Anreicherung
Eine Partitionierung der PAKs zwischen Schwebstoffen und Lösung wurde durchgeführt, um ein
bekommbesseres Verständnien. Die gems des Verlessenen Partauitifsonskoeffi der Anreizienten (cherung KD) zeidieser gen eiSchadstne beträchoffe intliche Streuung den Gewässern zuzwischen
den beprobten Stationen. Der mittlere KD-Wert im Flusslauf und in der Flussmündung variiert
zwischen 4 und 5 auf der logarithmischen Skala, an der Küste 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 Mündung und zwischen 3 und 5 an der Küste. Diese Variation deutet auf
eieine bedeune unterschtiedende Rolliclehe Qualit spieläten könne des partikuln. Anscheiären organinend erhöhtschen Mat dierie Zunahals hin, imen der Rußabldes Salzgehaltagerungen s und
eventuell des pH-Wertes den Koeffizienten KD. Auf der anderen Seite hat die Zunahme des gelösten
organischen Kohlenstoffs (DOC) einen umgekehrten Effekt. Dies deutet auf eine wichtige Rolle des
DOC für die Erhaltung schwerer PAKs in der Lösung hin, was auch eine Erleichterung ihres
Transports beinhaltet.
Ein Vergleich zwischen den Messungen am Siak-Ästuar (torfhaltiger Boden) und denen
an den Wenchang und Wanquan Flussmündungen (sandiger Boden) (Manuskript – III,
itel VI) KapDie Verteilung der PAK-Konzentrationen in den Sedimentfraktionen der Siak-Flussmündung und des
FlKüstussmengebiündungen ietes wurde n Haimitnan, Chi den Mna vergelissungen an den Wchen. Die Gebiete zeienchanchnen sig (WWch durch i)- uhnd Wre unaterschinquan (WedlichQ)-e
Bodenformation aus: torfhaltig am Siak-Fluss und eher mineralisch oder huminstoffarmer Boden auf
Hainan. Wie oben erwähnt, sind die PAK-Konzentrationen in den Siak-Sedimenten durch einen
hohen wurde niAntchteil i nvon P den WAW/WKs und organiQ-Sedimschement Maten geferiual inden n, inder Grobf denen diraktion charakterie PAKs hauptsiert. Disächlieses ch iMnu dsteer r
Feinfraktion zu finden sind. Die gemessenen PAK-Konzentrationen der 15 US EPA priority pollutants
(ausgenommen Acenaphthylen) bewegen sich in der Siak-Flussmündung zwischen 0,13 μg/g TG und

1,83 μg/g TG (median m = 0,69 μg/g TG) in der Grobfraktion und zwischen 0,09 μg/g TG und 0,43
μg/g TG (der WW/WmQ -Sedim= 0,20 μg/g ente zwiTG) in der schen 0,11 μg/Feinfraktig TG und 0,39 on. Dagegen μg/g TG (mwurden PAK-Wer = 0,19 μg/te g TG) und iin der Grobfraktionn der
Feinfhohe PAK-raktion zwiKonzentratischen 0,09 μg/on ing T der GrobfG raktiund 0,68 μg/on der torfg TG (mreichen Bodenf = 0,47 μg/ormg TG)ation gef von Sunden. umatDire relata konnte iv
den hohen Konzentrationen der kohlenstoffhaltigen Materialien wie Ruß, Torf und
Pflbeitragen. In den Wanzenablagerungen zugeordnetW/WQ-Sedim weentrden, welen wurden diche zur Anreiese hohen Kohlcherung enstder PAKs an den offkonzentratiMaonen niterialichen t
gefunden. In beiden Gebieten gab es keine Unterschiede in den Molekularverteilungen zwischen
ähnliGrob-chen und FeiQuelnfraklen sttion, was alammen. Dags Hinweis gewertegen deuteten di werden kann,e Iso damss dierenverhältnie PAK-Verunreisse, die fniügungen von r die
Quellenbestimmung hinzugezogen wurden, darauf hin, dass die PAKs der Siak-Flussmündung durch
Sedimente auBuschfeuer und ähnls der Kohliche e- und ÖlVerbrennungen entverbrennung ststaanden simmen. Dind, wohie Konzentratingegen dion der gele PAKs der östen PAKs iWW/Wn denQ-
-1küstennahen Ästuaren von WW/WQ war relativ gering. Die PAKs waren zwischen 7,36 und 16,2 ng
Lbet. Imrug zwischen 121 Gegensatz dazu waund 619 ng Lr die Konzent-1. Huratimion imnsto Siak-Ästuar soffe in den überliegenden wie an der KüstWassere erhebschliichch höher. Siten spielen e
ebenfalls eine Rolle für die Verteilung der PAKs in den Sedimentfraktionen. So enthält die Siak-
FlGebiussetmen nichtündung und di gefe Küstenregiunden wurden (Balzer, unveröfon signifikantefentlich Mengen an DOC, dite Daten). Die ine Vert den beprobteilungskoeffizientenen WW/WQ-
zwiSediment-schen 2,22 und Wasser der ei5,58 (nzelMedianen PAKs n m = im 3,37)Si füak-Ästr die Grobfuar ergaben raktion und zWerte (auwfi derschen logarithmi 1,53 und 5,03 (mschen Skala) =
3,01) in der Feinfraktion. So liegen die KD-Werte im Siak-Ästuar niedriger als in den WW/WQ-
Ästuaren, zwischen 1,12 und 5,89 (m = 3,93) für die Grobfraktion und zwischen 2,58 und 5,85 (m =
des Si4,40) füak eir die ne FeinAdsorptfraktiion. Dion an dies läe organisst vermuschen Sedimten, dass dientbestandteile hohe DOC-Konzente behindert. ration in der Wassersäule

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 μm 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.
Sedimentary PAHs (Manuscript – I, Chapter IV)
The PAHs for the sedimentary fractions in all sampled areas ranged between values of 0.13
to 5.47 μg g-1 dry weight (d.w.) sediment. The PAHs in the sand fraction ranged from 0.16 to 5.47
μg g-1 d.w. (median m = 0.84). In general, the sand fraction contained PAH levels higher by a factor
of ±2 as compared to those found in the mud fraction that ranged from 0.13 to 1.31 μg g-1 d.w. (m =
0.52). The enrichment of PAHs in the sand fraction was quite astonishing, especially since we
assumed that the fine fraction would generally evidence much higher levels of contaminants, due to
its large surface area per unit mass for adsorption. The same pattern of enrichment was shown by
the organic matters. The organic carbon (OC) contents varied greatly from 0.01% to 24% in the
sand, but only slightly in the mud from 0.34% to 3.70%. A linear relationship between the PAH and

the OC was shown only by the sand fraction. These all evidences lead us to the assumption that a
specific kind of organic matter should be responsible for high affinity for PAHs. Thus, it is most
likely materials such as black carbon, vascular plant debris, and peat as figured out by many other
studies. The spatial distribution showed no clear pattern in distance to the river mouth. But,
increased content of the PAHs was centred at urban and industrial areas. The high molecular weight
compounds were 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 systems by both land-water and air-water transports.
Dissolved and Particulate PAHs (Manuscript – II, Chapter V)
Dissolved PAHs ranged from 0.13 to 5.14 μg L-1, 0.32 to 0.62 μg L-1, and 0.12 to 0.13 μg
L-1 in the Siak River, its estuary and the coastal areas, respectively. The mean concentration
decreased by a factor of 3 towards the coast. The highest concentration was observed in the water at
the confluence of the black water Mandau River, a Siak tributary. The PAHs were dominated by 2-,
3-, and -14-ring compounds. The PAHs -1in the SPM varied greatly from 1.48 to 59.1 μg g-1, 0.16 to
7.67 μg g, and 0.33 to 10.2 μg g for the Siak river, its estuary and the coast, respectively. In
volume basis, the concentration of particulate PAHs ranged from 0.06 to 0.69 μg L-1, 0.03 to 0.29
μg L-1, and 0.01 to 0.15 μg L-1 in the River, the estuary and the coast, respectively. The PAHs
generally decreased towards the coast suggesting an entrapment and/or dilution effect of sea water.
PAH enrichment occurred in both wet and dry seasons characterized by different ring-size
dominance. It suggests different mode of transport by which PAH were integrated into the aquatic
environments. The accumulation of PAHs in the river during rainy season could be attributed to an
increasing land-water surface runoff. Meanwhile, in the dry season, the enrichment was most likely
caused by atmospheric deposition.
Partitioning of the PAHs between SPM and water solution was evaluated to understand the
fate of these contaminants in the given aquatic systems. Measured partition coefficient (KD) showed
a considerable variation between the sampling locations. The mean KD values in the River and the
estuary ranged from 4 to 5 on the logarithmic scale, while in the coast was 6. The mean values of
organic-carbon normalized partition coefficient (KOC) ranged from 2 to 4 on the log scale in the
River and the estuary, whereas from 3 to 5 in the coast. This variation suggests a different quality of
particulate organic matter, in which black carbon might play a significant role. The increase in
salinity and possibly also in the pH apparently turns to increase the KD, but enriched DOC affects
negatively. It indicates an important role of DOC in sustaining heavier PAHs in the dissolved phase,
including a facilitation of their transport.
A comparison between peatland aquatic system of Siak Estuary and a non-peatland
aquatic system of Wenchang and Wanquan Coastal Estuaries (Manuscript – III, Chapter
VI)Distribution of PAHs in the two grain-size fractions of the Siak Estuary and the Coast was
compared with those from non-peatland systems of Wenchang and Wanquan (WW/WQ) Coastal
Estuaries, Hainan, China. As described earlier, the PAHs in the Siak sediments were generally
characterized by high content of PAHs and organic matter in the coarse fraction. This kind of
distribution was not confirmed by the WW/WQ sediments which in most cases PAHs enriched in
the fine sediments. The level of the total 15 US EPA priority pollutants excluding acenaphthylene in

the Siak estuary and the coast ranged from 0.13 μg/g d.w. to 1.83 μg/g d.w. (median m = 0.69 μg/g
d.w.) in the coarse fraction, and from 0.09 μg/g d.w. to 0.43 μg/g d.w. (m = 0.20 μg/g d.w.) in the
fine fraction, while the the WW/WQ sediments PAHs ranged from 0.11 μg/g to 0.39 μg/g d.w.
(median m = 0.19 μg/g d.w.), and from 0.09 μg/g to 0.68 μg/g d.w. (m = 0.47 μg/g d.w.) in the
coarse and the fine fractions, respectively. The high content of PAHs in the coarse fraction of the
degraded peatland system of Sumatra was due to the existence of high carbon content carbonaceous
materials i.e. black carbon, peat, and plant debris acting as strong sorbents for PAHs, which were
not found in the WW/WQ sediments of Hainan. In both compared areas, there were no differences
in molecular distribution between the fractions 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. The concentration of dissolved PAHs in WW/WQ coastal estuary was
relatively low. The PAHs ranged from 7.36 to 16.2 ng L-1. In contrast, the level of the PAHs
dissolved in the Siak estuary and the coast ranged from 121 to 619 ng L-1. Humic substance in the
overlaying water plays a role in distribution of PAH in the sediment fractions. The Siak estuary and
the coast contained significant amount of DOC compared to the Wenchang and Wanquan coastal
estuaries (Balzer, unpublished data). DOC in the Siak water may sustain the PAHs in the water
column impeding their association onto the sediment organic matter as shown by sediment-water
distribution coefficient (KD). The sediment-water distribution coefficients (KD) values of the
individual PAH in the Siak estuary ranged in logarithmic value from 2.22 to 5.58 (median m = 3.37)
for the coarse fraction, and from 1.53 to 5.03 (m = 3.01) for the fine fraction. The KD values in the
Siak estuary are generally lower than those of WW/WQ estuaries, which greatly ranged from 1.12
to 5.89 (m = 3.93) in the coarse fraction, and from 2.58 to 5.85 (m = 4.40) in the fine fraction. It
suggests that high DOC in the Siak water may sustain the PAHs in the water column impeding their
association with the sedimentary organic matter.

TABLE OF CONTENTS

1INTRODUCTION ............................................................................................................. I.1.1.Polycyclic aromatic hydrocarbons: definition and physio-chemical characteristics ........... 2
.... 2Definition ....................................................................................................................1.1.1.1.2.1.1.2.PAH contamSelected physiination in the o-chemical characteristics aquatic environments: background to........................................................................ environmental problems 53
1.2.1.Toxicity of PAHs ............................................................................................................ 5
1.2.2.Bioconcentration and magnification in aquatic food webs ............................................. 7
1.2.3.Persistence, low degradation rates and pollution indicators ........................................... 9
1.3.The relevance of rivers, estuaries and coastal areas in Indonesia ...................................... 10
1.3.1.A Perspective on the global pollution dispersal ............................................................ 10
1.4.1.3.2.StudyEnvironm Objectives ental settings of the study areas: An Overview ........................................................................................................................................................... 13.. 19
II.SOURCES, DISTRIBUTION AND FATE OF PAHs IN AQUATIC
20................................................................... SHORT REVIEW COMPARTMENTS: A ...... 20Introduction ..................................................................................................................2.1.2.2.Source and Signatures ........................................................................................................ 20
2.2.1.2.2.2.PyrNatural PAHs ogenic PAHs ................................................................................................................ ........................................................................................................... 2220
PAHs ........................................................................................................... 29Petrogenic 2.2.3.2.2.4.Source Apportionment .................................................................................................. 32
2.3.Distribution in Aquatic Compartments .............................................................................. 39
2.3.2.2.3.1.Suspended PSurface Sediament and Grain Size Fractirticulate Matter and Water ons ...................................................................... ................................................................. 3942
2.3.3.Water Solution as dissolved PAHs ............................................................................... 43
2.4.The fate of PAHs in the water: a partitioning concept and the role of natural organic
......... 44matter ........................................................................................................................III.METHODS OF ANALYSIS ........................................................................................... 47
...... 47Introduction ..................................................................................................................3.1.3.2.Sample Collection and Treatments for PAH ..................................................................... 47
3.2.1.Surface Sediment and Size Fractionation ..................................................................... 47
3.2.2.Suspended Particulate Matter (SPM) ............................................................................ 48
3.3.3.2.3.Determination of polycyclic aroSolid phase extraction (SPE) for pre-concentration ofmatic hydrocarbons using high performance liquid dissolved PAHs ....................... 48
3.3.1.chromatographySoxhlet Extraction of sediment and SPM coupled with ultraviolet and fluorescence detector..................................................................... s (HPLC UV/FLD) .. 5050
3.3.2.3.3.3.Elution Extract Working-Up of the SPE Cartridges for dissolved PAHs ..................................................................................................... ....................................................... 5152
3.3.4.PAH determination: High Performance Liquid Chromatography with ultraviolet and
fluorescence detectors (HPLC UV/FLDs) .................................................................... 53
3.4.Quality Controls ................................................................................................................. 57
References (Chapter I – III) ...................................................................................................... 59
IV.DISTRIBUTION AND SOURCE OF POLYCYCLIC AROMATIC
FACE SEDIMENTS FROM THE SIAK HYDROCARBONS (PAHs) IN SURRIVER, ITS ESTUARY AND THE ADJACENT COASTAL AREA OF RIAU
69............................................................................................. PROVINCE, INDONESIA 4.1.Abstract ......................................................................................................................Introduction .................................................................................................................................... 69...... 70
4.2.Study Area and Methods .................................................................................................... 71

4.2.2.4.2.1.SamStudy Area & sample Collection and Frapling locations ctionation ................................................................................. ............................................................................ 7271
4.2.3.Analytical Methods ....................................................................................................... 72
4.3.Results & Discussion ......................................................................................................... 74
4.3.1.Geochemistry of sediment fractions ............................................................................. 74
4.3.2.Content and Distribution of PAH ................................................................................. 75
4.3.3.PAH & OC Relationship .............................................................................................. 77
4.3.4.Relative Composition of PAHs .................................................................................... 79
4.3.5.Source Apportionment .................................................................................................. 80
..... 82Conclusion ....................................................................................................................4.4.V.POLYCYCLICAROMATICHYDROCARBONSINSURFACEWATERSOF
THESIAKRIVER,ITSESTUARYANDTHECOASTALAREASOFRIAU
PROVINCE,INDONESIA:DISTRIBUTIONANDSOURCES ............................. 86
5.1.Abstract ......................................................................................................................Introduction .................................................................................................................................... 86...... 87
5.2.Materials and Methods ....................................................................................................... 88
5.2.1.Study Areas and Sampling Locations ........................................................................... 88
5.2.2.Sample Collection and Treatments ............................................................................... 89
5.2.3.Extraction & Work-Up Procedures for particulate PAH .............................................. 89
5.2.4.Solid Phase Extraction (SPE) system for dissolved PAH ............................................. 89
5.2.5.Determination of PAH by HPLC UV/FLD .................................................................. 90
5.3.Results and Discussion ...................................................................................................... 91
5.3.1.Dissolved PAHs ............................................................................................................ 91
5.3.2.PAHs in the SPM .......................................................................................................... 92
5.3.3.5.3.4.Distribution Source apportionment Coefficient of PAHs between SPM and ................................................................................................... Water Solution .......................... 9896
... 100Conclusion ....................................................................................................................5.4.VI.A COMPARISON OF POLYCYCLIC AROMATIC HYDROCARBONS (PAHs)
SEDIMEIN PEATNTLAND AND NON-PES: A STUDY OF THE SATLIAK ESTAND AQUATIC SYSTUARY, SUMATEM SURFACE RA, INDONESIA
AND OF THE WENCHANG AND WANQUAN ESTUARIES, HAINAN ISLAND,
... 104CHINA .........................................................................................................................6.1.Abstract ......................................................................................................................Introduction .................................................................................................................................. 104.... 105
6.2.Materials and Methods ..................................................................................................... 106
6.2.1.Study areas, Sample Collection and Fractionation ..................................................... 106
6.2.2.Determination of PAHs .............................................................................................. 108
6.2.3.Determination of Sedimentary Organic Matter .......................................................... 110
....... 110Results .......................................................................................................................6.3.6.3.1.PAHs and Organic Matter in Sedimentary Size Fractions.......................................... 110
6.3.2.Relative Composition of PAHs .................................................................................. 112
6.3.3.Source Apportionment ................................................................................................ 113
6.3.4.Sediment-Water Distribution Coefficient ................................................................... 114
6.4.Discussion ........................................................................................................................ 115
... 119Conclusion ....................................................................................................................6.5....... 124APPENDIXES ....................................................................................................................

INTRODUCTION I.

An examination the distribution and sources of polycyclic aromatic hydrocarbons (PAHs)
in aquatic systems (rivers, estuaries and coastal waters) tackles key factors, which concern both
fore they are ent and also these pollutants' behavior beenvironmthe overall health of the integrated into the open ocean. During the last three decades, there has been a mounting body of
scientific literature about PAHs in aquatic environments from many parts of the world. These
persistent pounds as manyese comhstudies indicate substantial and widespread concerns about torganic pollutants (POP) such as pestiorinated biphenyls (PCBs). It also chlcides and polyconfirms a significant breakthrough in analytical methods such as sample collection, working-
up procedure, and determination of PAH with analytical instruments such as capillary GC, GC-
MS, and high performance liquid chromatography with ultraviolet and fluorescence detectors.
Unfortunately, research in developing countries, in particular Indonesia and other tropical
regions of the globe, has up to the present been sorely lacking. On the other hand, the relevance
ngly r the global redistribution of organic pollutants has been increasioents fof tropical environmscharge of persistent that the di994) showed (1recognized by scientists. For instance, Iwata et al. and semi-volatile compounds taking place in eastern and southern Asia such as India, Thailand,
Vietnam, Malaysia, Indonesia and Oceania had a significant effect on pollutant redistribution on
a global scale, particularly important through air and water phases.
refine the scientific understanding of the distribution and pts to attem This studymagnitude of PAH contamination in such aquatic environments, especially those surrounded by
large areas of peat. It attempts to comprehensively examine the concentrations of PAHs in the
sediments, suspended particulate matter (SPM), and water solution of Siak River, its estuary and
the coastal areas of the Riau province, Sumatra, Indonesia. To start off, the definition and
give a general understanding on introduced to ico-chemical of selected PAHs are conciselysphye pounds investigated (Chapter I). Also, in this chapter, the relevance of thmthe subject of the coPAH contamination in the aquatic environment is presented for some points of motivation i.e.
and persistence agnification as well as ration/biomtoxic/carcinogenic effects, bioconcentdegradation aspects of these compounds. In response to those motivations, the distribution and
the sources of PAHs in the aquatic environment are shortly reviewed to examine the key
environmental problems underlying this PAH investigation (Chapter II). Then, the PAH
determination is presented for three aquatic compartments: sediment, SPM and water as for
discussion are sis are given in Chapter III. The results and dissolved PAHs. Methods of analyelaborated in three manuscripts for publication. The first manuscript deals with the distribution
and source of PAHs in the sediment of the Siak river system (Chapter IV). This manuscript
examines the levels and sources of anthropogenic PAH contamination in two sediment fractions

1

(sand/coarse: 2 mm – 63 m and mud/fine: <63 m on the Wentworth scale). The second
hropogenic PAH ibution and sources of antconcentration, spatial distrmanuscript evaluates the contamination on SPM and dissolved PAHs in surface waters of the given study areas (Chapter
ments V). The last manuscript deals with the character differentiation of PAHs in surficial sedifrom peat- and non-peatland aquatic systems, which is a comparative study of the Siak estuary
hapter VI). and Wenchang/Wanquan estuaries of Hainan, China (Catra of Sum was an integrated part of Cluster 3.1. of the SPICE The work undertaken in this studyProject (German-Indonesian Science for the Protection Indonesia Coastal Ecosystem) - a
ed out between 2004 and 2007. The generalrricaresearch collaboration on marine biogeoscience theme of Cluster 3.1 was "coastal ecosystem health: the transfer of natural and anthropogenic
focusing in particular on the Siak River in Riau m land to the coastal sea", materials froProvince, 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.

Polycyclic aromatic hydrocarbons: definition and physio-chemical 1.1.characteristics

Definition 1.1.1.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.
pounds. A fused riparent comPAHs are therefore explicitly associated with their ng 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
the sixteen parent PAH commixture in the environment. For the purposes of thpounds listed byis the US Environmstudy, however, we restrictental Protection Agencyed ourselves on its to
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
y include naphthalene (NAPH), Dalton (Fig. 1.1). Theranging from 128 Dalton to 278 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-
rene (IPYR).)pyc,d

cal characteristics sio-chemiSelected phy1.1.2.These unsubstituted aromatic compounds are non-polar, lipophilic and highly
hydrophobic in nature. Selected physio-chemical characteristics of given PAHs are summarized
in Appendix 1 (see for details and references). Briefly, the compounds are highly soluble in
er partition coefficient (Logic values of the octanol-watcertain organic solvents with logarithmKow) for each of the compounds ranging from 3.45 to 6.75 (Williamson et al., 2002). Their water
solubility is very low and ranges between values of only 0.3 g/L and 30.2 mg/L (Williamson et
al., 2002). Low molecular weight compounds i.e. naphthalene, acenaphthene and
acenaphthylene, have the highest water solubility with values of 30.2, 16.1, and 3.93 mg/L,
respectively. The solubility decreases with increasing molecular mass. PAHs generally tend to
be more easily adsorbed onto organic matter. In the environment, PAHs are readily associated
with other natural, organic substances such as biopolymers (e.g. polysaccharides, lipids, protein
and polynucleic acids), humic substances (e.g. humic acids and fulvic acids), kerogens and
and these geo-inants portant review of the interactions between contammblack carbon. One i given by Weber et al. (2001). sorbents was The vapor pressure of PAHs is quite low, ranging from 8.89 ·10-2 – 2.10 ·10-11 mmHg,
which often leads to their classification as semi-volatile compounds. Their boiling points ranges
from 218 oC to 542oC, and the melting point span from 80 oC to 279 oC. At ambient conditions,
they usually occur as almost colorless solids, normally being white or pale yellow in color e.g.
IPYR. In the aquatic environment, however, they occur either as free molecules or associated
with dissolved organic matter, particulate phases and sediments.
The benzene ring structures of these compounds are rigid. PAH molecules are
appreciably stable and prefer substitution reactions to additions. With respects to molecular
structure, there is a different degree of thermodynamic stability between peri-condensed PAH
compounds to cata-condensed ones (Grope, 2001). Peri-condensed PAHs such as fluoranthene,
pyrene, benzofluroanthene, benzo(a)pyrene, benzo(g,h,i)perylene, indeno(1,2,3-c,d)pyrene, are
less stable. On the other hand, within the cata-condensed structure, those with linear structure
s such as anthracene to its isomer phenanthrene (Grope, erngular isomable than their aare less st

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.

NAPHACYNACENFLUPHENANTH
NaphthaleneAcenaphthyleneAcenaphtheneFluorenePhenanthreneAnthracene
MWC=10128H8,17MWC=12152H8,20MWC=121H5410,21MWC13=1H6610,22MWC=141H7810,22MWC=141H7810,23

FLAPYRBaACHRY
FluoranthenePyreneBenzo(a)anthraceneChrysene
MWC=162H0210,26MWC=16H20210,26MWC=182H2812,29MWC=182H2812,29

BbFLABkFLABaPDANTH
Benzo(b)flourantheneBenzo(k)fluorantheneBenzo(a)pyreneDibenzo(a,h)anthracene
C20H12C20H12C20H12C22H14
MW=252,32MW=252,32MW=252,30MW=278,35

BPERYIPYR
Benzo(g,h,i)peryleneIndeno(1,2,3-c,d)pyrene
C22H12C22H12
MW=276,34MW=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.environmenPAH contaminationtal problems in the aquatic environments: background to

PAH contamination is one of the primary environmental problems facing humanity at
present. This is due to the fact that PAHs are toxic, mutagenic and/or carcinogenic to both
humans and other organisms. They also are subject to bioaccumulation and concentration in the
aquatic food web. Additionally, they are relatively persistent in the environment. Mounting
literature has provided sufficient evidence of their global distribution and high concentrations in
atmospheric, terrestrial and aquatic systems. For example, Zhang & Tao (2009) published the
global atmospheric emission inventory of 16 PAH priority pollutants from 37 countries. It was
estimated that PAH global emission in 2004 accounted for 520 giga grams per year, with 55%
a. China, India and the United State were the top three Asiming fromof the total emissions cocountries with the highest PAH emission. However, as environmental investigation increases worldwide it can be assumed that the number of and places in which significant amounts of
PAHs are found may also increase. This implies an increasing potential of human exposure to
PAHs and a growing number of possible sources for these compounds. Particularly important in
this respect are aquatic systems, which include rivers, estuaries and coastal waters, upon which
nd other resources. Both water upon for food amillions of people relytens or even hundreds of for drinking and hygiene and also the vast number of both freshwater and marine fish species
and other organisms used as food sources for humans are directly tied to such ecosystems. This
is especially true for a country like Indonesia where people rely on river, estuary and coastal
resources.

Hs AToxicity of P1.2.1.organisms. tagenic and/or carcinogenic threats to humans and other uPAHs pose toxic, mA number of toxicity and cancer cases in both human and aquatic organisms have partly been
associated with increasing chronic and acute exposure to high concentrations of PAHs from the
ambient environment or specific contaminated sites (e.g. Brasseur et al., 2007; Cachot et al.,
2006; Chiang et al., 2009; Hu et al., 2007; Smith et al., 2000). Many molecular epidemiological
studies have shown evidence of increased levels of several biomarkers indicating PAH
ple PAH-DNA adducts and oxidative DNA damage in populations y, for examgenotoxicitexposed to increasing levels of PAH (e.g. Shou et al., 1996; Hussain et al., 1998; Liu et al.,
2007; Singh et al., 2007). A relationship between PAHs and cancer causes of lung, skin, bladder
(Bofetta et al., 1997) and prostate (Rybicki et al., 2006) was shown to be conclusive.
The mutagenic/carcinogenic effects of PAHs are mainly exerted through electrophilic
metabolic activation of the compounds due to their planar, highly conjugated aromatic
structures. PAH metabolites are then capable of modifying DNA, which is the key to
mechanisms of metabolite activation have been widely proposed by carcinogenesis. Several

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
005). 2 ( Xue & Warshawskywas provided byAlthough it is still an area of intensive epidemiological study, toxicological profiles of
). Thebeen introduced (e.g. ATSDR, 1995 see www.atsdr.crc.gov PAHs have alreadyResearch on Cancer (IARC), an institute within the World Health for International Agencypounds in several of the comdividual PAHnOrganization, has classified the carcinogenicity of ievidence derived strength of based on thefication was parent groups (Table 1.1.). This classifrom 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
etta et al., 1997;RC) and is often used as a hazard index for PAH exposure (BofA(Group 1 of IRavindra 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 n exposure can occur through inhalation,amlikelihood of human exposure could raise. Hu. Inhalation and TSDR, 1995)etta et al., 1997; Aabsorption/adsorption (skin), and ingestion (Bofskin 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
ough food and ingestion thr., 1997). However, paving and carbon production (Bofetta et aldrinking remains the most significant route for PAH contamination in humans. As much as 90%
could result o the human organismpounds int intake of persistent pollution comof the total dailysolely from diet (Binelli & Provini, 2004; Wenzl et al., 2006). In this context, animal food
afood. a significant role, particularly fish and se sources play

6

qualitTable 1.1.y guidel List of priority ines (content in g/L for waPAHs and their carcinogenicityter and ng/g dry sediment weight). classification, water and sediment
Water Quality Compounds CarcinogClassification* enicity Standard** Sediment Quality Guidelines***
b,c,d(group) ERL ERM
Acenaphthene b,c, 3 d 16 500
AntAcenahracene phthylene a,b,c,d 3 NI 0.0 06** 8544.3 164100 0
Benz[a]anthracene a,b,c,bd,c,d 2B e261 1600
BenzoBenzo[a][b]pfluyreornane thene 1a,b,c,d 2B 0.0.000011e 430 1 600
dBenzo[e]pBenzo[g,h,i]perylene yrene 3 a,b,c,d 3 0.00 1e
dBenzoBenzo[j][k]fflluuoorraannthethene ne a,b,c, 2Bd 2B 0.00 1e
d,c,bDibeChrysene nz[a,h]ant 2hrancene b,c,d 2AB 36384 .4 226800 0
b,c,da,Fluorantheb,c,dne 3 0.01** 600 5100
IndeFluorene no[1,2,3-c, 3 d]pyrene a,b,c,d 2B 0.00 1e 19 5 40
Naphthalene a,bb,c,c,d 2B 0.01** 160 2100
PhePyrenenant b,c,hred 3 ne 3 6265 40 21600 500
ba EU W the US EPA F(http://www.epaD, 2000/60/EC in Annex X (http://e.gov/epaoswer/hazwaste/uropa.eu/scadplus/leg/minimize/chemen/lvlistb/l.ht2810m); 8.htm);
dc NPI Australia; Canadian NPRI Substance 2007;
e Priority* IARC: http://m & hazardous substances basonographs.iarc.fred on the d/ENG/Classificatioecision # 2455/n/index.ph200p. Group 1: Carcinogenic to hu1/CE of the European Parliament mans; Group 2A: probably
carcinogenic to humans; Group 2B: possibly carcinogenic to humans; Group 3: not classifiable as to carcinogenicity to humans;
Group 4: probably** Maggi et al 2008; not carcinogenic to humans;
*** adoNI = informpted from ation not available Long et al., 1995: ERL= the effects range-low, ERM= the effects range-median
in aquatic food webs agnification Bioconcentration and m1.2.2.rine organisms. Bioconcentration and a magnified byPAHs are bioconcentrated and biombioaccumulation of PAHs in organisms occurs via all three chemical exposure routes, including
dietary absorption, transport across respiratory surfaces and dermal absorption (Mackay &
. The degree of portantmost imFraser, 2000). Of these possibilities, the first two routes are the bioconcentration is determined by tissue lipid content (Kayal & Connell, 1995). An appreciable
increase in PAH concentration has been observed in various marine organisms as compared to
their environment (water or sediment). For instance, Barbour et al. (2008) observed appreciable
bioaccumulation factors in oysters harvested from a war-induced oil spill zone in the Eastern
Mediterranean Sea, which extend from 242 to 3700.
Along with bioconcentration, biomagnification has been recorded from lower to higher
trophic levels of organisms, e.g. plankton (Carls et al., 2006), benthic amphipods (Viganò et al.,
2007); mussels (Okay et al 2000; Richardson et al., 2003; Pérez-Cadahía et al 2004; Hellou et
al., 2005), other bivalve organisms (Oros & Ross 2005), oysters (Mondon et al., 2001), eels
(Ribeiro et al 2005), feral finfish (Hellou et al 2006), and other fish species (Liang et al., 2007).
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. Martí-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,
late these toxins. umthey tend to accuBioconcentration/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
matter found in tter content, SPM and sediment grain-size. Organic amproperties i.e. organic 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
acteristics. specific charent-environmaccording to ter and the fineness ofmate presence of suspended particulate Further factors such as thsediment grain-sizes are also important for the bioaccumulation of organic pollutants, especially
mard et al. (1998) valves. Baums such as biin filter/suspension-feeding and detritivorous organiswith e contact found a significant bioconcentration of PAHs on organisms living in clossediments 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.

Persistence, low degradation rates and pollution indicators 1.2.3.PAHs are persistent over longer periods of time when found in bottom sediments. Once
bound to aquatic sediment particles, PAHs can effectively survive for years. This fact stems
from their relatively stable chemical structures, particularly under anaerobic conditions (Neff,
1979; Mihelcic & Luthy, 1988). Due to this, PAH signatures in sediments are often used as
indicators in identification of pollutant sources. PAHs have also been tested by geochronicle
ita unker et al., 1999; Yamash(e.g. Gevao et al., 1998; Yng at dated sediment cores studies lookiet al., 2000; Fabbri et al., 2003; Ricking et al., 2005). Thirty years ago, Hites et al (1977)
published an experiment which showed the relative stability of PAH composition over hundreds
of years. Their analysis documented unsubstituted PAHs and their alkyl homologues in three
sections of core sediments taken from Buzzards Bay, Massachusetts, USA. The researchers
found that the distribution of PAHs remained qualitatively constant, even though the intensity of
. source had increased considerablythe pollution Degradation of PAHs might, however, potentially affect the relative levels and makeup of
persistent PAHs in aquatic environments. Such degradation might occur by photo-/chemical
oxidation (e.g. Behymer & Hites, 1985; Lehto et al., 2000; Shemer & Linden, 2007) or
sik et al., 2004). Miller and et al., 2000; Kot-Wanalyal., 1999; Kabiodegradation (Poeton et Olejnik (2001) studied the photolysis of water-borne PAHs (BaP, Chry, Flu) via UV radiation.
The study revealed that the photo-degradation of PAHs in water involves rather complicated
mechanisms involving oxygen, the function of pH, and scavengers (organic materials).
Degradation of BaP and Chry (high molecular weight PAHs) was found to be retarded in water
with a lack of oxygen, high pH values (alkalinity) and an increase in the level of organic
scavengers. Conversely, FLU (low molecular weight) proved itself to be independent of those
parameters, except for the fact that FLU was eliminated more quickly when oxygen
e foundgradation is often enhanced when chemicals arconcentrations were lower. Microbial dein the dissolved phase (high bioavailability). Low molecular weight PAHs (2 – 3 rings) are
more susceptible to microbial degradation due to bioavailability than high molecular mass

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
increase in the concluded that an sediment-bound PAHs. Xia et al. (2006)ndegradation ipopulation 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
(Männistö et al., 1996). dto being used as indicators for anthropogenic pollutants, the presence anIn addition 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
es ples of legal directivtence over longer periods of time. Examagnification and their persisbiomregulating 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
m the Stockholelve POPs (Persistent Organic Pollutants) underwmentioned in the list of tConvention, which has so far been signed and ratified by more than 150 countries including
.pops.int/). p://chmIndonesia (htt

1.3.The relevance of rivers, estuaries and coastal areas in Indonesia

1.3.1.A Perspective on the global pollution dispersal
y a transitional boundarand coastal areas represent Rivers and their tributaries, estuaries between the terrestrial and marine aquatic system. These bodies of water act as the "front line"
with respect to receiving the majority of land-based loading materials, including organic
s into the ocean icalof chempollutants. Therefore, their role in the distribution and transport reservoir is crucial. Chester (2003) pointed out that river runoff is one of the primary, global-
scale sources for material to enter the oceans when taken together with atmospheric deposition
and hydrothermal activity. With regard to this, rivers play a large and important role as the main
an. s of numerous chemical signatures into the ocecarrierA variety of surface runoff types exists. The flows from diverse landscapes, e.g.
municipalities, various sorts of heavy, medium and light industry, and agriculture, groundwater
seeps into riverine systems, and into the ocean. Atmospheric deposition also enriches the

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
gions represents one of the keyewaters of these rin the rivers, estuaries and coastal 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
stems.aquatic syworldwide to Scientists have established the global significance of the rivers draining southern Asia,
als into the world ocean. On a global scale, recentmateriounts of terrestrial which flush large amestimation 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
vitski et al., 2003). load (Sy th around 70% of theent, wimAsia and Oceania are the largest producers of fluvial sedioverall annual sediment loads coming from these regions (Milliman et al., 1999). In comparison
uding Africa, Asia, Europe, North America, and South dmasses, inclwith the globe's largest lanAmerica, 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
are responsible for about 20-25 % of globalands these islthe global ocean. The rivers located on 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,
ght not have been included in the above-mentioned imRokan, Indragiri and Batanghari calculations, further estimates suggest that the sediment volumes are substantial.
n large area of peatland ern coast of Sumatra draiMost of rivers and estuaries in the eastwhich 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
ng to drainage and forest clearing e tropical peatlands owichange in thental persistence environmpeatlands being have threaten the stability of ca. 20-m thick of peat deposit, and make the

11

(see al problementsusceptible to fires. In Indonesia, peatland fires have long been an environmNiño event (section 1.3.2.1997/1998) dam for further explanation). The worsaging of ca. 6.8 Mha (or 34%) of Indonesia peatland, and emt peatland fire episode occurred during severe El itted
ilar to the global net Gt Carbon in 1997 (Page et al., 2002). It is relatively sim2.57 up to 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
age et al., 2002). Pbefore establishing crops (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.
Indonesian rivers canuxes stemming fromc pollution flNevertheless, the significance of organibe assumed to be directly proportional to the significance of material fluxes previously
g me that increasinle to assumentioned by the above literature sources. It is therefore reasonablevels 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., 2003; Ross & Oros, 2004 and Cao et al., Witt & Siegel 2000; Kowalewska et al., 2000; 2005), polychlorinated biphenyls (PCBs) (e.g. Mai et al., 2002; Telli-Karakoç et al., 2002),
polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) (e.g.
n thus be viewed as being very susceptible to e coastal zone of Sumatra cahIshaq et al., 2003). Torganic contaminants. Conversely, dissolved organic matter such as dissolved humic substances
dissolved PAHs in aqueous solution (e.g. Liu & ty of e the solubilihas been shown to enhancAmy, 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
et al., 2007). been recognized (e.g. Baum

12

dli BsaDnn niakchtna sei Dn.rdee wtgiezgeur z übeesierwheciglöm ügtrfe vreutpmoC re .gtdihäcs betsi dli Bs daredo ,nenff öuz dli Bs daum r,cheiepsstiberg Aniew tro sn dahiretiewnn e W.ieta Dedi utnernn eda e Sinenffund ö u, nereutpmoCn deen SietraStdliB s daeSin essü mrd,iw tgiezgen a xesö lesierwheciglö mn hecund darenn n.ügenfi eutne

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).

erview tal settings of the study areas: An OvEnvironmen1.3.2., and the coastal areas include the Siak River, its estuary areas Our chosen studyIndonesia's Riau Province, extending from the Northwest to the Southwest coast in the Selat
Panjang (the coastal channel running between offshore islands and the Sumatra mainland) (Fig.
1.3.). Details of the exact sampling locations are provided in each result’s chapter. The areas
selected for this study provide an interesting opportunity to comprehensively study the spatial
and phase distributions of PAHs in different river systems, all of which ultimately empty their
waters into the Malacca Strait. The sampled areas are located in the equatorial wet climate of
Sumatra Island, which is affected by a monsoon season mainly bringing rainfall between the
months of September and March. However, rainfall can also occur at almost any time
throughout the year. The average annual rainfall in 2004, for example, was 2088 meters with the
heaviest rainfall occurring between October and December (BPDAS, 2004, unpublished
seminar notes). However, even such small changes in regional weather patterns can affect the
flow of terrestrial pollutants and organic materials into the marine environment through various
pathways such as varying land erosion, storm water discharge, and surface runoff volumes.
The Siak River system and its catchment area are composed of ca. 300 km of waterways,
pung Kanan, Tapung Kiri and Mandau) and various Taincluding several tributary rivers (the sub-basin streams. Including the Siak's estuary system, the entire catchment area totals roughly
area of Riau Province (BPDAS, illion hectares, amounting to ca. 10% of the total surface 1 m2004). The average river flow rate is normally 200 m3 s-1 (a total of 6.307 x 109 m3 y-1), reaching
a peak flow rate of 1700 m3 s-1 during the monsoon season and a minimum of 45 m3 s-1 in the
course of droughts (unpublished data, PEMPROV RIAU, 2005). The Siak and its estuary

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-
receives large y (BPDAS, 2004). The main river correspondinglyuse coverage, respectivelse. smaller channels and tributaries along its cour ounts of water input stemming fromamMoreover, 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
outh, thus making it inevitable that urban and industrial discharges will enter the river's water.mstal channel located between dump their waters in the coaestuaryThe Siak River and its mainland. Bengkalis Island and the Sumatra 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,
masses.mes of the coastal water dence tithere is no information available on the resi

14

toasau CiR

SiakEstuary

SiakRiver

BengkalisIsland

MALAYSIA

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.

AB

Fig. 1.around a 4. (apalm)-oil plantation, Surface runoff of organic(b) typical sma-rich black water fromll water channel a s found in tmahll wae estuary. These aterway entering the Siak River re typical water
inputs feeding the Siak River (source: courtesy of SPICE).

15

RokanRiver

Sumatra,
SIANEINDO

SiakEstuary

SiakRiver

Kampar River

River Fig. 1.5.(as see Plumn from nortes of SPM and dissolvehwest to soutd humhwesic t) into mathterial e Mafromlacca strait. At several rivers: the Roka low tide then, plum Siak and e is flusKamhed par
outwards Sea Research by the Siak River and Institute (IOW) Warnemuende, Roat high tide it is pushed backwardstock, Germany usins. Img MagODIS e fromTerra, H. Siegel (2004), Baltic Data: NASA-RRS.
to PAH pollution, there are two potential sources which have their roots in With regards 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.coast of 6.Dumai city (left), ri Some oil-related activities observeddges (middle) in the chann in the stel (Panjaudied areas. Refinng Strait), and typeries are mainly located in the ical port activities in the
Siak River (source: courtesy of SPICE).

16

Moreover, oil industries can also be found in surrounding areas of two neighboring
is center in Asia). Malacca Strait sia and Singapore (the biggest oil refinerycountries, Malaylikely destined to become one of the busiest straits in the world, one which is highly susceptible
due mto oil pollutiainlyon. Zakaria et al. (2000) found that oil to spillage (through accidents or routine tanker operations such as ballast-water pollution levels detected in the Strait were
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 coinstances of naturallymbustion, in particular anthropo-occurring forest and swamgenip fires. Especiallc, slash-and-burn agriculty important for this region is ure and intense
the documhas worsenedent overall air qualityed fact that uncontrolled a for over ga decade. ricultural burning for purposes such as land clearing
ple of a shows an exam8 Fig. 1.7 shows the trend of hotspots from 1996-2006 and Fig. 1.daily hotspotthe Indonesian Ministr distribution.y of Forestry Data was extracted fro (www.dephut.go.idm the hotspot daily). Elevated numbers o observation provif hotspots were ded by
observed during the severe El Niño event of 1997-1998. It is not to extrapolate that the numbers
of hotspots correlated directly with El Niño, because high numbers have also occurred during
2005 and 2006, which dihappening during 1997/1998 resulted in a strong imd not fall under the pronpounced effects of Elact on the distribution Niño.of aerosols o Severe burning ver
Sumatra and the neighboring counties (e.g. Fang et al., 1999) and the effects even reached into
(2004) observed a large aerosol plume which formedan et al.the Indian Ocean. Parameswarover the eastern equatorial (5oN to 10oS) and eventually reached 60o E latitude during
September-Novemin Southeast Asia, particularlyber of 1 I997. This plume was directlyndonesia, at the tim tied with te of a severe droughth caused by an Ele large-scale fires occurring Niño
event. Unfortunately, the observed number of annual hotspots has remained at a level of >3000
become even worse. The occurrence of agricultural burning is en and has recentlyever since thmost likely during the dry season, the period between March and September. Nonetheless, (as
rainycan be seen in the Fig. season. This is to say that forest and swamp1.7b), large numbers of hotspot have fires, been added to uncontrolled agricultural observed even in the assumed
burning, are potentially the largest source of PAH contamination in the studied areas.

17

18959

13711

A20000189596451818000170901600014000120001371193601000075878000eervsbo topsto hf oersbmuNd2000Sampling
732378186000607740004865El Niño3780SPICE
019961997199819992000200120022003200420052006

Wet Season
0009>

19972002200420052006

BDry SeasonWet Season
60000009>50004000199720023000tpostho gninrbu f orbemnu1000
20042005200020060MayJunJulAugSepOctNovDecJanFebMarApr
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

dli BsaDnn niakchtna sei Dn.rdee wtgiezger z übeesierwheciglöm ügtrfe vreutpmoC re .gtdihäcs betsi dli Bs daredo ,nenff öuz dli Bs daum r,cheipesstiberg Aniew utro sn dahiretiewnn e W.ieta Dedi utnernn eda e Sinenffund ö u, nereutpmoCn deen SietraStdliB s daeSin essü mrd,iw tgiezgen a xesö lesierwheciglö mn hecund darenn n.ügenfi eutne

IndoFig. 1.ne8.sia (imAn eagxeam source: www.dple of daily obserephut.go.idvation of hots ). This pot distpictureri showsbution, pr intensive ovided burniby the ng (rmeid dotsnistry of F) around oresthe try
catchment areas of Siak River, estuary and some other rivers on June 19th, 2004.

Study Objectives 1.4.

The objectives of this study were to: 1)Determine the concentration and distribution of PAHs in three aquatic compartments:
surface sediment fractions, suspended particulate matter (SPM), and water, taken from
eas,s: riverine, estuarine and coastal arstemthree distinctly different aquatic sy2)Compare the level of PAH contamination, both within the three different aquatic systems
3)and also to similar systemApportion possible contaminant sources through ms in other geographical areas, olecular weight and isomer ratios,
4)Study the fate of PAHs in water phases by examining the partition equilibrium to SPM
the bulk water solution (here considered as dissolved phase), from inant factor affecting PAH fate inze the role of organic carbon content as a determAnaly5)the various aquatic environments and water chemistry (particularly salinity and pH).

19

C DISTRIBUTION AND FATE OF PAHs IN AQUATISOURCES,II.COMPARTMENTS: A SHORT REVIEW

n Introductio2.1.ews and elaborates upon various aspects of PAH sources, reviyThis chapter briefldistributions 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
ent, suspended particulate mient is discussed based on their existence in sedthe aquatic environmelaborated upon based on their solid- PAHs is matter and water solution, whereas the fate ofrtitioning. awater phase p

Source and Signatures 2.2.hropogenic ural and antwide range of nat a PAHs in aquatic environments stem fromliterallysources. The hundreds of differlatter is of serient comous concern bustion processes to humans, due to the fact from human that PAHs arcivilization. These range fe by-products of rom
n, incineration, stems to industrial processes like power generatioresidential heating symanufacturing, agricultural burning and petroleum combustion for transportation, among many
al., 1992; 05; Westerholm et others (e.g. Kakareka & Kukharchyk, 2003; Conde et al., 20Zielinska et al., 2004; Yang et al., 2007). Recent global estimates of the atmospheric emission
ls (56.7%), wildfires (17.0%) ear) showed that biofue substances in 2004 (520 Gg per yof PAH16and 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
al., 1996). d spillages (e.g. Requejo et discharges anPAHs 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
("petrogenic" PAHs). mresult in petroleu

Natural PAHs 2.2.1.Use of the term natural PAHs differs somewhat in scientific literature, since this term
could potentially include both diagenic and catagenic processes. However, naturally-occurring

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
t-depositional transformation which changes a sical or biological pos chemical, phyto anye , 1992). Thest-geological period (Berner, 1980; Libes shorbiogenic precursor over a relativelyPAHs 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
g. 2.1 shows an Silliman et al., 1998). Fient (e.g. Lipiatou & Saliot, 1991; mPAHs in the sediexample 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
). et al., 1980diterpene abiatic acid into retene (Wakehambvertical profile when coThese PAHs are primarilympared to anthropoge enriched in deeper, anoxic sediments, indicating a distinct nic 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
ch older than the earliest industrial times. Third, concentrations of anthropogenic PAHs were umclose 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

fromFig. 2.1. LaFlam A hyme pothetical arom& Hites., 1979). atization scheme for natural precursors: (a) -amyrin, (b) lupeol (adopted

Pyrogenic PAHs 2.2.2.Unlike natural PAHs, pyrogenic PAHs are produced in an extremely short period of time
through high temperature reactions, particularly the incomplete combustion of organic matter
(in the broadest terms: biomass and fossil fuels). The products are unsubstituted compounds
ranging from low molecular weight (100 – 200 Dalton, mostly 2-3 ring groups) to high
molecular weight (>200 Dalton, or mostly 4-ring groups) compounds, e.g. those composing
the 16-PAH list. The formation mechanisms of PAHs have been the subject of intensive research over the
years (e.g. Neff, 1979; Glarborg, 2007; Appel et al., 2000; Rockne et al., 2000; Frenklach, 2002;
Ladesma et al., 2000; Dobbins et al., 1998). Two mechanisms have generally been
acknowledged as the best explanation of how PAHs are thermally generated: pyrolysis and
pyrosynthesis. Pyrolysis involves the cracking of complex and high molecular mass organic
molecules into lower molecular weight free radicals. This is immediately followed by
pyrosynthesis in which the newly-created free radicals are reassembled. Benzene and further
non-alkylated PAHs are produced by joining simple, individual benzene rings into double, triple
and larger, multi-ringed, high molecular mass ring structures (see Fig. 2.2). Most recently,
s of PAH potential reaction pathwayHoward (2000) reviewed and discussed the Richter and formation which follow pyrolysis. Several kinetically-governed processes have been added to
the list, namely 1) oxidation, resulting in the formation of the first aromatic ring (benzene) and

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
s scheme principle, Bockholn' In ack carbon formation (Fig. 2.3). precursors for soot and blincludes 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. would on formation, the concentrations of PAHs in the flame of black carb At the onsetAHs are transformed into soot particles, as PBut not all a et al., 2005). therefore be reduced (Limis 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;
et al., 2006). ans Koelm

23

Fig. 2.3. A conceptual picture proposed for soot formation in homogeneous mixture (adopted from
Bockhorn, 1994).
The magnitude and relative compositions of PAH16 compounds released by combustion
processes vary, resulting from a combination of factors including fuel sources (biomass vs.
fossil fuel, or substrate structures) and combustion/burning conditions (temperature, oxidants).
Literature data taken from various combustion experiments and field measurements is reviewed
here to calculate out the amount (expressed in terms of the mass of PAH emitted per unit mass
of fuel burned) and composition of PAHs. The products are then grouped together as petroleum,
coal or biomass (wood, grasses, agricultural mixtures, and paper) combustions (Fig. 2.4. and
bustion produces the mong these groups, coal cosupporting information in Appendix 2.1) Amhighest PAH16 emissions, ranging from ~100 – 1000 mg/Kg. Biomass burnings emit a wide
range of PAH16 concentrations, varying from ~10 – 500 mg/Kg, while petroleum combustions
(mainly diesel fuel) release PAHs in the range of 1 – 10 mg/Kg. Combustion of gasoline fuel
emits PAH16 up to two orders of magnitude less than that of diesel fuel (e.g. Marr et al., 1999;
1998).Miguel et al., The relative predominance of aromatic or aliphatic fractions in the fuel structure controls
the amount of PAHs emitted. The higher the aromatic fraction of the fuel structure, the greater
plete es. Mastral et al (1998) explained that incommission level of PAHs becothe possible emcombustion of coal fuel results in the emission of unburned fragments consisting mainly of
mentioned above, e atics from the coal structure. Following the PAH formation schemmaroher dicals or otaosynthesis with other rthese unburned aromatics can readily undergo pyraromatic rings, thereby building higher molecular weight substances at low combustion
temperatures. Coal contains more aromatic structures than similar fuels. For instance,
bituminous coal consists of aromatic (roughly 45% of the total mass) and aliphatic (ca. 30%)

24

ar wood - also contain high fuels - in particulass fractions (Yan et al., 2004). Likewise, biompercentages 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
ared to the other groups. pmcoHigh temperature (plus oxidant level) decreases the overall emissions of PAHs (e.g.
Jenkins et al., 1996). Pyorogenic PAHs can be formoed in a wide range of temperatures, stretching
from relatively low (ca. 300C) to high (~1000C), 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
ally are optimmpounds from naphthalene to coronenePAHs produced in the series of cogenerated at 780oC. Bituminous coal combustion was shown to release an optimal emission of
o(2001) observed that increasing the burn C (Liu et al., 2000). McGrath et al. 800PAHs at 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
es. robust flamoldering stages and less sm

25

00010

1000

(mg/Kg)10016PAH

10

1

Emission Factor of PAHs

Coal Biomass Petroleum
CombustionsBurningsCombustions
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
details to the references). for literature sources (see Appendix 2.1. The composition of PAH emissions serves to characterize the sources. Combustion
processes favor production of unsubstituted compounds as compared to their alkyl homologues
(Lima et al., 2005). The PAH16 represent the most common unsubstituted PAHs which are
produced by such processes. Therefore, they have been quite often examined by and employed
in environmental studies and assessments. Combustion of diesel fuel in modern vehicles
generates high levels of lighter PAHs (~300 Da). It emits no heavier PAHs (>300 Da, e.g.
coronene), unlike gasoline (Riddle et al., 2007a). It is due to this that modern diesel vehicles
have been equipped with more advanced technology, enabling high combustion temperatures
on and aid in the breakdown of heavier PAHs. ati operation which hinder the formduring engineIn contrast, older vehicle technologies produced higher amounts of PAHs (Riddle et al., 2007b).
Increasing engine temperatures during the combustion cycle fosters the production of lower
molecular weight compounds. Liu et al (2000) observed an increase in the relative composition
of 2- and 3-ring structures as operating temperatures increased from 783oC to 843oC, even
though the total overall magnitude of PAHs was significantly reduced.
In order to better understand the source characteristics of PAHs with regards to their
PAH16 composition, various literature data is presented which evaluates their relative individual
and ring-group compositions. The relative composition of a particular compound from a given
source is evaluated by normalizing the individual concentration from the corresponding
PAH16. Fig. 2.5 and Fig. 2.6 show the relative composition (median values) of the common
sources of pyrogenic PAH16. The dashed line represents the composition pattern which

26

s peatland burning m Sumatra'characterizes different sources. In addition, the literature data froepisode 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
took place. where this studyThe results shows that the compositions of PAH16 stemming from pyrogenic sources is
with respect to high levels (>30%) of naphthalene (NAPH) and low levels similar relatively(<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.
ass-coal and biom position shows a different pattern for petroleumHowever, the ring-group comcombustion, 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
oduced. In contrast, the high levels of 3-rand acenaphthene (ACEN) plene (ACYN) acenapthyring 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
positions of the 2- and 3-ring groups can comTherefore, the relative grass burnings (Fig. 2.5b). 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
pounds can be used as additional clues during separation, due to their lecular weight comomunique 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
ce help provide clues for sourveloped to pounds can be demass ratio between those comdifferentiation. In comparison to biomass burnings, Fig. 2.5b shows the relative compositions of
and Pekanbaru (the capital pounds between two distinct locations. Dumai mdual PAH coindivicity of Riau province) were affected by the tremendous volumes of smoke stemming from
and ess NAPH it l peatland burnings empeatland burnings in 2005. It shows that SumatranACYN. 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

local sources. This data can therefore be a useful aid in position or additions frommdecocomparison for PAH assessments in aquatic systems of those particular studied areas.
BA3565,1%PyrogenicPAHs40Biomass Burnings
30Biomass 35
25Burnings30
20Coal 25Wood Burnings
iospmo CveitaleR)%(n oit5)%(n oitiospmo CveitaleR5
15Combustions20
Petroleum 15Grass Burnings
10Combustions10
00C35Sumatra PeatlandBurnings in 2005
30imaDu25Pekanbaru
20evitalRe)%( noitisopm Co5
15100 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
nt.rediffe AB80PyrogenicPAHs80Sumatra Peatland Burnings in 2005*
707060Biomass 60Dumai
BurningsPekanbaru
50Coal 50
40Combustions40
)%( noitisopm CoevitalRe10)%( noitisopm CoevitalRe10
30Petroleum 30
20Combustions20
002 rings3 rings4 rings5 rings6 rings2 rings3 rings4 rings5 rings6 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

Hs APetrogenic P2.2.3.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
ridines, quinolines, carbazoles, thiophenes, sulfoxides, cloparaffin rings), the resins (pyfused cysuifides, atics, naphthenic acids, aromides), and the asphaltenes (extended polyand ampolyhydric 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-Álvarez 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.
unts of PAHs to the aquatic o oil spills which occur would add significant amyTherefore, anent. environmIn contrast with pyrogenic origins, the composition of petrogenic PAHs is notably
characterized as having an abundance of alkyl-homologue PAHs (substituted) as compared to
s (Youngblood & Blumer, 1975; Lafamme & Hites, 1978; Neff, formthe parent (un-substituted)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

data was drawn mologues were 5%. This and the total alkylated PAH hoAHs ring parent Pfrom PAH analysis performed on over 60 different crude oils and petroleum products, including
oil, e oils, California oils, UK Brent oil, Alaska Cook Inlet 1-3, Iranian HeavyArabian crudRussia Komi, Norway Statfjord Oil, Terra Nova, jet fuel, diesel, Bunker C and many others.
ologues relative to their l homdistribution for alkypical “bell curve” Fig. 2.7 shows a typarent 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
1-C4)-naphthalenes, (C1-C3)-, including (Ce petroleum sources for PAHshdistinguish trene, and C1-fluoranthene/pyfluorenes, (C1-C4)-phenanthrenes, (C1-C3)- dibenzothiophenes, (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
of the degree turn out to be the same as total C1, C2 and so on. Due to this,effectively interpreted to avoid mistakes in classification. ullybe careflation should alkyThe 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 4–6 ring compounds in crude compose only relatively small
percentages. Wang et al. (1999) found that naphthalene and its alkyl-homologues (C1-C4)
86% of total PAHs in Diesel No.2 and up to 99% in Jet B fuel. In contrast, oil rised up to pmcospills 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
waste lube oil. les was ptested in the sam

30

homologues “Bell Shape” distribution

lsilpil SOCrude Oil**

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).
AB3055,5%PetrogenicPAHs80
7025Oil Spills60Oil Spills
20Crude Oil**50Crude Oil**
4015pmo CveitaleR)%( noitios5)(% niotisompo CevtilaeR10
301020002 rings3 rings4 rings5 rings6 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).

2 rings3 rings4 rings5 rings6 rings

31

Source Apportionment 2.2.4.This section elaborates the source apportionments of anthropogenic PAHs based on
ent of anthropogenic PAHs in eric ratios. Source apportionmlecular weight ratios and isomomthe aquatic environment is very challenging. This is due to that fact that anthropogenic PAHs,
m various sources. hose of unsubstituted compounds, coexist with substances fro tparticularlyAlso, 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.

Molecular Weight Profile 2.2.4.1. characterized high proportions ofnerally earlier, petrogenic PAHs are geAs describedlow molecular weight (LMW), typically 2- and 3-ring compounds. In contrast, pyrogenic PAHs
tend to feature higher levels of high molecular weight (HMW), 4- to 6-ring substances. In
response to these generic profiles, the mass ratio of LMW/HMW has been widely introduced
as a benchmark for distinguishing petrogenic from pyrogenic PAH sources (Neff, 1979; Soclo
et al., 2000; De Luca et al., 2005). Therefore, a LMW/HMW ratio with a value greater than
1 indicates petrogenic origins. However, this ratio should be cautiously interpreted, since the
emission sources of petroleum and biomass burnings produce high LMW profiles (Fig. 2.6).
The emission source profile can be changed during the atmospheric phase due to both
photo-degradation and transformational processes before the PAHs ever reach the acceptor
substrates. For example, gas-phase PAHs react rapidly with OH radicals in the present of NOx
gases in the atmosphere. This transformation leads to a PAH atmospheric lifetime of roughly 1–
12 hours total (Atkinson et al., 1987). Behymer & Hites (1985) performed a photolysis
orne PAHs also found that the degradation of particle-bent with particulate PAHs. Theyexperimdepends on the type of substrates to which they were adsorbed. The lifetime of PAHs adsorbed
onto fly ash is greater than 29 hours, and black carbon acting as a substrate might extend this
lifetime to >1000 hours. Such natural particles retard degradation effectively and may facilitate
a long journey. The longer the atmospheric residential time, the greater the profile shifts which
occur towards HMWs. Therefore, PAH profiles in remote areas (those far away from the
les for regions source) tend to favor HMWs (Fernández et al., 2002). Conversely, PAH proficlose to the original source closely mirror the profiles for specific emission sources given above.
In aquatic environments, we should expect suspended particulate matter to possess signatures
which are to a large extent similar to those of the surrounding atmospheric profiles. But

32

m those of SPM (Fernandes & be expected to differ somewhat froent profiles can alsomsediSicre, 1999). They will tend to favor HMWs due to the complex sedimentary degradation
gradation due to susceptible to biodepounds are veryich take place. LMW comprocesses whtheir 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
expected in the sedisurfaces. As a directm coent. nsequence, an increase in the ratio of LMW/HMW would be

Diagnostic Mass Ratio of Isomers 2.2.4.2.

Isomers of unsubstituted PAHs have different kinetic and thermodynamic characteristics
due to varying structural stability. Compounds with a linear structure (e.g. anthracene,
le than corresponding e less stabrene, dibenzo(a)anthracene) ar(a)pybenzo(a)anthracene, benzoisomers containing angular, branched structures. Therefore, greater proportions of less stable
bustion e.g. anthracene over phenanthrene (MW=178), are produced during compounds, mcowhen compared to other isomers. Budzinski et al. (1997) demonstrated that the ratio of
PHEN/ANTH was temperature dependent, with its value decreasing as the temperature
. In espectively 300, 700 and 1000 K, the P/A values were 49, 8.3, and 5.5, rincreased. Atcontrast, lower thermal production (e.g. during petroleum maturation) lead to higher
pounds when salient comyPHEN/ANTH ratios. Phenanthrene and anthrene are therefore highlseparating pyrogenic from petroleum sources. A similar hypothesis has been proven for FLA
and PYR. With respect to this, pairs of parent PAH isomers have commonly been used for the
purpose of source apportionment, i.e. compounds with molecular weights of 178 (PHEN,
(FLA, PYR), 228 (BaA, CHRY) and 276 (BPERY, IPYR). Yunker et al. (2002) ANTH), 202 reviewed those mass groupings and proposed the ratios ANTH/(ANTH+ PHEN),
RY) as the best potential parentYR), BaA/(BaA+CHRY) and IPYR/(IPYR+BPEFLA/(FLA+Pratios for discerning between natural and anthropogenic sources. PAHs from combustion
YR) >0.5, and FLA/(FLA+Ppical values of ANTH/(ANTH+PHEN) > 0.1; sources have ty sources like crude oil ated with petroleumciPAHs assoBaA/(BaA+CHRY) > 0.35. In contrast, typically have values of the same isomeric ratios of <0.1, <0.4, and <0.2, respectively (Table
2.1). These mass ratios consist of the mass of the less stable compound divided by the total
isomer mass for a particular molecular weight.

33

52 – 0.0.

rogenic sources petrogenic and pyagnostic mass ratios for identification of Table 2.1. Di LMW/HMW ANTH/(ANTMW 178H+P HEN) FLA/(FMW 202LA+P YR) BaA/(BaA+CHRMW228 Y) IPYR/(IMW 276PYR+B PERY)
Values Identificatiaon
ComPetrogenic > bustion < 1 1 >0.1 <0.1 >0.5 <0.4 >0.35 <0.2 >0.5 <0.2
Mixture petrogenic/ 0.2 – 0.35
bustion comcomPetrolebustion um 0.4 – 0.5 0.2 – 0.5
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
c values. This rogenicted range of petrogenic and py lies within the expeliterature generallyg. c sources (Fiogenirsuggests that these ratios can be used to distinguish petrogenic versus py2.9 & 2.10). For the petrogenic sources, the ratios with MW178, 202, and 228 are more
crude oil concentration of HMW PAHs in the fact thatsensitive than MW 276. It is due to the 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
nd rogenic asources. This also suggests that these values are acceptable for partitioning py seen in Fig. 2.9.several data which do not follow suit, as are petrogenic sources. However, there Detroit oil spills and 228 for crude oil and spillage groups the ratios of MW202 First, in the (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-

cross-plot graphs, which allow for optimal discrimentioned ratios is through the use ofion inatm

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

MW178, 228, and 276) (MW202 vs. clear segregation between oil (left yshows a relativel

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

1,00ACrude Oil and Spillages
090,080,070,060,050,040,030,020,010,000,MW 178MW 202MW 228MW 276

B1,00Coal and Petroleum Combustions
090,080,070,060,050,040,030,020,010,000,MW 178MW 202MW 228MW 276

Alaskan North Slope
eduCrOil spills "Oil Tanker
Enrika"
Oil spills "Enrika"
Beach Sample1
Oil spills "Enrika"
Beach Sample2
Detroil Oil Spill_1
Detroil Oil Spill_2
Detroil Oil Spill_3
Pyrogenic
Petrogenic

Coal-Cement Industry
Bituminous Coal
Charcoal
Coal Briquette
Coal Domestic
HO + natural gas, Ind
DBoiesileelr, Industrial
FBoueille Orsil -HOP
Diesel 2 -HDV
Heavy oil, Industrial
liBogiht-ledrsuty Diesel
Pyverhiocgleensic

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 a2002). Tphe portionmratio valuesent petroge were nic (dascalculated fromhed lin es) and many sourcepyrogenic (ss (see: Fig. 2.4 olid lines) sincludiources ng the(after references). Yunker et al.,

36

A1,00Wood/Bamboo Burnings
900,800,700,600,500,400,300,200,100,000,MW 178MW 202MW 228MW 276
B1,00Biomass and Peat Burnings
900,800,700,600,500,400,300,200,100,000,MW 178MW 202MW 228MW 276

ondmlAnutlaWChinese clay woodstoves
Pine-domestic heating
rFiEucalyptus wood 1
Wood, Domesting Heating
oodk WaOLao trad. woodstoves
Thai bucket woodstoves
Cambodian trad. Woodstoves
Vietnam trad. Woodstoves
Eucalyptus wood 2
repPaboomBacnirogeyPPetrogenic
Sugarcane
Pampas grass
Mixed ryegrass
Rice grasses
Corn grasses
Agricultural Debris
Peat Burning Dumai
Peat Smoke Pekanbaru
Pyrogenic
Petrogenic

Fig. 2.wood/bam10. Masboo sand ratio (B) biomdistribution ofass and peat burni specific PAng sH isoomurcesers from. The lines re otherpr various esent refepyrreogencenic sources values used of (fAor)
apportionmThe ratio valueent petrs weore genic calculat(dasheed fromd lines ma) any nd soupyrrcesogenic (see: (sFig. 2.olid lines4 incl) sudiources ng the re(afterfere Yuncenkes). r et al., 2002).

37

Combustion

Mixed Sources
Petroleum

Petroleum
CombustionGrass/Wood/Coal
PetroleumCombustion
01,90,0,8Grass/Wood/Coal
0,7Combustion
60,50,)RYEPR+BYP(IYR/PI0,3Combustion
0,4Petroleum
20,0,1Petroleum
00,0,00,10,20,30,40,50,60,70,80,91,0
01,90,0,8Combustion
70,60,50,RY)+CHAa(BA/aB0,3Mixed Sources
40,20,0,1Petroleum
00,1,00,00,10,20,30,40,50,60,70,80,91,0
90,80,70,60,0,5Combustion
N)EH+PHT(AN/HANT0,2
40,30,0,1Petroleum
00,0,00,10,20,30,40,50,60,70,80,91,0
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.

Combustion

38

Distribution in Aquatic Compartments 2.3.PAHs evidence widespread distribution in the hydrosphere of rivers, estuaries and coastal
et al, omb et al., 2001; Woodhead 1999; GolHites, 1981; Mitra et al., areas (e.g. Gschwend & 1999) where the sources are mostly concentrated. This also holds true for far-distance and
remote aquatic systems such as mountain lakes (e.g. Fernández 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
and coastline areas. solution, with a particular focus on rivers, estuaries

2.3.1.It is widely accepted that sediSurface Sediment and Grain Sizment layers re Fractions ecord diverse environmental changes, which
include PAH loads both over short-term and geologic periods of time. Sediment therefore plays
an extremely important role in pollution assessment. Surface sediments (ca. 20 m depth) in
rivers, estuaries and coastal waters are especially dynamic, since remobilization and
resuspension occur constantly due to physical processes. Surface sediments in such dynamic
environments are therefore considered not only to be a sink (sequestration) but also a source
PAHs. (desorption) of A sediment's capacity to concentrate and retain elements and hydrophobic organic
compounds results primarily from two sets of physical (grain size and type) and chemical
(organic composition and content) properties (Horowitz & Elrick, 1987). For example, a fine
grain size provides a larger amount of total surface area per unit mass for adsorption and is often
associated with a large organic matter fraction (a natural geosorbent for most hydrophobic
compounds). Luthy et al. (1997) proposed a schematic conceptual model for the sequestration of
hydrophobic organic contaminants by the sediment (Fig. 2.12). In this concept, sediment is
composed of various aggregates/particles of different origins and sizes, such as mineral
n therefore refers for sequestratiobustion residues and plant debris. The capacitymparticles, coto a combination of specific interactions of substrates with organic pollutants (i.e. binding
energy and rates of adsorption/desorption). These interactions include both particles and non-
dissolved liquids in the aqueous medium, such as oils, tars, and solvents adhered to or trapped in
sediment pores. The sequestration of hydrophobic organic pollutants in sediments is a
combination of factors including diffusion limitation, sorption and partitioning. If the
distribution of individual PAH molecules in sediment is controlled by an equilibrium governing
sorption to the solid surface, we might expect that the fine (or mud) fraction of the bulk
sediment should accumulate significantly high levels of pollutants due to its large surface area

39

and high or et al., 1996; Tolosa et al., aganic carbon content (Karickhoff et al., 1979; Maruy 2004).

Fig. 2.12.NAPL= nonaqueous A conceptual m-phase liquiodel for theds; seSOM= sorbequestration nt of orgahydrnic maophobic orgatter. Sorption mnic contamechanisminant by geosors include (A) bents.
absorption into amorphous or “soft” natural organic matter or NAPL; (B) absorption onto condensed or
“harsolvent (ed” orga.g. snicoot polym); (D) aeric dsmoatter or comrption onto exposebustion red watesidue (e.r-wet mg. sooti); (C) neral surfaadsorces (e.g. quaption ontro watz); (E) ater-wet ordsoganirption c
onto microvoids or microporous mineral (e.g. zeolites) with porous surface at water saturation <100%
(adopted from Luthy et al., 1997).
ong the various ed ams are, in fact, heterogeneously distributmentPAHs in surface sedihl a et al., 1996; Budzinski et al., 1997; Tolosa et al., 2004; Praparticle-size fractions (e.g. Maruy& al 2001; Rockne et al., 2002; Ahrens son et al., 1998; Wang etp& Carpenter, 1983; SimDepree, 2004). PAH enrichment is not found solely in the mud fraction. It has also been
r observed in the sand fraction, which can also carry significant loads of various PAHs. Foexample, 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 – 63μm; and mud (fine) <63μm, 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.
001; Maskaoui et al., 1999; Guinan et al., 2 980; Kim etKarickhoff et al., 1979; Means et al., 1al., 2002; Viguri et al., 2002). Such a correlation applied to sediment size fractions can help
of PAHs (e.g. Prahl and Carpenter, 1983). ationselaborate the preferential particle associCoarse and fine sediment fractions contain different types of organic matter which affect
PAH distributions. Increasing PAH content for the coarse sediment fraction has been
for PAH y organic particles that have a high affinitfacknowledged, due to the presence o portion of represents only a tinyallysorption. This is despite the fact that the OM fraction normthe 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 250μm–1mm 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
ntent of the sand increases the PAH cocally black particles dramativegetable debris and shinyfraction. 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
ent size mning the PAH content of the various sediireach the sediment. Therefore, examfractions 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
be reluctant to associate large surface area. However, PAHs mayonto its exceedinglyof uptake Carpenter, OM (e.g. Prahl & bustion-derived mwith fine fraction-OM in the presence of co1983). 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 (>250μm – 2mm) and fine (<63 μm) 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
a ight be an indication of mthe fine fractions. Therefore, PAH enrichment in the sand fraction these PAH-sized fraction vestigation ofopogenic source for PAHs. An instrong anthr

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.

rticulate Matter and Water aSuspended P2.3.2.Suspended particulate matter (SPM) is the main carrier by which most terrestrially-
derived materials - including anthropogenic pollutants - are transferred from land to aquatic
tituents and the water ents. It also provides a fundamental link between chemical consenvironmtermcolumn, bed sedim SPM refers to all particulate ents and food chain matt(Turner & Milward, 2002;er with different natures and Suzumorigins, but isura et al., 2004). T operationallhe y
defined as those materials retained by a filter with a specific pore size. Therefore, the definition
of SPM can operationally vary between studies. However, a maximum pore size of 0.7 μm
river, estuary(GF/F) is often em and coastal ployed for differentiating waters for pollution and geochemistrybetween the particulate and dissolved phases fro studies (e.g. Zhou et al., 1998;m
2005; Gebhardt et al., 2004). Boldrin et al.,ura et al., 2004; Luo et al., 2006; SuzumPAHs move from terrestrial environments into the oceans via river, estuary, and coastal
pathway(e.g. Fernandes et al. 1997). This s. The concentrations of PAHs and SPM means that PAH loads entering the ocean have been shown to be posare clitiveloselyy linked t correlated o
in the hydrthe overall SPM load emologic cyerging fromcle (e.g. increased precipitation or extreme riverine, estuarine and coastal drainage basins. Anyfloods caused by climate change
change) can therefore modify and possibly intensify the temporal load of PAHs. The
ple, Witt and Siegel ve been studied. For examof flood events for PAH loading haplications im(2000) observed a significant flux (two orders of magnitude higher than normal) of PAHs into
the Baltic Sea, stemming from municipal and industrial areas in the Oder River basin as a
al. (2008) calculated that 90% of the annual load of of a 1997 flood event. Sicre et consequence Mediterranean Sea took place rance) into the Rhône River (Fparticulate PAHs flowing fromduring flood episodes in 1994. These facts are extremely important for tropical rivers,
particularly in Sumatra where overall precipitation is high, and floods are occurring more
frequently due to climate changes. Thus, the transport of pollutants via Sumatran waterways
significant. xpected to be d be eocean shoulinto the positionc pollutants and SPM depend on the comdrophobic organiInteractions between hyof SPM in the water column. This is due to the fact that different types of particles embody
pollutants. In general, SPM in riverine, ng capacities for specific, hydrophobicvarious bindiestuarine and coastal waters represents a composite of lithogenous, hydrogenous, biogenic and
anthropogenic particles. Lithogenous particles are inorganic materials derived from the
weathering of rocks and other substances in the Earth's crust, which are composed mainly of
quartz and other aluminosilicate minerals. Hydrogenous matter is generated in-situ by chemical

42

processes, resulting in such materials as humic substances, carbonates and both iron and
manganese othose stemming from xides. Theymi occur eithercroorganisms, as coatings or plankton and the decaydiscrete phases. Biogenic ing remains of particles inclmacroorganisms ude
proteins,n also refer to those derived fromand terrestrial plant debris. Bio-particles cacarbohydrates, 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
However, SPM particles are surfactants (Turner & Millward, 2002). as plastic, tar, solvents and often diviinorganic maded into inorganiterial (PIM) includes lithogenous mc and organic particles based on tatter (mheir cheminerals and insoluble ical properties. Particulate salts), whereas
particulate organic materials (POM) are composed of a rather broad mixture of hydrogenous,
htforward measures for the PIM and POM are straigbiogenic and anthropogenic particles. ve sorbent forple. The latter also acts as an effectiposition in a samoverall SPM comants. utpolldrophobic organic hyThe molecular composition of PAHs in particulate matter is somewhat different from that
River estuary contained laof those found in sediments. Luo et al.rge am (ounts of bot2006) concluded that SPM samh 2- and 3-ring PAHs. On the other hand, tples taken from the Pearl hese
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 &
PAHs resulting from Oder River floods were ution of observed that the distribSiegel (2000)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
examination of a specific to great variation due to differing degradatiPAH profile in SPM yion processes (photonic and elds clues to the fate of PAHs in a particular microbial). Therefore,
ental setting.environm

Water Solution as dissolved PAHs 2.3.3.In addition to SPM association, PAH compounds can alternately remain in solution as
truly dissolved substances or also be bound by dissolved organic matter. Differentiation
between those two aqueous fractions is important for particular purposes like bioavailability or
2007). However, for the general assessment of the studies (Hawthorne et al., toxicityo aqueous fractions is not wof PAH in natural waters, separation of those tdistribution

43

substantial. This is due to the fact that the fate of truly dissolved PAHs is appreciably controlled
utman & Morganmatter (DOM) as a geosorbent. Schla the existence of dissolved organic by(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
is despite the techniques to effectively separate these two aqueous fractions. And thisavailability 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
"dissolved phase", which operationally defines dissolved PAHs as those passing PAHs as the through the GF/F. The most popular extraction techniques for determining dissolved PAHs are
croextraction (SBME) (Falcon et al., 2004;i bar msolid phase extraction (SPE) and stir Fernández-Gonzáles et al., 2007; Poerschmann et al., 1997).ends on the solubility in the dissolved phase depposition of unsubstituted PAHs mThe coand hydrophobicity (Kow) of a given compound. The former decreases as molecular weight
ght (see Appendix 1). With molecular weiincreasing increases and the latter increases with regard to a compound’s 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
selves to be in the dissolved phase. However, interactions between PAHs and DOM prove themDOM source-dependent (Liu & Amy, 1993). Therefore, examining the concentration and
comenvironmposition of materialental settings on the fate of particular PAHs. s in the dissolved phase can reveal the relevance of particular

2.4.natural orgThe fate of PAHs in the wanic matter ater: a partitioning concept and the role of
The fate of hydrophobic organic pollutants in aquatic systems has been widely studied,
(particulate and distribution in two immiscible phases including which factors control their water matter can possibly act to retard these solution). This is due to the fact that transfer fromolecules fromm degradation, volatilization the water solution onto particuland desorption ate
& Powers, 1987). (Mackay

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
ties for sorbate relative affinia result of its partitioning of a given chemical into two phases is 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 isothermThere 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
matter has no limitation of sites and surface built upon the hypothesis that the sediment organic 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 sorbent’s 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
fic means the presence of specin < 1, a concave down shape curve, heterogeneity. A value of 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
that the sorptivitysolute concentration in the of the solid phase increases as the soaqueous phase. The case n > 1, a concave up shape curve, suggests rbate concentration increases.

45

Fig. 2.Cs, and t13.he dissolved state, C Three types of observew. d All can berelationship fit with a between crelationshioncep ntration of the formof a chem Cs = K · Cwical in the sorben where Kd sta and te, n
are constants (adopted from Schwarzenbach et al., 2003).
Due to high hydrophobicity, concentration of PAHs in the water is limited, and
determined by the affinity of particulate organic matter as a geosorbent (e.g. Weber et al.,
of low concentration (ppb or less), distribution accepted that within very1991). It is widelyPAHs between suspended particulate matter and water solution can be estimated from linear
sorption isotherms (Hwang et al., 2006). Equilibrium partition of PAHs onto the SPM is
actually determined by complex molecular interactions that determine the sorption of PAHs
onto the organic phase (Schlautmann & Morgan 1993; Christl & Kretzschmar, 2001; Weber et
rstand the extent of PAH ore, to undess & Schwarzenbach, 2001). Therefoal., 1991; Gdistribution affected by the particulate organic matter of given phase, the partition coefficient
(Kd = Cs / Cw in mg/L) is often normalized to the particulate organic carbon content (foc)
according to Koc = Kd / foc . Koc is so-called the organic carbon normalized partition coefficient.
Variation of Koc suggests a difference in the relative affinity of PAH for the SPM in water
stems. sy

46

METHODS OF ANALYSIS III.

n Introductio3.1.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
l (C18 octadecymatter (SPM) and water solution as dissolved PAHs, using wide-poreparticulate ) reverse phase column with high performance liquid chromatography (RP-C18-HPLC) detected
ce detectors (FLD). The use of HPLC e fluorescen ultraviolet (UV) and programmablbyUV/FLD has been well-recognized for PAHs instead of gas chromatography mass spectrometer
sts n, EPA Method 610 sugge(GC/MS) (e.g. Grope, 2001; ICES, 1997; Wise et al., 1990). EvePAHs of the EPA priority list as GC/MS can hardly that HPLC is the best used for the 16 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
SPM, and solid ent and c solvent percolation for sedimfractionation; (3) extraction with organiocedures including clean-up, (4) work-up prphase extraction (SPE) for dissolved PAHs;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
andards. nd spiked reference staperdeuterated PAHs, procedural blank

Sample Collection and Treatments 3.2.

Surface Sediment and Size Fractionation 3.2.1. smalle collected directly using sediment grab from a Surface sediment samples wervessel, and immediately homogenized with a stainless scoop. Any relatively large foreign
hetic wastes were ntas plant debris (stick or leaves), stones (rocks) or any other syobjects such discharged. The homogenized sediments were then placed in pre-combusted (heated at 250oC
for 5 hours) aluminum jars, and closed to avoid any possible contamination. The samples were
kept cool (ca. 4oC) during transportation to the laboratory, where they were then frozen at -20oC
adequate on under relativelysis. Due to PAHs undergo photo-degradati analyuntil furtheroxidant and ultraviolet (UV) radiation (e.g. Sebaté et al., 2001), direct exposure to sunlight and
on. ng handle, storage and transportatipossible strong UV sources were avoided duriSediment size fractionation were carried out by wet sieving to render two general
fractions according to the Udden-Wentworth Scale: (1) the coarse (or so-called sand) fraction
ud) fraction with mand 63 m; and (2) the fine (or size diameter between 2 mm with particle particle size of < 63 μm. The fine particle was obtained by centrifuging the remaining material

47

passing through the 63-μm sieve at 1500 rpm for 20 minutes. Those sediment fractions were
sis. ozen until analythen stored fr

rticulate Matter (SPM) aSuspended P3.2.2.Surface waters for SPM and dissolved PAH samples were collected with the Niskin
ment in the bottle, and placed in a pre-cleaned glass bottle, sealed, and stored until further treatlaboratory. Surface water was defined as that of the surface and down up to 1 meter depth. Up
to 5-L water was sampled from the river and the estuary, and up to 10-L water was sampled
from the coast. Water filtration was undertaken on-board and in the laboratory.
SPM was sampled by filtering the samples through pre-combusted (at 400 oC for 4 hours)
Whatman GF/F (0,7 μm in diameter) in triple sets of cleaned 250-ml glass containers. A
stainless-steel filtration unit with a vacuum pump was used for the collection. Prior to filtration,
les was pogenize the particle concentration. Up to 5-L water samhomthe water was shaken to filtered for river and estuarine water samples. Due to high density of particulate matter
particularly from black water Siak and its estuary, more than one filter was therefore employed
for one station. However, the use of filter in parallel was confirmed with blank filter values. For
coastal water, the volume of filtration was increased up to 10 L depending on the amount of
suspended particles obtained. the unit, wrapped into aluminum foil, and stored The filters were then removed fromfrozen at ca. -4oC (freezer temperature) to avoid microbial degradation until further analysis.
The collected for dissolved PAH sample. e filter) was hThe filtrate (water passing through tvolume of filtered water was recorded in order to calculate the concentration of the suspended
matter in a given volume of water. However, the content of PAHs was calculated on a dry-
weight basis.

concentration of dissolved PAHs Solid phase extraction (SPE) for pre-3.2.3.Solid phase extraction (SPE) is one of high-performance methods in a sample preparation
liquid samples including PAH, which has ponents fromfor extracting and separating target combeen increasingly used for environmental analysis (e.g. Burkhardt et al., 2005; Urbe & Ruana,
1997). In comparison to classical liquid-liquid extraction (LLE), in modern analytics SPE
ption, time nsumw solvent coprovides several pre-concentration advantages with respects to loy and recovery, as oducibilitle, high repr due to various phase availabsaving, high selectivitywell as automatization (e.g. Rossi & Zhang, 2000; Sargenti & McNair, 1998). In general, SPE
works as follows: (1) the target analytes in the given aqueous samples will retain in the selected
sorbent, (2) interfering (undesired) components will be phased out, and (3) the retained target
on with appropriate solvent. e sorbent through an eluti thtes will be then discharged fromanaly

48

n between the PAHs as target analytes and the sorbent – lecular interactioomThe stationary phase – of the SPE has been generally acknowledged as non-polar interactions taking
developed for the non-polplace between alkyl group of the sorbent and the analyar interaction are C18- or C8- (e.g. Machereytes. The most ty-Nagel Gmpical alkybH, Duren, l groups
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
ic substance humilable sorption site. Therefore, for rich-micropollutant for the avaand organic ple (Baum et al., 2007) we applied a specific dual phase –water like the Siak water samaminopropyl 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
from MachereyCartridge used in this study-Nagel GmbH (Dueren, was Chromabond® NHGermany). Th2e extraction /C18 (6 ml, 500 mgwas undertaken using a so/1000 mg), obtained lid
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
filtrate’s 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-
data plish procedural efficiency and and d12-perylene) were spiked to accomfluoranthene er prepared watduring extraction and work-up procedure. Then, the losses correction from anysample was aspirated through the cartridge at flow rate of ca. 5 ml/min. The flow rate was
cartridge was then again controlled by adjusting the pressure of twashed withhe ma Milli-Q watnifolds. After er. Finallyall of t slhight film (ca.e filtrate was aspirat 0.5 ml) of the ed, the
remfoil, sealed aining water was left owith a parafnfin film the top of t, hand stored cool until analye cartridge. Then, the colsumis. Sample n was firmlywas topped collected inwith
duplicate.

49

3.3.Determination of PoPerformance Liquid Chromatograph coupled wlycyclic Aromatic Hydrocarbith Ultraviolet and ons using High
FLD)Fluorescence Detectors (HPLC UV/

Soxhlet Extraction of sediment and SPM 3.3.1.The method was intended to do extraction for wet/moist sediments and dried-filters with
between organic solvents and solvent percolation technique. It is based on the intimate contact the particles of sediment or suspended particulate matter, which facilitates desorption of PAHs
from particles and diffusion into the organic solvents. Sediment size-fractions were extracted in
two cycles using a combination of two systems of solvent: (1) acetone (water-miscible, polar) to
extract the water and PAHs from the sediment; and (2) less polar mixture of acetone/hexane
(1/9 ; v/v) to complete the desorption of PAHs out of the particles. Although different organic
solvents have their potential capacity to extract PAHs, these particular solvents have been
widely proposed (e.g. Grope, 2001; ICES method, 1997). The efficiency of extraction systems
as well as the method procedures were tested using spiked surrogate standards (see section 3.4.).
tractionSediment Ex

the pre-cleanned (acetone/hexane, nepared iment fractions were prUp to 10 g of the sediobles (25 x 60 mm obtained from n thimC for 6 hours) cellulose extractio1/1 : v/v at 120and spiked with three surrogate perdeuterated PAH standards: d10-phenanthrene, nn), amWhatglass ugged with pre-cleaned ment was pllene. Then, the sedid10-fluoranthene and d12-perycotton to avoid spill out. The extraction was performed by means of SoxTec HT6 (Soxhlet-
modified extractor) at effective heating temperature of 120oC – 140oC for about 4 – 6 hours.
The use of SoxTec extractor is beneficial for time and solvent consumption since it can perform
6 different extractions in parallel and require less solvent amount (ca. 50 ml) compared to a
traditional Soxhlet extractor (> 100 ml). Operationally speaking, before the heating-up the filled
thimbles were attached to the condenser at the “Rinsing” position where the thimbles hang. The
solvent container were then inserted into the extractor, and tightly clamped into the condenser.
After making sure all the connections were tight, the thimbles were moved into the “Boiling”
position where the thimble immersed in and the sediment came in contact with the solvents.
The extraction time was allocated for maximum of 6 hours (boiling position). At the first cycle,
bles were disconnectedmmed for ca. 3 hours. Then, the thiextraction with acetone was perform the condenser oved frowith the solvent (at rinsing position). The solvent cups were gently remThe second extraction was m (i.e. hexane/acetone). ste with other solvent syand replaced. Thereafter, stemr another 3 hours following the procedure as the first solvent syperformed fothe extracts were combined, and proceed into the next step of working-up procedures (section
3.3.2). To check nothing is left behind after that given extraction time, the extracted sediment

50

was experimentally extracted with aceton/hexane (1/9) for 4 hours. The results confirmed no
peaks. Therefore other portion ght/weight). -weight basis (weiThe result is presented on a dry(aliquot) of each fraction was prepared for dry/wet coefficient for moist-sediment weight
n at ple aliquots were dried in the ovetical ones. The samcorrection at the same time as for analy60 – 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
- 3%. %ent ranged between ca. 1portion in sedim

SPM ExtractionUnlike 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.

Extract Working-Up3.3.2.Following extraction, the extract working-up procedure includes concentration (or
volume reduction), clean-up from polar co-extracting compounds, and sample matrix exchange
sis. to acetonitrile forHPLC analy

y evaporationConcentration using rotar3.3.2.1.Concentration (or volume reduction) was undertaken two times using rotary evaporator
out after extraction, and the OR-M, Büchi). The first concentration was carried(ROTAVAPsecond one applied after column chromatography clean-up process. Instead of the PAH analytes
ment contained a non-azeotrope from sedipounds, the first extract and other co-extracting comxture of ind extract has an azeotrope mts. The secomixture of acetone and water solvenacetone/hexane. A mixture of acetone (boiling point, BP, 56.2oC) and hexane (BP, 68.8oC)
forms an azeotrope mixture with boiling point at 49.8oC with 68% / 32% acetone/hexane by
weight in its vapor. The extracts were at the end combined. The concentration was carried out at
the cooling water rate ca. 1.5 liter/minute for two steps. First, the evaporation was undertaken
at a combination of pressure (400 – 500 mbar under vacuum pump) and water bath temperature
(40oC). Second, the evaporation was accomplished by applying the pressure and bath
temperature of 500-600 mbar and 45o – 60oC. The evaporation ended with hexane (ICES, 1997).
. lca. 1 - 2 mume attained The final vol mixture of (3/7 : v/v)The second evaporation was applied for a non-azeotrope dichloromethane (BP, 40oC) and hexane after cleaning-up process. The evaporation was carried

51

out for two steps: (1) evaporation for dichloromethane with the pressure of 250 – 400 mbar and
oC, and (2) evaporation of hexane with pressure of 500 – 600 the bath temperature of 30 - 35mbar and the bath temperature of 50-60oC. The final volume attained ca. 1 ml. The loss of
al ith the surrogate standard for procedurtes during concentration was confirmed wanaly (section 3.4.). efficiency

3.3.2.2.Drying and Alumina/Silica (Al2O3/ SiO2) column for clean-up of polar mixtures
clean-up process cts were subject to ess, the extra concentration procFollowing the firstusing 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
n used for clean-up. oxide phase in a columthe top of aluminumClean-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
ng sulfur-containi co-extracted such as blypolar and non-polar compounds which is inevitacompounds 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
l. The first fraction was eluted with hexane; the second and third fractions were elutedwith 20 maction was again eluted by hexane. The roromethane/hexane (3/7 : v/v). The fourth f dichlbyPAHs were mainly detected in the second fraction, and slightly in the third fraction. The clean-
mixture standard. One PAHs rst with blank run, and with spiked 16 n was checked fiup columcolumn 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 column’s volume
). l(ca. 40 m

stream and Matrix Exchange ) Nitogen (N3.3.2.3.2 the evaporator (see 3.3.2.1). byl reduced to ca. 1 mThe clean extract was again gentlyFurther concentration was carried out using a gentle stream of N2 to dryness. Finally, 1000 l of
sis. HPLC analyle for pacetonitrile was added to the sam

e SPE Cartridges for dissolved PAHs Elution of th3.3.3.Dissolved PAHs retained in SPE cartridges were eluted with 4 ml of dicloromethane
(DCM) (repeated three times) at flow rate of 5 ml/min. Prior to elution, SPE cartridge was dried
under vacuum and gently stream of N2. The eluates were reduced to a dry state, then 300 -
400L of acetonitrile was added to them for HPLC analysis.

52

3.3.4.and fluorescence detPAH determination: High Performanectors (HPLC UV/FLDs)ce Liquid Ch romatography with ultraviolet
3.3.4.1.Baseline separation with reverse phase octadecyl (RP-C18) column chromatography
ed using a reverse phase mPAHs were perforquantification of the Baseline separation and wide-pore octadecyl -RP-C18- column (250 mm x 46 mm, 5 μm, 300 ) obtained from
ance , USA) with a high performpsburg, New JerseyBAKERBOND, J.T. Baker Inc (Phillisolvent delivery pump (LKB Bromma 2249 Gradient Pump) for HPLC. The sample injection
loop was 20 μl. 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
mixture of the same 16 PAHs ence standard containing a separation was exercised for PAH refercompounds (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).

Table 3.1. Elution Mode (flow rate: 1 ml/min.)
Time Program ABRemarks
Acetonitrile (%)Water (%)(minute)10.0 00.0 – 30.0 – 10.0 45 45 – 0 55 55 - 100 Isocratic (at start timlinear gradient (2.25% ACN/me) in.)
isocratic 100 0 40.0 30.0 – 45.0 40.0 – 50.0 – 45.0 45 0 – 45 55 100 - 55 isocratic (at stop timlinear gradient (9% ACN/min.) e)

3.3.4.2.Detection Systems Two different detectors were operated: (1) an ultraviolet (UVD) detector (2151 Variable
Wavelength Monitor, LKB Bromma) with a wavelength of 254 nm for acenaphthylene, and (2)
other 15 PAH ackard 1046A programmable fluorescence detector (FLD) for thea Hawlett-Pcompounds with three shifts of excitation/emission (ex/em) wavelengths (Table 3.2.). The
elution order of the compounds was confirmed by injected individual PAH reference standard.
Electronic features of the HP 1046A FLD were set to get optimum detection including the peak

53

amplification factor, PMTGAIN = 11; the flash frequency, LAMP = 1, 1.25 W / 55 Hz; and data
sec”. rval, RESPONSETIME = 4, 1000 mreduction inte Table 3.2. Selective pairs of fluorometric wavelength and retention time (minute) of the PAHs
ode. and the surrogate standards with the given elution mNo. Analyte Wavelength Retention Time (minute)
Target Analytes ex / em UVMean ± SD D 254 nm (N=17)RSD Mean ± SD FLD (N=31) RSD
nm (%) (%)
21 NapAcenaphthalehthyne, lenNAe, ACPH YN 250 / 341 9,7,0972 ± ± 0 0,,0054 0,0,5249 7,88 ± 0,03 0, 41
43 FluoAcenarepne, htheFLUne, ACEN 25250 / 0 / 334411 1211,4,7 ± ± 0 0,,0097 0,0,7263 1211,6,8 ± ± 0 0,,0076 0,0,5548
56 PheAntnanthracehrene,ne, A NPHETH N 25254 / 0 / 34400 1 1417,4 ,9 ±± 0,1 0,12 2 0,0,7968 1517,6 ±,2 ± 0, 0,10 10 0,0,6658
87 PyFluorenera, PntheYRne, FLA 25254 / 4 / 440000 2119,0,7 ± ± 0 0,,1111 0,0,5257 2119,2,9 ± ± 0 0,,1100 0,0,4848
9 Benzo(a)anthracene, BaA 254 / 400 25,7 ± 0,12 0,48 25,8 ± 0,13 0,49
1110 ChryBenzose(b)flne, CuoHraRY nthene, BbFLA 25254 / 4 / 440000 2926,6,6 ± ± 0 0,,1154 0,0,5052 2926,8,7 ± ± 0 0,,1144 0,0,4852
12 Benzo(k)fluoranthene, BkFLA 254 / 400 30,7 ± 0,13 0,62 31,3 ± 0,16 0,51
1413 DibeBenzo(a)nzo(a,h)apyrene, BaPnthracene , DANTH 25254 / 4 / 44000 0 31,2 ±34,5 ± 0,19 0,17 0,0,56 53 32,3 ±34,6 ± 0,18 0,16 0,0,53 49
1615 IndeBenzono(g(1,h,2,i),3p-c,erd)ylpyreene, BPne, IPERYYR 24256 / 4 / 448080 3635,1,0 ± ± 0 0,,2138 0,0,6252 3635,3,1 ± ± 0 0,,1197 0,0,5448
Surrogate Standards N = 10 N = 10
dd10-ph10-fluoranenantthhenrene e 225540 / / 40340 1 1183,9 ± 0,15 ,6 ± 0,23 01,,7783 1193,1 ± 0,15 ,7 ± 0,24 01,,8706
d16m2-ethyperylchrylene sene 25254 / 4 / 440000 2728,6,9 ± ± 0 0,,1250 0,0,5468 2729,6,0 ± ± 0 0,,1159 0,0,6754

54

Elution program: from 55% ACN to 100% ACN
55

5min1015202

HANT

NEACHPUFLNANREPY1 DNEPH0
PHYN0A D1LFFLA
AC

3/25041

5

100

54033

ALFBk

ALFBaABbRYCHenesyrhcylthe6 M
DYRPE21

4004/25

BaP

YERBPHTYRDANIP

8486/24

100

0

Fig. 3.1. Comparison of chromatograms for 16 PAHs between UV 254 (red) and FLD (black) with the
ue). rated PAHs (bldeute Hs Afication of PIdentification and Quanti3.3.4.3.used for standard was Retention time (RT) of the peaks of the 16 PAHs of the reference analytes’ peak identification. The standard was injected at the beginning of daily measurement.
The precision (confirmed by standard deviation) of the RT of the 16 PAH standards throughout
the analyses can be seen in the table 3.2. In general, the precision of the retention time between
e hation of the shift in tminutes. The surrogate standards were also used for confirm0.03 and 0.2 retention time since PHEN D10, FLA D10, PERY D12 coming out just before PHEN, FLA,
2). and BbFLA (Fig. 3.Quantification was made by integrating the peak area of the analytes using an external
standard method with five to six point calibrations. The repeatability of the peak area of each
analyte measured by relative standard deviation of repeated measurement of the working
range of detector response m 3 to 10% (Table 3.3.). The linearityreference standard extends frowas exercised in the range of 0.0025 ng/μl to 1 ng/μl for FLD, and from 0.2 ng/μl to 2 ng/μl for
UVD 254 nm. The range of linearity follows the range of concentration of linearity suggested
by the work of Grope (2001). Dilution system of the 16 PAHs Mix61 standards was given in the

55

m as obtained froble 3.4. It wit of detection (LoD) are provided in the taAppendix 3.1. Limrepeated analysis of a sample with a very low content of the analytes (after Huber, 2003).
PBaenesyrhcylhte6 M
HDANTALFBk1RY DEP2ALFBbERYBPYRIP
RYCH01 DNEPHHANTRPYABa
ENPHHNAPNACEFLU0A D1LFAFL
250/341254/400246/488
Fig. 3.2. An example of peaks identification using retention time of the standards (black) and
dericonfirmved fromation on the shift in fluorescence detector. the retenti The red on time using chromatogramthe was adeuterated stan extract ofndards. The c mud frhaction ofromatogram sedimes werent 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 RSD (%)SDMean 3,29 2454746531 Naphthalene 2 Acenaphthy3 Acenaphthene lene 1185732148110219109585,10 ,62
4,08 3083756504 Fluorene 6 Anthracene 5 Phenanthrene 232070584941915649608,48 8,25
8 Py7 Fluoranthenerene 38689800622154095,10 5,73
10 Chry9 Benzo(a)anthracene sene 13847711474211213680385,93 ,10
12 Benzo(k)fluoranthene 11 Benzo(b)fluoranthene 299455279267159581559855,33 ,59
9,88 537454373rene 13 Benzo(a)py7,08 826111666814 Dibenzo(a,h)anthracene 15 Benzo(g,h,i)perylene 3841035819,32
16 Indeno(1,2,3-c,d)pyrene 118573102198,62
56

the PAHs mit of detection (LoD) for LiTable 3.4.AbsoluteConc. of amount No. PAHs LoD (ng/μl) (pg) 1 Naphthalene 0,01 266
2 Acenaphthy3 Acenaphthene lene 0,020,081569 441
4 Fluorene 5 Phenanthrene 0,010,01115 154
16 0,0016 Anthracene 8 Py7 Fluoranthenerene 0,0020,024453 5
10 Chry9 Benzo(senea )anthracene 0,0010,001125 6
120 )fluoranthene 0,0111 Benzo(b13 Benzo(12 Benzo(ak)pyrene 0,001)fluoranthene 0,001214 0
63 )anthracene 0,00314 Dibenzo(a,h15 Benzo(16 Indeno(1,g,h,i2,3-)peryc,d)pylene 0,004rene 0,00235 79

ntrols Quality Co3.4.These quality control of method procedures involved measurements of routine procedural
blank, procedural efficiency, and instrumental performance. The procedural blank was
performed for every two batches of the sample extraction. Procedural or method efficiency for
the sample analysis was evaluated by the recovery of surrogate deuterated PAHs: d10-
phenanthrene, d10-fluoranthene, and d12-perylene. Those deuterated PAH standards were
ng PAHs. The , 4-ring PAHs, and 5- and 6-ri surrogating 2- and 3-ring PAHsrespectivelysummary of the recovery of each surrogate was given in the table 3.5. One working standard (16
PAH Mix61) was injected at the beginning of daily measurement for the instrumental
errors due to changes in the performance check i.e. precision, repeatability, and randomequipment conditions during the period of study.
Table 3.5.reproducibit Recoveryy. Data were driven from of spiked deuterated PAHs to ultraviolet detectors (see Appthe samples foendix 3.2 for r procedural efficiencydetail). and
CompoundsSedimentN = 51 SPMN = 32 WaterN = 10
Mean ± SD Mean ± SD Mean ± SD Fluoranthene Phenanthrene D10 D10 97.5 ± 14.6 82.8 ± 15.2 96.8 ± 10.2 95.2 ± 10.1 91.7±6.96
Perylene D12 94.6 ± 12.6 95.7 ± 8.90 88.8±9.88

57

with 16-PAH standard spiked method. 16 PAHs also checked was Procedural efficiencyer for dissolved ent and SPM, and Milli-Q watmspiked into the thimble blank for sediwere the sis. For PAHs. These spiked standards then proceeded through the step of procedural analydissolved 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
49% (BaP) to 96% (PHEN) for the water. fromsedimTable 3.6. Rent and SPM analyecovery ofs spiked PAH standards (16 is. The data was calculated fromPAH Mix 61) into t the peak area of the blahnk thime ultraviolet bles for
onse. detector resp (ng) Compounds Spiked Mass 1 2 Recovery Test (%) 3 Mean
Naphthalene 500 111 89 101 100
AcenaAcenaphphthethynleen 50e 10000 101081 10969 8399 10963
Fluorene 100 98 94 89 94
AnPhenathntracene 5hrene 500 9936 19819 18901 19305
Fluoranthene 100 87 98 94 93
138 76 Pyrene 50 103 95 BenzChryseneo(a 50 )anthracene 50 93 85 101 107 85 82 93 91
BenzBenzo(o(kb)fl)fluuororantanthheennee 50 100 1193 4 9195 9193 9994
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
analyTable 3.7.sis. The Recovery of spidata was calculated fromked PAH standards into the peak area the blank Milli-of the ultraviolet detector response. Q water for dissolved PAH
Compounds (ng) Spiked Mass 1 2 Recovery Test (%) 3 Mean
AcenaNaphthaphlenthyele 30ne 60000000 9247 9682 9988 9572
FluAcenaorenphe 6thene 30000000 18402 19100 19503 19001
Phenanthrene 3000 98 93 97 96
AnFluorathntracene 3hene 6000000 19708 18606 19512 19309
90 83 93 93 Pyrene 3000 ChryBenzo(senea 30)anthracene 3000 00 94101 6468 6675 7581
Benzo(b)fluoranthene 6000 102 63 66 77
BenzBenzo(o(ak)py)flureorneant 30hene 300000 5874 4244 4648 4955
Dibenzo(a,h)anthracene 6000 106 53 53 71
IndeBenzo(no(1,2,g,h,i3-c,d)perylene)pyrene 6000 3000 10104 0 5652 5953 7270
58

References (Chapter I – III) Achten, C., Hofmann, T., 2009. Review: Native polycyclic aromatic hydrocarbons (PAH) in coals – a
hardly recognized source of environmental contamination. Science of the Total Environment 407,
2461-2473.
Ahrens, differeM.J., Depree, nt size Cand de.V., 2004. Insity frnhomactions of contogenous distribution aminated sedimof polent fromycyclic arom Aucatkland ic hHarbour, ydrocarbons in New
Zealand: an opportunity for mitigation. Marine Pollution Bulletin, 48, 341-350.
Appel, J., Bockhorn, H., Frenklach, M., 2000. Kinetic modelling of soot formation with detailed
chemistry and physics: laminar premixed flames of C2 hydrocarbons. Combustion and Flame, 121,
. 13622-1Atkinson, R., polycyclic orArey, ganic mJ., Zielinska, Ba., tter in the atmoPitts, Jr. J.N., sphere. WineAtmr, ospheric EnvironmA.M., 1987. Evidence ent, 21(1for th0), 2261-2264.e transform ation of
ical Profile for Polycyclic Aromatic mical and Physical Information, in: ToxicologATSDR, CheHydrocarbons (PAHs), ATSDR, Atlanta, Georgia, USA, 1995, pp. 209-221
). profiles/tp69-c3.pdf.gov/tox(http://www.atsdr.cdcBaars, B-J., 2002. The wreckage of the oil tanker ‘Erika’ – human health risk assessment of beach
Barbour, E.cleaning, sK., uSabra, A.nbathing anH.d , Shaib, H.swimmA., iBeng. Toxicrckley, oA.M.logy Letters,, Fara 128,jalla, N.S 55-68.., Z urayk, R.A., Kassaify, Z.G.,
harvested from2008. Baseline a war-i data of polycyclicnduced arooil spill zone ofmatic hydroca the rbons correlation to Eastern Mediterraneansize of m Sea. Mariarine organe Pollution nisms
Bulletin 56, 770-797.
Baum, A., Rixen, T., Samiaji, J., 2007. Relevance of peat draining rivers in central Sumatra for the
riverine input of dissolved organic carbon into the ocean. Estuarine, Coastal and Shelf Science 73,
563 – 570.
Baummuard, P., Budzissels of the westernski, H., Garrin Medigues, P.terranea,n sea 1998. Po. Environmlycyclic aromental Toxicatic ohydrocalogy and Crbons hemistry in sedim17(e5), nts and 765-
6.77Baumard, P., Budzinski, H., Garrigues, P., Dizer, H., Hansen, P.D., 1999a. Polycyclic aromatic
hydrocarbons in recent sediments and mussels (Mytilus edulis) from the Western Baltic Sea:
occurrence, bioavailability and seasonal variations. Marine Environmental Research, 47, 17-47.
BaumPoard, P., Budzilycyclic aromatic hnski, H.,y Garridrocgues, P.,arbon (PAH) bu Narbonne, J.Frden of m., Burgeussels (ot, T.,Mytilus Michel, X., Bellocq, J.sp.) in different m, 1999arine b.
Envenviironronmmeental nts in relation Research, 47: 4with15-439 sedim. ent PAH contamination, and bioavailability. Marine
Behymer, T.D., Hites, R.A., 1985. Photolysis of polycyclic aromatic hydrocarbons adsorbed on simulated
atmospheric particulates. Environmental Science and Technology, 19, 1004-1006.
BernBihari, Ner, R.A., ., Faf19a80ndel, M. Early ., HaDiagmeenr, B., Kesis: A rTheoralj-Bilen, Bitical Ap., pro2006. Pach, 24AH c1 ppo. Prinntent, toceton Unxicity and ivgeersity Press. notoxiciy of
coastal marine sediments from the Rovinj area, Northern Adriatic, Croatia. Science of the Total
EnBinelli, A., Provivironmni, ent, 366, 602A., 2004. Risk -611. for human health of some POPs due to fish from Lake Iseo.
Ecotoxicology and Environmental Safety, 58, 139-145.
Bockhorn, Henning, 1994. Soot formation in combustion: mechanisms and models. Springer series in
physics, 59. 596 pp. ical chemBoehm, P.D., Douglas, G.S., Burns, W.A., Mankiewicz, P.J., Page, D.S., Bence, A.E., 1997. Application
of petrValdezo oleumil sp ill. Marinhydrocae Pollurbons chemtion Bulletin, 34ical fingerprinting a(8), 599-613n. d allocation techniques after the Exxon
Bofetta, P., Jourenkova, N., Gustavsson, P., 1997. Cancer risk from occupational and environmental
exposure to polycyclic aromatic hydrocarbons. Cancer Causes and Control, 8: 444-472.
Boldrin, contineA., Lnatal sngone, Lhelf: dispe., Miseroccrsion anhi, Sd sedim., Turcehetto, ntation ofM., Acri, dissolveF., d a2005.nd suspe Po Rivended mr plaumtter durie on the ng diffAdriatic erent
river discharges rates. Marine Geology 222-223, 135-158.
BPDApS Irnesendragted iniri Roka the 1n.st SP, 2004. PICE hWorksysical conditihop Cluster on 3.of Si1., Pekanbaak River wateru, Inr (in Idonesia. ndonesian language). Paper
Brasseur, C., Widart, S., Muller, M., Maghuin-Ragister, G., Scippo, M-L., 2007. Alteration of the
estrogen hormone pathway in hepatic cells after exposure to polycyclic aromatic hydrocarbons.
Toxicology Letters 172(1), S38.
Budzinski, H., by polycyclic aromJones, I.atic hydr, Bellocq, J., Pieraocrarbons in the d, C., GarGironderiques, estuary.P., 1997. Eval Marine Cuation hemof sediistry 58, me85-9nt contam7. inant

59

Burkhardt, M.R., Zaugg, S.D., Burbank, T.L., Olson, M.C., Iverson, J.L., 2005. Pressurized liquid
extraction using water/isopropanol coupled with solid-phase extraction cleanup for semivolatile
organic compounds, polycyclic aromatic hydrocarbons (PAH), and alkylated PAH homolog groups
Butler, Jin se.D.,dim eCrossley,nt. Analytica Ch P., 1981. Rimica Acta eactivit549, 104-116.y of polycyclic arom atic hydrocarbons adsorbed on soot
particles. Atmospheric Environment, 15, 91-94.
Cachot, J., GeDevier, M.H., Pottier, ffard, O., AugagneD., Bur, S.udzin, Lacroix, Sski, H., ., Le Me2006. Evnach, K.idence of genotoxicity , Peluhet, L., Coutearelated to u, J., Denier, high PAH X.,
content of sediments in the upper part of Seine estuary (Normandy, France). Aquatic Toxicology
. 57-267, 297Cao, Z., Wang, Y., Ma, polycyclic aromatic hydrocaY., Xu, Z., Shi, rbons inG., Z reclaihuang, med waY.ter a, Zhu, nd surface T., 2005. water Occurrenof Tianjin, Cce and distrihina. Jobution of urnal
51-59. als A122, Materiof Hazardous Carls, M.G., Short, J.W., Payne, J., 2006. Accumulation of polycyclic aromatic hydrocarbons by
Chester, R., Neocalan2003. Marius copne epodGes inochem Port istry, 2Valdndez, Alaska. Marin Edition. Blackwell Science Ltd, e Pollution Bulletin, 506 52, pp. 14 80-1489.
Chiang, K-C., Chio, C-P., Chiang, Y-H., Liao, C-M., 2009. Assessing hazardous risks of human exposure
to temple airborne polycyclic aromatic hydrocarbons. Journal of Hazardous Materials 166, 676-
5.68Chiou, C.T., McGroddy, S.E., Kile, D.E., 1998. Partition characteristics of polycyclic aromatic
Christl, I., Kretzschmhydrocarbons aon soils and ser, R., 2001. Relating idiments. Environ onmbinding byental Science & fulvic and Technolhumic acogy 32, 264-id269.s to chem ical
25com05-251position a1. nd molecular size. 1. Proton Binding. Environmental Science and Technology, 35,
Conde, F.J., Ayala, J.H., Afonso, A.M., Ganzalez, V., 2005. Emissions of polycyclic aromatic
hydrocarbons from combustion of agriculture and sylvicultural debris. Atmospheric Environment,
de Abra39:ntes, R 6654 –., de 6663Assunçã. o, J.V., Pesquero, C.R., 2004. Emission of polycyclic aromatic hydrocarbons
De fromLuca, G.D., light-duty diesel Furesi, A., Micera, vehicles exhaust. G., AtmPanzanelli, A., Piu, ospheric EnvironmP.C., Piloent 38, 1631-1640. , M.I., Spano, N., Sanna., 2005.
Nature, distribution and origin of polycyclic aromatic hydrocarbons (PAHs) in the sediments of
Olbia harbor (Northern Sardinia, Otaly). Marine Pollution Bulletin 50, 1223-1232.
Deng, H., Peng, P., Huang, W., Song, J., 2006. Distribution and loadings of polycyclic aromatic
hydrocarbons in the Xijiang River in Guangdong, South China. Chemosphere, 64, 1401-1411.
flames, in diesDobbins, R.A., Fletcher, R.A., Beel fuels, and innn diesel emer Jr. B.A., Hoefissions. Combustion t, S., 2006. Polyand Flamcyclic e, 144, arom773-781. atic hydrocarbons in
Fabbri, D., Vassura, I., Sun, C.-G., Snape, C.E., McRae, C., Fallick, A.E., 2003. Source apportionment of
Marine Cpolycyclic aromhemisatry, 84tic hydr, 123oca-135. rbon in a coastal lagoon by molecular and isotopic characterisation.
Falcon, M.S.G-., Lamela, C.P-., Gandara, J.S-., 2004. Startegies for the extraction of free and bound
polycyclic aromatic hydrocarbons in runn-off water rich in organic matter. Analyt. Chim. Acta,
508: 177 – 183.
Fang, M., Zhconpounds ieng, M., n Wthe ang, F., TIndonesia o, K.L., Jbiomaafar, ass burning aeroA.B., Tong, S.Lsols – cha., 1999. The solvracterization studies. Atent-extractable orgamospherinic c
Environment 33, 783-795.
Fernandes, M.distributions in the SeiB., Sicre, M.ne -A., Briveoireau, r and its estuaryA., Tronczy. Marnski, J., ine Pollution B1997. Poulyaromlletin, atic hy34(11): 857-867. drocarbon (PAH)
Fernandes, M.B., Sicre, M.-A., Broyelle, I., Lorre, A., Pont, D., 1999. Contamination by polycyclic
aromatic hydrocarbons (PAHs) in French and European rivers. Hydrobiologia, 410, 343-348.
Fernández, P., Grimalt, J.O., Vilanova, R.M., 2002. Atmospheric gas-particle partitioning of polycyclic
aromatic hydrocarbons in high mountain regions of Europe. Environmental Science and
Technology, 36, 1162-1168.
Fernández, P.Polycyclic Ar, Vilanova, R., omatic CoGrimmapounds 9(t, J.O., 1996. P1), 121-1AH 28.di stribution in sediments from high mountain lakes.
Fernández-Gonzáles, V., Concha-Graña, E., Muniategui-Lorenzo, S., López-Mahía, P., Prada-Rodríguez,
D., 2007. Solid-phase microextraction-gas chromatography-tandem mass spectrometric analysis of
polycyclic aromatic hydrocarbons towards the European Union water directive 2006/0129 EC.
FrenklacJournh, M.,al of Ch 2002. Reacromatogrtion maphy A, echanis1176m of s, 48-56. oot formation in flames. Physical Chemistry Chemical
2028-2037. Physics, 4,

60

Garbarini, D.R., Lion, L.W., 1986. Influence of the nature of soil organics on the sorption of toluene and
trichloroethylene. Environmental Science and Technology 20, 1263-1269.
Gauthdissolier, T.D., Seltz, ved humic Wm.aR., Grant, C.L., terials on pyrene Koc va1987. Effects lues. Envirofonm structural and comental Science and Technolpositional variations ogy, 21(3), of
. 24843-2Gebhardt, A.C., Gaye-Haake, B., Unger, D., Lahajnar, N., Ittekkot, V., 2004. Recent particulate organic
carbon and total suspended matter fluxes from the Ob and Yenisei Rivers into the Kara Sea
(Siberia). Marine Geology 2007, 225-245.
Gevaand o, B., Jones, K.Cprocessing in a sm., Hamall ruralilton-Taylor, J. lake, Cum, 1988. bPoria UKlycyclic arom. The Science atic hydrocarbon of the (PAH) Total Environment, 215, deposition to
. 24231-2Ghosh, contamU., Zimmerminated harbor sediman, J.R., Lutents hy, R.Gand ., 2003. effects PCB and Pon PAH bioavailability. AH speciation amEnvironmeong particle types in ntal Science &
Glarborg, P.Technol, 2007. ogy 37, Hidde220n9-2217 interactions - t. race species governing combustion and emissions. Proceedings
of the Combustion Institute, 31, 77-98.
Golomb, D., Barry, E., Fisher, G., Varanusupakul, P., Koleda, M., Rooney, T., 2001. Atmospheric
deposition of polycyclic aromatic hydrocarbons near New England coastal waters. Atmospheric
Environment 35, 6245-6258.
ed to evaluate equilibrium . Linear free energy relationships usGoss, K-U., Schwarzenbach, R.P., 2001partitioning of organic compounds. Environmental Science and Technology, 35 (1), 1-9.
Grathwsorpohl, P.,tion 1990. I of some chnfluelorinnce of ated aliporgahanic mtic haydrotter fromcarbons: ip soils and selicationdim on eKocnts from correlations. Environm various origins on tehntal e
Science and Technology 24, 1687-1693.
Grope, N., 2001. Natürliche und anthropogene organische Spurenstoffe in küstennahen
Meeressedimenten: Gehalte und Verteilung von polyaromatischen Kohlenwasserstoffen. PhD
9. . 32. PpDissertationGschwenlacustrine sedid, P.M., Hites, R.A., ments in the 1981. nortFluxes of the heastern United States. Gepolycyclic aromatic ochimica et compCosmounds to mochimica aActa, rine and 45,
2359-2367.
Guinan, J., Charlesworth, M., Service, M., Oliver, T., 2001. Source and geochemical constraints of
polycyclic aromatic hydrocarbons (PAHs) in sediments and mussels of two Northern Irish Sea-
loughs. Marine Pollution Bulletin 42(11), 1073-1081.
Haitzer, M., on the biocHöss, Sonce., Traunsntration of orpurger, W.ganic ch, Steinbeemicals inrg, C., 199 aquatic organism8. Effects of dissols, a reved view. Corgahemnic maosphere, tter (DOM) 37(7),
Hawt1335-1362.horne, S.B., Azzolina, N.A ., Neuhauser, E.F., Kreitinger, J.P., 2007. Predicting bioavailability of
sediment polycyclic aromatic hydrocarbons to Hyalella asteca using equilibrium partitioning,
supercritical fluid extraction, and pore water concentration. Environmental Science and
HeemTechnoloken, O.P., satchel, B., gy, 41, 6297-630Theobal4. d, N., Wenclawiak, B.W., 2000. Temporal variability of organic
miat Dessacropollutantu, Germs in any. Asusperchiendevd e Envirparticulate monmatter of ental Contamthe Riveination rT Elbe oxicoat Hamburlogy 38, 11-g an3d the1. River Mulde
Hellou, J., Steller, S., Leonard, J., Langille, M.A., Tremblay, D., 2005. Partitioning of polycyclic
aromatic hydrocarbons between water and particles compared to bioaccumulation in mussels: a
Hellou, J., harbour case. Marine EnSteller, S., Leonard, J., Langille, M.A., Trevironmental Research, 59, 101-mb117.lay, D., 2005. Partitioning of polycyclic
hararombour caseatic hydrocar. Marine Ebons nvironmbetween water aental Research, 59, 101-nd particles com117. pared to bioaccumulation in mussels: a
Hites, R.A., Laflamme, R.E., Farrington, J.W., 1977. Sedimentary polycyclic aromatic hydrocarbons: The
Science, 198, 829-831. historical record. Horowitz, A.Jcomposition t., Elrick, o trace elemK.A., 1987. ent chemThe istry. Applied relation of streaGeocmhem sedimistry, 2, 437-451. ent surface area, grain size and
Hu, Y., Bai, Z., Zhang, Ltraffic policemen exposed to ., Wang, X., Zhapolycyclic aromng, L., aQingchan, Y., Zhu, T., 2007. tic hydrocarbons (PAHs) in Tianjin, CHealth rishk assessmina. Science ent for
of the Total Envrionment 382, 240-250.
Huang, W., Peng, P., Yu, Z., Fu, J., 2003. Review: Effects of organic matter heterogeneity on sorption
and desorption of organic contaminants by soils and sediments. Applied Geochemistry 18, 955-
2.97

61

Huang, W., Weber, W.J., Jr. 1997. A distributed reactivity model for sorption by soils and sediments. 10.
Relationships between desorption, hysteresis, and the chemical characteristics of organic domains.
Huber, W.Environm, 2003. Basic calculatiental Science and Ton about the limit echnology 31, 2562-2of569. detection and its optimal determination.
Hussain, M.Accreditation, Rae, J., Gilm and Quality Assuan, A., Karanussce 8,, P., 1998. 213-217. Lifetime health rissk assessment from exposure of
Contamrecreastional ination and Tuserso to xicololpology 35, 527-ycyclic arom531. atic hydrocarbons. Archives of Environmental
Hwang , H-. M., Foster, G.D., 2006. Characterization of polycyclic aromatic hydrocarbons in urban
stormwater runoff flowing into the tidal Anacostia River, Washington, DC, USA. Environmental
PolIARC, 1987. IARC lution 140, 416Monogra-426. phs on the evaluation of carcinogenic risks to humans, Suppl. 7, overall
evaluations of carcinogenicity: an updating of IARC Monographs volumes 1 to 42, Lyon, IARC
Press. ICES,me 1997. thods. InDeterm Reination of port of the ICpolycyclic arES Advisoomryatic Commihydrttee ocaronbons (P the Marine AHs) in Environmsedimeent, 1997. ICEnts: Analytical S
Cooperative Research Report 222, 118-124.
UniIPCC 2000. Land versity Press, 377 Use, Land-Use Cpp (avahilable onliange anne: http://www.ipccd Forestry, A Special Report of the .ch). IPCC. Cambridge
Ishaq, R., NäPAHs in air af, C., nd Zebühr, water particY., Broman, ulate samD., Järples – nberg, U.patterns and va, 2003. PCBs, Priations. CChemNs, PCDD/Fosphes, PAre, 50, 1131-1150.Hs and Cl-
Iwata, H., Tanabe, S., Sakai, N., Nishimura, A., Tatsukawa, R., 1994. Geographical distribution of
impersistenplications for t organocglobal rehlorines idistrin air, bution water fromand lower latitsediments frudes. Environmom Asia and ental PoOceallution, 85, nia, and t15-33. heir
Jeanneau, L., Faure, P., Jardé, F., 2007. Influence of natural organic matter on the solid-phase extraction
Joof urnoral ofganic m Chiromatography cropollutants application tot heA, 1173, 1-9. water-extract from highly contaminated river sediment.
Jenkins, B.M., Jones, A.D., Turn, S.Q., Williams, R.B., 1996. Emission factors for polycyclic aromatic
Jiang, C., Alexandehydrocarbons frr, R., om biomKagi, R.I., Murrayass burning., Envir A.Ponm., 2000. Origin ental Science and Tecof peryhnollene in ancientogy, 30, sedim 2462-2469.ents andtis
geological significance. Organic Geochemistry, 31, 1545-1559.
Johnson, M.D., Huang, W., Weber, W.J., Jr. 2001. A distributed reactivity model for sorption by soils and
sediments. 13. Simulated diagenesis of natural sediment organic matter and its impact on
sorption/desorption equilibria. Environmental Science and Technology 35, 1680-1687.
Juhaz, hydrocarbons:A.L., Naidu, R., 2000. a review of the mBioremediation oficrobial de high mgraodation of lecular benzo[a]pyreweight polycyclic aromne. International atic
Biodeterioration and Biodegradation 45, 57-88.
Kakareka, S.Science ofV. , Kukharcthe Total hyk, T.I.Environm, 2003. PAental, 308: H em257-ission 261. from the open burning of agricultural debris. The
Kanaly, R.A., Harayama, S., 2000. Biodegradation of high-molecular-weight polycyclic aromatic
Karickhhoffydro, S.cW.,arbon Brs bowy bn, D.acteria. JouS. anrnal d Scott, T.Aof Bacterio., 1979.logy S, 182orp(8), 20tion of 59-206hy7. drophobic pollutants on natural
Kayal, S.sedime, Connel,nts. W Da.ter W., Researc1995. h 13, 241-Polycyclic arom248. atic hydrocarbons in biota from the Brisbane river
estuary, Australia. Estuarine, Coastal and Shelf Science 40, 475-493.
Khalfi, A., Trouve, G., Delobel, R., Delfosse, L., 2000. Correlation of CO and PAH emission during
rnitures. Journal of Analytical Application wood waste fue incineration of -scallaboratory243-262. Pyrolysis, 56, Kim, G.B., Maruya, K.A., Lee, R.F., Lee, J.-H, Koh, C.-H., Tanabe, S., 1999. Distribution and sources of
polycyclic aromatic hydrocarbons in sediments from Kyeonggi Bay, Korea. Marine Pollution
. , 38(1), 7-15lletinBuKo, F-C., Baker, J.B., & plankton in the m1995. esohaline Partitioning Chof hydrophobesapeake Bay. Marine Cic orhganic contaminants toemistry, 49, 171-188. resuspended sediment
Koelmans, A.A., Jonker, M.T.O., Cornelissen, G., Bucheli, T.D., Van Noort, P.C.M., Gustafsson, Ö.,
2006. Black carbon: the reverse of its dark side, review. Chemosphere, 63, 365-377.
Kot-Wasik, A., Dbrowska, D., Namienik, J., 2004. Photodegradation and biodegradation study of
benzo(a)pyrene in different liquid media. Journal of Photochemistry and Photobiology A:
Chemistry 168, 109-115.
Kowalewsof orgakan, G., ic contaKonat-Stepminants to towicz, Jh., Wae Baltic in thwrzye niak-WydrowsOdra Estuary. Mka, B., Szarine ymPollution czak-Zyla, M., 2003. TBulletin, 46, 703-718. ransfer

62

Ladesma, E.B., Kalish, M.A., Nelson, P.F., Wornat, M.J., Mackie, J.C., 2000. Formation and fate of PAH
Laflammeduring t, R.he E., Hites, R.Apyrolysis and .fuel, 1978. The gl-rich combustiobal distrion of coal bution of primary tarpolycyclic arom. Fuel, atic hydr79, 1801-1814. ocarbons in recent
Laflamme, R.sediments. GeochimiE., Hites, R.A., 1979. Tetra- ca et cosmochimand pentacyica Acta, 42: 289-303.clic, na turally-occurring, aromatic hydrocarbons in
recent sediments. Geochimica et Cosmochimica Acta, 43, 1687-1691.
Langmann, B., 2007. A model study of smoke-haze influence on clouds and warm precipitation formation
in Indonesia 1997/1998. Atmospheric Environment 41, 6838-6852.
Law, R.inJ., Da seawwes, V.Jater around ., WoodheaEnglandd, anR.Jd Wa., Matthiessen, les. Marine PoP., llution1997. P Boulletinlycyclic arom 34(5), 30atic hydr6 – 322. ocarbons (PAH)
Leahy, J.MicrobiG., ologicColwell, R.R.al Reviews 54(, 1990. Micr3), 305-315.obial de gradation of hydrocarbons in the Environment.
Lee, R.G.M., Coleman, P., Jones, J.L., Jones, K.C., Lohmann, R., 2005. Emission factors and importance
of PCDD/Fs, PCBs, PCNs, PAHs and PM10 from the domestic burning of coal and wood in the
U.K. Environmental Science and Technology, 39, 1436-1447.
Lehto, K-(PAHsM., ) in Vourimaa, E.,dilute aqueous s Lemmoetyinen, H.lutions detected , 2000. Phby fluoresotolysis of cence. polJourycyclic aromnal of Photocatic hydrhemiocastry and rbons
istry, 136, 53-60. emChPhotobiology A: Li, C-T., Mi, H-H., Lee, W-J., You, W-C., Wang, Y-F., 1999. PAH emission from the industrial boilers.
Journal of Hazardous Materials, A69, 1-11.
Liang, Y., Tse, M.F., Young, L., Wong, M.H., 2007. Distribution patterns of polycyclic aromatic
Water Researchhydrocarbons (PAHs) in , 41, 1303-131the sedim1. ents and fish at Mai Po Marshes Nature Reserve, Hong Kong.
LimaLibes, S.M., 1992. , A.L.C., Farrington, J.WAn introduction to mari., Reddy, C.M., 200ne biogeochem5. Comistry. John Wiley bustion-deriv& edSons, Inc. polycyclic aromatic
hydrocarbons in the environment – a Review. Environmental Forensics, 6:2, 109-131.
Lipiatou, E.hydro, carbonSaliot, A., s in th1991. Fle western uxesMed and traiterrannean sport ofSea. Mari anthropne Chogeemniistry 3c and nat2, 51-71ural . polycyclic aromatic
Liu, H., Amand y, polynuclear arG., 1993. omatic hydrModeling partitioniocarng bons in and groutranndwasport interactions ter. Environmentalbetween Science and natural organic mTechnolattogyer ,
27, 1553-1582.
Liu, K., Xie, W., Zhao, Z-B., Pan, W-P., Riley, J.T., 2000. Investigation of polycyclic aromatic
Technolhydrocarbons ogy 34(11),in fly ash fr 2273-2279. om fluidized bed combustion systems. Environmental Science and
Liu, W.X., polycyclic aromDou, H., Waei, Z.C., tic hydrocarChang, bons fB.ro, Qiu,m co W.Xm., Libustion u, Y.of di, Taffeo, S.,rent resi 2009. Emdential coals in Nortission characterh Chinaistics of.
ronment 407, 1436-1446. Envithe Total Science of Liu, Y.,of Tao, Sficers to., Ya polng, Y.ycyclic aro, Dou, H., matic hYang, ydrocY., Covearbons (PAHs) ney, R.during thM., 2007. Inhalation ee winter inx Beijposinure g, China. of traffic policeScience
ent, 383, 98-105. onmof the Total EnvirLong, E.R., MacDonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adverse biological effects
within ranges of chemical concentration in marine & estuarine sediments. Environmental
97.– ent, 19, 81 ManagemLuo, X-J., Chen, S-J., Mai, B-X., Yang, Q-S., Sheng G-Y., Fu, J-M., 2006. Polycyclic aromatic
hydrocarbons in suspended matter and sedimens from the pearl River Estuary and adjacent coastal
areas, China. Environmental Pollution, 139: 9 – 20.
Luthy, R. G.,Reinhard, M Aiken, G.R., Traina, ., BrusseaS.J.,u, M 1997. Se.quesL., Cunninghamtration of hydr, S.D., oGschwephobic ornd, P.Mganic c.,ontam Pignatello, J.inants J.,by
geosorbents. Environmental Science and Technology, 31, 3341-3347.
Mackay, D., Fraser, A., 2000. Bioaccumulation of persistent organic chemicals: mechanisms and models.
tion, 110, 375-391. ntal PollueEnvironmMackay, D.mechanism, Powers of the pa, B., 1987. Srticle concentorpration tion of hydreffect. ophobic Chemchemicals osphere, 6(4), 745-757. from water: a hypothesis for the
Maggi, C., National Onorati, F., riles and environmLamberti, C.ental quality standaV., Cicero, A.M., 2008. Trd in mhae rine environmhazardous epriority snt. Enviubstaronmences intal In Itmaly: pact
ent Review, 28, 1-6. AssessmMai, B.-X., Fu, J.-M., Sheng, G.-Y., Kang, Y.-H., Lin, Z., Zhang, G., Min, Y.-S., Zang, E.Y., 2002.
Chlorinated and polycyclic aromatic hydrocarbons in riverine and estuarine sediments from Pearl
River Delta, China. Environmental Pollution, 117, 457-474.

63

Männistö, M.K., Melin, E.S., Puhakka, J.A., Ferguson, J.F., 1996. Biodegradation of PAH misture by a
marine sediment enrichment. Polycyclic Aromatic Compounds, 11(1), 27-34.
Marce, R.M., Borrull, F., 2000. Solid-phase extraction of polycyclic aromatic compounds. Journal of
Marr,Ch LC.,rom Katoigraphrchstetter, y A, 8T.85,W., Ha 273-290rley, . R.A., Miguel, A.H., Hering, S.V., Hammond, S.K., 1999.
Characterization of polycyclic aromatic hydrocarbons in motor vehicle fuels and exhaust
Martí-Cid, R.,emissions Bocio, A. Environ., Llmenobet, Jtal Sci.enM., ce anDomid Technngo, Jo.lL.ogy, 33, 2007. , 309Inta1-3ke of099. chemical contaminants through
fish and seafood consumption by children of Catalonia, Spain: Health risks. Food and Chemical
Toxicology, Maruya, K.A., Risebrough, 45, 1968-1974. R.W., Horne, A.J., 1996. Partitioning of polynuclear aromatic hydrocarbons
Technbetweeolnog sediy, 30m, e29nts from42-2947. San Fransisco Bay and their porewater. Environmental Science and
Maskaoui, K., Zhou, J.L., Hong, H.S., Zhang, Z.L., 2002. Contamination by polycyclic aromatic
hPolydrolutcioarbonn 11s 8,in 10 th9-12e Jiu2. long River Estuary and Western Xiamen Sean, China. Environmental
as a function of issions t of PAH emenMastral, A.M., Callén, M., Murillo, R., García, T., 1988. Assessmcoal combustion variables in fluidized bed. 2. Air excess percentage (short communication). Fuel
77Mazzera, D., Hayes, (13), 1513-1T., 516. Lowenthal, D., Zielinska, B., 1999. Quantification of polycyclic aromatic
65-71. hydrocarbons in soil at McMurdo station, Antarctica. The Science of the Total Environment, 229,
McGrath, T.E., Chapolycyclic aromn, aW.G., tic hydrocaHajaligol, Mrbons .fromR:, 2003. the pyrolysiLow temps of cellulose.erature me Jchanismournal for t hof Anale formation ytical and of
66, 51-70. Applied Pyrolysis Means, J.C., 1995. Influence of salinity upon sediment-water partitioning of aromatic hydrocarbons.
Means, J.CMarin., e ChemiWood, S.G., stry, 51, 3-16. Hassett, J.J., Banwart, W.L., 1980. Sorption of polycyclic aromatic
Menon, N.hydrocaN.rbons , Menon, N.Rby sedime., 1999. Upnts and soils. Etake of polycycnvironmlic aromental Science aatic hydrocnd Tecarbons fhnolrom suspeogy, 14, 1542-nded 1528.oil borne
Miguel, A.sedimH.e, Kircnts by the mhstetter, T.arine bivaW., Harllve ey, Sunetta scriptaR.A., 1998.. A On-rquatic oaTd oxicemoloissigyons, 45 of , 63-6parti9. culate polycyclic
aromatic hydrocarbons and black carbon from gasoline and diesel vahicles. Environmental Science
and Technology, 32, 450-455.
Mihelcic, J.R., Luthy, R.G., 1988. Degradation of polycyclic aromatic hydrocarbon compounds under
various redox condition in soil-water systems. Applied and Environmental Microbiology, 54(5),
1182-1187.
Miller, J.S., 35(1), 233Olejni-24k, D., 3. 2001. Photolysis of polycyclic aromatic hydrocarbons in water. Water Research,
Milliman, J.D., Farnsworth, K.L., Albertin, C.S., 1999. Flux and fate of fluvial sediments leaving large
islands in the East Indies. Journal of Sea Research, 41, 97-107.
Mitra, S., lower HudsDellapenna, T.M., on River estuaryDickhut, R sedim.ents: phM., 1999. Polycyclic aromysical mixing vs sedimatic ent geochemhydrocarbon distribution witistry. Estuarihine,n
Coastal and Shelf Science, 49, 311-326.
Mondon,gig J.asA. a, Nnd owak,sand flathea B.F.,d SodePlrgren, atycephalus basA., 2001. sensisPersist froment Torasmganicanian estuarine a pollutants in oysntd coasers tal watersCrassostrea .
Mar. Poll. Bull., 42(2), 157-161.
Neff, J.M., 1979. Polycyclic aromatic hydrocarbon in the aquatic environment: sources, fates and
biological effects. Aplied Science Publisher Ltd, Essex, UK, 262 pp.
Oanh, hydrocaN.T.K., Albinarbons from, D.O., Ping, selected cookstL., Wang, X.ove – fuel system, 2005. Emission of s in Asia. Biomparticulate and ass and Bioepolycyclnergy, ic arom28, 579-atic
0.59Oanh, N.T.Kparticulate m., Reutergåartter frdh, Lom.B., D domuestic cong, N.Tm., 1999bustion . Emof selecission of ted fuels. Epolycyclic aromnvironmatic hydrental Science aocarbons and nd
Technology, 33, 2703-2709.
Oen, A.M.P., Cornelissen, G., Breedveld, G.D., 2006. Relation between PAH and black carbon contents
in size fractions of Norwegian harbor sediments. Environmental Pollution 141, 370-380.
Okay, enrichmO.S., Donkin, ent on the bioaccP., Peters, L.D., umulation Livingstonof benze, o[a]pyrene aD.R., 2000. The nrod its effects on the blue mle of algae (Isochurysis gassel lbanaMytilus )
edulis. Environmental Pollution, 110, 103-113.

64

Ollivon, D., Garban, B., Chesterikoff, A., 1995. Analysis of the distribution of some polycyclic aromatic
hydrocarbons in sediments and suspended matter in the river Seine (France). Water, Air and Soil
Oros, PoD.R., llution, 81Abas, M.R.B., 135-152, Om. ar, N.Y.M.J., Rahman, N.A., Simoneit, B.R.T., 2006. Identification and
eApmplied Geission factors of mochemistryo, 21, 91lecular tracers9-040. in organic aerosols from biomass burnings: Part 3. Grasses.
Oros, D.R., Ross, J.R.M., 2005. Polycyclic aromatic hydrocarbons in bivalves from the San Francisco
estuary: Spatial distribution, temporal trends, and sources (1993-2001). Marine Environmental
Research, 60, 466-488. Page, S.E., Siegert, F., Rieley, J.O., Boehm, H-D. V., Jaya, A., Limin, S., 2002. The amount of carbon
Parameswaran,released from K., Nair, S. peat and K., Rajeeforest fires iv, K., n Indone2004. Imsia dupactring 1997. Na of Indonesiature 420, 61-65. n forest fires during the 1997 El
Nino on the aerosol distribution over the Indian Ocean. Advances in Space Research 33, 1098-
. 1031DAS SPEMPROV RIAU, 2005. IAK Jakarta Ke11 bijakan peAugust 2005, ngelolaan Agency fordaerah a the Assliran sungai Siessmak. Preseent and Application of Tnted at Woechnologyrkshop for ,
Indonesia.Pérez-Cadahía, B., Laffon, B., Pásaro, E., Méndez, J., 2004. Evaluation of PAH bioaccumulation and
DNA damage in mussels (Mytilus galloprovincialis) exposed to spilled Prestige crude oil.
Comparative Biochemistry and Physiology, Part C, 138, 453-460.
Poerschmann, J., Zhang, Z., Kopinke, F-D., Pawliszyn, J., 1997. Solid phase microextraction for
determPoeton, T.S., Stensel, ining the distribution H.D., Strand, S.E., of chemica1999. ls in aqueous mBiodegradation of polyaromatrices. Analytical Chatiemc hydrocarbons istry, 69, 597-600. by marine
Prahl, F.G., bacteria: EfCarpenfectter, R of so., 1lid pha983se . Poon delycyclic argradation omatickinetics. h Wydroactearbonr Research,s (PAH) ph 33(3), 868-ase asso880. ciations in
Washington Coastal sediments. Geochimica et Cosmochimica Acta, 47, 1013-1023.
Quah, E., 2002. Transboundary pollution in southeast Asia. World Development 30(3), 429-441.
Rappaoport, S.ccupationM., Wal exapoidyasunare to potha, S., lySercyclic arodar, B., matic h2004. Naydrocarbphthalene aons. Jonurnal of d its biomEnvironmarkers as mental Monitoringeasures of ,
6, 413-416.
Ravindra, K., Sokhi, R., Van Grieken, R., 2008. Atmospheric polycyclic aromatic hydrocarbons: source
attribution, emission factors and regulation. Atmospheric Environment, 42, 2895-2921.
RequePolynuclear aromjo, A.G., Sassen, R., McDonald, atic hydrocarbons (PT., Denoux, AH) as indicators G., Kennicof the source utt II, M.C., Brooks, Jand maturity .M., of marine1996.
), 1017-1033. stry, 24(10/11iGeochemcrude oils. Organic organocRibeiro, C.A.O., Vollaire, hlorine pesticides, PAH and Y., Sanchez-Chardi, heavy A., Rometals inche, H., 2005. Bioaccum the Eel (Anguilla anguilla) at the Caulation and the emffectsargue of
53-69. Toxicology, 74, Aquatic Natura Reserve, France. Richardson, B.J., Zheng, G.J., Tse, E.S.C., De Luca-Abbott, S.B., Siu, S.Y.M., Lam, P.K.S., 2003. A
(Percomna parison ofviridis) and sem polycyclic ari-permomeable atic hydrmemocbarbonrane devi and ces (petrSoleumPMDs) i hydrnoca Hong rbon uptake Kong coby mastal waters.ussels
Environmental Pollution 122: 223-227.
Richter, H., Howard, J.B., 2000. Formation of polycyclic aromatic hydrocarbons and their growth to soot
– a review of chemical reaction pathways. Progress in Energy and Combustion Science, 26, 565-
8.60Ricking, ComM.,p Kocarison h,of M., the mRaotard,rine Ar W., 2005. Orkona Basin witgah fnirc eshwaterpollutants in se sedimediment cores nts. Marine Pollution Bof NEu-Germlletin, 50,any:
Riddle, S. G., 1699-1705.Jakobe r, C.A., Robert, M.A., Cahill, T.M., Charles, M.J., Kleeman, M.J., 2007a. Large
PAHs detected in fine particulate matter emitted from ligh-duty gasoline vehicles. Atmospheric
, 8658-8668. nt 41eEnvironmRiddle, S. G., Robert, M.A., Jakober, C.A., Hannigan, M.P., Kleeman, M.J., 2007b. Size distribution of
trace organic species emitted from light-duty gasoline vehicles. Environmental Science and
Rockne, K.JTechnolo., Shor, gy 41, L.M., 7464-7471Young, L.Y., . Taghon, G.L., Kosson, D.S., 2002. Distribution sequestration and
release of PAHs in weathered sediment: the role of sediment structure and organic carbon
properties. Environmental Science and Technology, 36, 2636-2644.
Rossi, D.Journal T., Zof hChang, romN., atograph2000. Automy A, 88a5, 97-1ting solid-pha13. se extraction: current aspects and future prospects.

65

Rybicki, B.A., Nock, N.L., Savera, A.T., Tang, D., Rundle, A., 2006. Polycyclic aromatic hydrocarbon-
Ryder, A.G., Glynn, DNA adduct formT.J., ation in Feely, M., Baprostate carcinogenesis. Carwise, A.J.G., 2002. Chancer rLetter, 239, acterization 157-167. of crude oils using
Sabaté, J., Bayonafluorescence li, J.fetimeM., Solanas, A.M., 2001. Ph data. Spectrochimica otolActa ysis of PAHsPart A, 58, 1025-1037. in aqueous phase by UV irradiation.
re 44, 119-124.ospheChemSaco-Álvarez, Bellas, J., Nieto, Ó., Bayona, J.M., Albaiges, J., Beiras, R., 2008. Toxicity and
phototoxicity of water-accomodated fraction from Prestige fuel oil and marine fuel oil evaluated
by marine bioassays. Science of the Total Envrionment, 394, 275-282.
Samanta, S.K.,and biorem Singh, O.ediation. V.TREN, Jain, R.K.DS in Bi, 2002. Polycyotechnology, 20(clic arom6), 243-atic hydroc248. arbons: environmental pollution
Sargenti, S.R., McNair, H.M., 1998. Comparison of solid-phase extraction and supercritical fluid
extraction for extraction of polycyclic aromatic hydrocarbons from drinking water. Journal of
Microcolumn Separation, 10(1), 125-131.
Schauer, J.J., Kleeman, M.J., Cass, G.R., Simoneit, B.R.T., 2001. Measurement of emission from
Envpollution sironmenotal Scienurces. 3. Cce and1-C Tech29 noorgalogy, 35nic com, 17pou16-1728. nds from fireplace combustion of wood.
Schlautman, M.A., Morgan, J.J., 1993. Effects of aqueous chemistry on the binding of polycyclic
aromatic hydrocarbons by dissolved humic materials. Environmental Science and Technology, 27,
. 96961-9SchwarzenbacB., 2006. h, R.PTh., Esce Challenge her, B.I., Feof micropollutantnner, K., s in aHofstetter, quatic systemT.B., Johnss. Science, on, C.A., 313, 1072-von Gunten, 1077.U., Wehrli,
Sebaté, J., Bayona, J.M., Solanas, A.M., 2001. Photolysis of PAHs in aqueous phase by UV irradiation.
re 44, 119-124. ospheChemSee, S.W., Balasubramanian, R., Rianawati, E., Karthikeyan, S., Streets, D.G., 2007. Characterization and
fire epsource apportiisode. Envonmironment of paenrttal Scieniculate ce anmatter d Techno 2.5 μmlogy, 41, in Sum3488-3494. atra, Indonesia during a recent peat
Sharma, R.K., Hajaligol, M.R., 2003. Effect of pyrolysis conditions on the formation of polycyclic
aromatic hydrocarbons (PAHs) from polyphenolic compounds. Journal of Analytical and Applied
144.Pyrolysis 66, 123-Shemer, H., Linden, K.G., 2007. Photolysis, oxidation and subsequent toxicity of a mixture of polycyclic
aromatic hydrocarbons in natural waters. Journal of Photochemistry and Photobiology A:
, 186-195. try, 187isChemShi, Z., Tao, S., Pan, B., Fan, W., He, H.C., Zuo, Q., Wu, S.P., Li, B.G., Cao, J., Liu, W.X., Xu, F.L.,
Wang, X.J., Shen, W.R., Wong, P.K., 2005. Contamination of rivers in Tianjin, China by
polycyclic aromatic hydrocarbons. Environmental Pollution, 134: 97-111.
Shou, M., Ktausz, K.W., Gonzalez, F.J., Gelboin, H.V., 1996. Metabolic activation of the potent
carcinogen dibenzo(a,h)anthracene by cDNA-expressed human cytochromes P450. Archives of
Sicre, M-Abioc., Fgemernaistry andndes, M.B biophy., Pont, Dsics, 38(1), 20., 2008. Poly-1-207. aromatic hydrocarbon (PAH) inputs from the Rhône
PollutionRiver to the M Bulletine, 56diterra, 193nean S5-1942. ea in relation with the hydrological cycle: impact of floods. Marine
Silliman, J.E., Meyers, P.A., Eadie, B.J., 1998. Perylene: an indicator of alteration processes or precursor
materials?. Organic Geochemistry, 29(5-7), 1737-1744.
Simpson, C.D., Harrington, C.F., Cullen, W.R., 1998. Polycyclic aromatic hydrocarbon contamination in
marine sediments near Kitimat, British Columbia. Environmental Science and Technology, 32,
3266-3272.
Singh, R., Sram, R.J., Binkova, B., Kalina, I., Popov, T.A., Georgieva, T., Garte, S., Taioli, E., Farmer,
P.B., 2007. The relationship between biomarkers of oxidative DNA damage, polycyclic aromatic
hydrocarbon DNA adducts, antioxidant status and genetic susceptibility following exposure to
environmental air pollution in humans. Mutation Research, 620, 83-92.
Smedes, F., de Boer, J., 1997. Determination of chlorobiphenyls in sediments – analytical methods. Trend
16(9), 503-517. istry, in Analytical ChemSmith, L.E., Denissenko, M.F., Bennett, W.P, Li, H., Amin, S., Tang, M-S., Pfeifer, G.P., 2000.
atic hydrocarbons. Journal of the polycyclic aromtational hotspots by uTargetting of lung cancer mNational Cancer Institute 92(10), 803-811.
Soclo, H.H., Garrigues, PH., Ewald, M., 2000. Origin of polycyclic aromatic hydrocarbons (PAHs) in
Pollucoastal mtion Baulletinrine sedim 40e(5), nts: 387-396case studies i. n Cotonou (Benin) and Aquitaine (France) areas. Marine

66

Stolyhwo, A., Sikorski, Z.E., 2003. Polycyclic aromatic hydrocarbons in smoked fish – a critical review.
91, 303-311. istry Food ChemSugiura, K., Ishihara, M., Shimauchi, T., Harayama, S., 1997. Physicochemica properties and
biodegradability of crude oil. Environmental Science and Technology, 31, 45-51.
Suzumura, M., Kokubun, H., Arata, N., 2004. Distribution and characteristics of suspended particulate
matter in a heavily eutrophic estuary, Tokyo Bay, Japan. Marine Pollution Bulletin 49, 496-503.
of n, R., Mulder, T., 2003. Predicting the terrestrial flux a, S.D., HilbermSyvitski, J.P.M., Peckhamsediment to the global ocean: a planetary perspective. Sedimentary Geology, 162, 5-24.
Telli-Karakoçarom, atic hydrF., ocarbon (PTolun, L., HenkelmAHs) anann, B., d polychlKlimmori, nated C.,bi Okay, phenyls (PCBsO., Schramm) , K.-Wdistributions., in th2002. Polycyclice Bay of
Thorsen, W.A., Marmara sea: IzmCope, W.G., Shea, it Bay. EnviD., ronm2004. Bioaental Pollution, vailability of 119, 383-397. PAHs: Effects of soot carbon and PAH
source. Environmental Science and Technology, 38, 2029-2037.
Turner, A., Millward, G.E., 2002. Suspended particles: their role in estuarine biogeochemical cycles.
Urbe, I, RuaEstuarinne, Coastal and Sha, J., Application of solid-phaelf Science, 55, se ext857-883. raction discs with a glass fiber matrix to fast
determination of polycyclic aromatic hydrocarbons in water. Journal of Chromatography A, 778,
. 34537-3Valero-Navarro, A., Fernández-Sánchez, J.F., Medina-Castillo, A.L., Fernández-Ibáñez, F., Segura-
Carretero, A., Ibáñez, J.M., Fernández-Gutiérrez, A., 2007. A rapid, sensitive screening test for
Venkatesapolycyclic aromn, M.I., 1988. Ocatic hydrocacurrence rbaons nd applied tpossible o soAnurces of tarctic water. Cperylene in hemmosphearerine sedim, 67, 903-e910.nts – a Revie w.
Marine Chemistry, 25, 1-27.
Viganò, L., FarkasPCBs, and DDTs are re, A., Guzzella, L., Roscilated in an oli, C., Einverraticrse way o, C., 2007. Thto the size of a bente accumulation lehic avels of PAHsmphipod ,
(Echinogammarus stammeri Karaman) in the River Po. Science of the Total Environment, 373,
. 14531-1Vilanova, R.Mremote m., Feountarnáin ndez, lake watersP., Martí. Water nez, ReseaC., Grimrcalt, h, 35(16), J.O., 3916-3926. 2001. Polycyclic aromatic hydrocarbons in
Voice, T.so, lidWes-I (Thber Jre, ory W.Jand ., 1983. SBackgoraorpundtion of hydr). Water Research ophobic com17(10), 1pounds 433-1by sedim441. ents, soils and suspended
Wakeham, S. G., Schaffner, C., Giger, W., 1980b. Diagenetic polycyclic aromatic hydrocarbons in recent
sediments: structural information obtained by high performance liquid chromatography. Physics
Earth, 12, 353-363. istry of the and ChemWakehamsedim, S.G.,ent-II. Sc Comhaffner,pounds C., deriGiger, ved fromW., 1980 biogenic a. precursors duriPolycyclic aromatic hydrocarbonng early diagenesis. s in Geochimrecent lake ica et
Cosmochimica Acta 44, 415-429.
Wang, X. -C, Zhang, Y.-X., Chen, R.F., 2001. Distribution and partitioning of polycyclic aromatic
Marhydrocaine Pollutirbon (PAHs) on Bulletinin diffe 42r(1ent1), 113 size9-1149 fractions. in sediments from Boston Harbor, United States.
Wang, Z., Fiidentification ngas, M., Lambert, P., of the Detroit RiverZeng, G., mystery oil spill (2002). JournalYang, C., Hollebone, of B., 2004. ChromChaartography A 1038, acterization and
. 21401-2Wang, Z., Fingas, M., Page, D.S., 1999. Oil spill identification. Journal of Chromatography A 843, 369-
1.41Weber orJr,ga W.J.nic m, Leaboeuf, tter: insights E.J., Ydraowung,n from T.M., pol Huymang, W.,er sciences. 2001.Water Contam Researcinh,ant intera 35(4), ction 853-868.with geosorbent
Weber Jr, W.Jand sedim., McGients. 1. Cnley, P.M., Katz, onceptual basis and L.E., 1991. A equilibrium assessmdistributed reactivity ents. Enmodel vironmental Scifor sorption by ence and soils
Technology 26, 1955-1962.
Wenzl, T., Simon, R., Kleiner, J., Anklam, E., 2006. Analytical methods for polycyclic aromatic
Euhydrocaropean Unrbons ion. (PATrenHs) in fds in Anood analytical Chd the eemnviroistry, 25nm(7ent ), 716-72needed for new5. food legislation in the
Westerholmlight duty ve, R., Almén, J., Lihicles operate, H., Rad innnug, difeU., Rreont drisén, Å., ving c1992. Eoxhanditions:ust em a issions frchemomical and gasoline-fuebiologicalled l
characterization. Atmospheric Environment, 26B(1): 79-90.
Williampollutason, K.S., nt PAHs frPetty, J.D., Huckiom sedimnent pore s, J.N., Lebo,water J.A., emKaiser, ploying semE.M., ipermeable mem2002. Sequestration of prioritybrane devices.
re, 49, 717-729.ospheChem

67

Wise, S.A., Hilpert, L.R., Byrd, G.D., May, W.E., 1990. Comparison of liquid chromatography with
fluorescepolycyclic aromnce adetection atic hydrocanrbons id gas chromn environmatographyental sam/mass spectrples. Poolycycmelic Artry for tomhatic Coe detemrpmioundsnation of, 1(1),
81-89.
Wise, S.A., Schantz, M.M., Benner, B.A., Hays, M.J., Schiller, S.B., 1995. Certification of polycyclic
aromatic hydrocarbons in a marine sediment standard reference material. Analytical Chemistry,
Witt, G., 67, 111995. 71-1178. Polycyclic aromatic hydrocarbons in water and sediment of the Baltic Sea. Marine
237-248. , 31(4-12), lletinuPollution BWitt, G., Siegel, H., 2000. The consequence of the Oder Flood in 1997 on the distribution of polycyclic
11arom24-1131. atic hydrocarbons (PAHs) in the Oder River Estuary. Marine Pollution Bulletin, 40(12),
Woodhead, R.J., Law, R.J., Matthiessen, P., 1999. Polycyclic aromatic hydrocarbons in surface sediments
around England and Wales, and their possible biological significance. Mar. Poll. Bull. 83(9): 773-
0.79Xia, X.H., Yu, H., Yang, Z.F., Huang, G.H., 2006. Biodegradation of polycyclic aromatic hydrocarbons
in the natural waters of the Yellow River: Effects of high sediment content on biodegradation.
re, 65, 457-466.ospheChemXue, W., Whydrocaarsharbons anwsky, D., d DNA 20damage: A re05. Metabolic activaview. Toxition cology aof nd Applied Pharmpolycyclic and heterocyclic aromacology, 206, 73-93.a tic
Yamashita, N., Kannan, K., Imagawa, T., Villeneuve, D.L., Hashimoto, S., Miyazaki, A., Giesy, J.P.,
2000. Vertical profile of polychlorinated Dibenzo-p-dioxins, Dibenzofurans, Naphthalenes,
BipheBay, Japanyls, Poln. Environmycyclic aroental Sciematic hydrnce and ocarTechnolbons, aogy,nd al 34, 3560-kylphenols in a se3567. diment core from Tokyo
Yan, J-H., You, X-F., Li, X-D., Ni, M-J., Yin, X-F., Cen, K-F., 2004. Performance of PAH emission from
bituminous coal combustion. Journal of Zhejiang University Science 5(12), 1554-1564.
Yang, H-H., Chien, S-M., Lo, M-Y., Lan, J.C-W., Lu, W-C., Ku, Y-Y., 2007. Effects of biodiesel on
emissions of regulated air pollutants and polycyclic aromatic hydrocarbons under engine durability
testing. Atmospheric Environment, 41: 7232-7240.
Yang, H-H., Jung, R-C., Wang, Y-F., Hsieh, L-T, 2005. Polycyclic aromatic hydrocarbons emission from
ospheric Environment, 39, 3305-3312. r furnaces. Atmjoss papeYang, H-H., Lee, W-J., Chen, S-J., Lai, S-O., 1998. PAH emission from various industrial stacks. Journal
of Hazardous Materials 60, 159-174.
Youngblood, W.W., Blumer, M., 1975. Polycyclic aromatic hydrocarbons in the environment:
homologous series in soils and recent marine sediments. Geochimica et cosmochimica Acta 39,
1303-1Yunker, M.B., Macdonald, R314. .W., Goyette, D., Paton, D.W., Fowler, B.R., Sullivan, D., Boyd, J., 1999.
Natural and anthropogenic inputs of hydrocarbons to the Strait of Georgia. The Science of the
Total Environment, 225, 181-209.
Yunker, M.B.,the Fraser Ri Macdonalver d, R.basin: a W., Vingarzacritical apprain, R., Mitcsal of PAH ratio as indicahell, H., Goyette, D., Sylvesttors re, of PAH S., 2002. PAHs insource and
composition. Organic Geochemistry 33, 489-515.
Zakaria, M.P., Horinouchi, A., Tsutsumi, S., Takada, H., Tanabe, S., Ismail, A., 2000. Oil pollution in the
Straits of Malacca, Malaysia: Application of molecular markers for source identification.
Environmental Science and Technology, 34, 1189-1196.
Zhang, Y., Tao, S., 2009. Global atmospheric emission inventory of polycyclic aromatic hydrocarbons
(PAHs) for 2004. Atmospheric Environment, 43, 812-819.
Zhou, J.L.,Rowlan Filemd, S.a, n, T.1998.W., FluoraEvans, nthene aS.,n Donkid pyren, P.,ne in the susLlewellyn, C., Reapended dparticles man, J.W.,and surface Mantoura, sedime R.Fnts of.C.,
the Humber Estuary, UK. Marine Pollution Bulletin, 36(8), 587-597.
Zhou, J.L., Fileman, T.W., Evans, S., Donkin, P., Readman, J.W., Mantoura, R.F.C., Rowland, S., 1999.
The partition of fluoranthene and pyrene between suspended particles and dissolved phase in the
3Hum05-321. ber Estuary: a study of the controlling factors. The Science of the Total Environment 243,
Zielinska, B., Sagebiel, J., Arnott, W.P., Rogers, C.F., Kelly, K.E., Wagner, D.A., Lighty, J.S., Sarofim,
A.F., and gaPalmsolineer, G., 2004. vehicle emissions. Phase and size distEnvironmental Scienceribution of and Tecpolycyclic aromhnology,atic hydr 38, 2557-2567.ocarbons in diesel

68

IV.DISTRIHYDROCARBONS (PBUTION AND SOURCE OF POLYCYCLIC AROAHs) IN SURFACE SEDIMENTS FROM THE MATIC
SIAK RIVER, ITS ESTUARY AND THE ADJACENT COASTAL AREA INDONESIA OVINCE,ROF RIAU P

er* and Christine Jose** zMuhammad Lukman*, Wolfgang Bal *Marine Chemistry Working Group, DeLeobener Strasse, 28359 partment of BiBremen, Germany ology/Chemistry, University of Bremen,
**Department of Chemistry, University of RiRiau, Indonesau, Jl. Siia mpang Baru Panam, 28293 Pekanbaru,

AbstractThe 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 – 63μm; 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
esidential and industrial areas. of rysignificant signatures in the vicinit u Coast ; Ria; Estuarywords: PAHs; Sediment; Siak RiverKey

BMITTED UMANUSCRIPT PREPARED TO BE S

(TABLES MENTIONED IN THIS MANUSCRIPT ARE PROVIDED IN APPENDIX 4: p.131-133)

69

n Introductio4.1.

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,
petroleum products (Requejo et al., 1996; de oil and its e a substantial fraction cru constituttheyWang 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
PAHs experienced bio-concentration and bio-ated food in which inption of contamconsum 5; Ribeiro et al 2005; Bai et al., 2009).al., 200magnification, and inhalation (Hellou et 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 Niño
age of ca. 6.8 itted up to 2.57 Gt Carbon in 1997 during the dam1998), which emevent (1997/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
ass burnings. During another are inevitable products of peatland and biomet al. 2004). PAHs 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
s expected that peatland and biomass burning Beijing, China (Zhou et al., 2005). Thus, it can bein 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
undertaken. not been comprehensivelySumatra has 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 μg 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 – 63μm) or fine (mud: <63μm), is strongly related
of environmental conditions. g the state PAH-geosorbent interactions reflectinto specific 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
Ghosh et al., 2000,al 2001;pson et al., 1998; Wang et (e.g. Prahl & Carpenter, 1983; SimRockne 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.,
portance of the fraction <63μm in assessingal. (2002) revealed the imesworth et 1996). Charlthe distribution of PAHs in areas distant from direct input, and vice versa.
ine the PAH distribution between two size fractions of aimed (1) to examThis studysurface sediments from the Siak river, its estuary and the adjacent Riau coastal areas of Riau,
) to understand the role of the possible sources; and (3Sumatra, Indonesia; (2) to appointsedimentary organic matter for each fraction in PAH distribution, for which the very
appear to be especially suited. ic-rich condition of the Siak river systemhum

Study Area and Methods 4.2.

Study Area & sampling locations 4.2.1. Tapung Kanan tributaries of the the upstreamThe study areas cover the Siak River fromand the Tapung Kiri down to the mouth of the estuary; it further includes the coast extending
me oil ridges are Selat Panjang where sohern part of the oil harbour Dumai to the soutfrom and drain a large area stretch out over 300 kmrysituated (Fig. 1). The Siak River and its estuaof lowland and peat swamps within various landscapes, including huge palm-oil plantations,
rainforests, small urban centres, the capital city of Pekanbaru, a pulp and paper factory, and oil
refineries near the Siak mouth. During 2004 to 2006, four expeditions were carried out to take
stations. m a total of 27 ples frosamWith regards to potential PAH sources, the study areas are affected by frequent events of
dense smog from commonly practiced agricultural/biomass burnings and forest/swamp fires,
which are significant contributors to health problems in the region. (e.g. Davies & Unam,

71

m as well as from routine river-boat transports ion, oil discharges fro1999; Quah 2002). In addite y related activities (production, transportation and disposals of residues) aroil industrobservable.

SuamatrAISNEINDO

S269S226S227
S228S267
66S 2253S03S2251S 250S13S283S1232S24S1143S145S

10S12S4SS110405S116
S20S24S35

e map of the sampling stationsh. T Fig. 1

Sample Collection and Fractionation4.2.2.The samples were collected directly from a small vessel using a sediment grab sampler.
They were immediately homogenized with a stainless scoop before being placed in closed
aluminium jars. During homogenization, foreign objects such as big plant sticks, stones or any
other synthetic waste were removed. The samples were kept cool (ca. 4oC) during transported to
oment. Size-C) and stored until further treat were frozen (-20the laboratory, where theyfractionation was carried out by wet sieving to get the sand/coarse fraction (2mm - 63 m) and
the mud/fine fraction (< 63 μm after Udden-Wentworth scale).

thods eAnalytical M4.2.3. PAH Determination4.2.3.1. selected by US EPA PAHs priority pollutantsles were analyzed for 16 pThe samacenaphthene (ACEN), fluorene lene (ACYN), including naphthalene (NAPH), acenaphthy(FLU), phenanthrene (PHEN), anthracene (ANTH), fluoranthene (FLA), pyrene (PYR),
benzo(a)anthracene (BaA), chrysene (CHRY), benzo(b)fluoranthene (BbFLA),
H), rene (BaP), dibenzo(a,h)anthracene (DANTbenzo(k)fluoranthene (BkFLA), benzo(a)pyrene (IPYR). Baseline separation and 3-c,d)pylene (BPERY) and indeno(1,2,perybenzo(g,h,i)

72

n (250 x 4.6 reverse phase RP-C18 colum on a tes were performedquantification of these analymm, 5μm, BAKERBOND, J.T. Baker Inc) by using a high performance liquid chromatograph
(HPLC LKB 2249 Broma) with ultraviolet (2151 Variable Wavelength Monitor, LKB Bromma)
a obile phase was Packard 1046A). The mors (Hawlett-and programmable fluorescence detectcombination 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
nutes. itotal of 45 mSample extraction and work-up procedure were as follows. 10 g of the sediment fractions
D10), ne (PHEN standards: d10-phenanthrespiked with three surrogate perdeuterated PAH were odified lene (PERY D12), and extracted in Soxhlet-mD10) and d12-peryd10-fluoranthene (FLA 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)
evaporator to was removed byane/hexane. The excess solvent of the clean extracts ethdichloromca. 1 mL. Then, the extracts were subject to solvent exchange into ACN for HPLC analysis.
hane and etHPLC grade acetonitrile and analytical grade solvents (acetone, dichloromhexane) 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
plish the procedurale used to accomUV detection. The three perdeuterated surrogate PAHs werefficiency, 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%),
D10 and PER69.4% to 141% (m = 97.5%), and froY D12 with their relative standard m 73.9% to 121% (m = 94.6%) for for PHEN deviations (RSD) of 15.2%, 14.6% and 12.6%. D10, FLA

Determination of Sedimentary Organic Matter 4.2.3.2.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

Results & Discussion4.3.

t fractions Geochemistry of sedimen4.3.1. Organic carbon contents (OC) greatly varied from 0.01% to 24% by weight in the sand
fraction, but only slightly in the mud from 0.34% to 3.70% (Table 1, p. 131). In general, the
coarse fraction contained higher OC, but the fraction contributed less than 25% to the bulk
sand fraction such -weight. It indicates the presence of organic-rich particles in the ent drymsedias wood remnants, fragmented plant debris and black particles which were apparently abundant.
tween locations suggests a relevance of localA great variation of OC in the sand fraction beinputs. Coarse estuarine sediments had higher OC than both river and coastal sediments,
particularly the station S142 (24%) was characterized by a considerable presence of black
particles. The highest OC in the river was observed at S42 (14%) between Pekanbaru city and
ud fraction varied less betweenthe Perawang industrial area. In contrast, the OC content in the m decreased toward the coast. locations and The C/N ratios (Table 1) suggest dissimilar sources of organic matter between the
fractions. The 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 &
Goi, 1997). High percentages of terrestrial organic matter were found in the sand fractions
with median C/N ratio of 19.4, 12.8 and 31.8 for the river, estuary and the coast, respectively.
e fine fraction in the river hmedian ratios were about two-fold higher than those of tThese sediment ( 9.1) and in the coastal sediments (14.3). However, C/N ratios of both sand and mud
fractions of the estuarine sediments showed relatively similar values with the mean of 14.
Higher C/N values (>20) are commonly associated with terrestrial plants, thermal degradation
of biomass, or peat (Holtvoeth, 2004, Pillon et al., 1985). On the other hand, a lowered C/N
ratio in terrestrial OC is often tied to decomposition processes such as humification and
mineralization (e.g. Zech et al., 1997; Holtvoeth et al., 2005). Furthermore, a partial retardation
high ON contents in resulted in relativelyc nitrogen remineralization could haveof the organiarable patterns of the C/N ratio pmthe organic-rich sediment (e.g. Balzer et al., 1998). Cobetween the sand and mud fractions were confirmed from similar peatland system of the
Mahakam Delta in Borneo (Pillon et al., 1986). The lower C/N ratio in the fine fraction of the
Mahakam Delta sediments was related to high percentage of hydrolysable materials represented
by amino acid and ammonium which might be considered of animal origins rather than of
ud fraction suggest up, low OC and C/N ratios in the m mterrestrial higher plant sources. To su mud fraction was different from that of the sand fractionof organic matter in the pe that the tywhich is associated with terrestrial plant debris, peat and thermal degradation of biomass (black

74

land abrasion during high carbon). These sources were likelyprecipitation. to reach the aquatic environment through soil washout or

Content and Distribution of PAH 4.3.2.The contents and distribution of the 16 PAHs (expressed as PAHs) in the sediments
from the three different environments are summarized in Table 2 (p. 132 see also Fig. 2). Owing
to a low mud fraction ( 2%), river stations of S104, S105 and S35 were analysed only for the
s mentSiak river, estuarine and coastal sedisand fraction. The PAHs in the sand fraction of the range from 164 to 5474 (median=556) ng g-1 d.w., 208 – 3913 (425) ng g-1 d.w., and 594 – 2495
(1142) ng g-1 d.w., respectively. While in the mud sediment, corresponding contents varied from
319 to 1143 (521) ng g-1 d.w., 126 to 584 (468) ng g-1 d.w., 443 to 1314 (633) ng g-1 d.w. The
highest PAHs content (>5000 ng g-1 d.w.) in the sand fraction was found at S42 in the river,
followed by S138 in the estuary (~4000 ng g-1 d.w.), S253 and S269 in the coast (>2000 ng g-1
d.w.). In the mud fraction, the highest PAHs contents (1000-1300 ng g-1 d.w.) were observed
at S42 in the river and S269 and S226 in the coast. The mud fraction of the estuarine samples
with a mean content of 410 ng g-1 d.w. had intermediate PAHs concentrations, which were not
appreciably different between sampling locations. The PAHs were generally about two times
higher in the sand fraction. Sometimes, the PAHs concentrated up to four times higher in the
es higher S232 (coast) , and even to seven timoast) and ver), S250 (csand fraction e.g. at S42 (riat S138 (estuary) suggesting the existence of high affinity organic matter for PAHs associated
with the sand fraction. Enriched PAH contents in the coarse/sand fraction were also reported
2001; s (e.g. Oen et al., 2006; Wang et al., stem other riverine, estuarine and coastal syfromAhrens & Depree, 2004; Rockne et al., 2002; Yang et al., 2008). These studies figured out the
and black carbon in role of carbonaceous geosorbents such as coal-/wood-derived particles re PAHs in the sand fraction. osorbing m

75

6000

5000

40003000 (nsAHP).w.d g/g2000

1000

nSaddMuklBu

04S 2S 1010S 2S 104S 1055S 361S 12S 4S 145S 143S 142S 138S 134S 252S 125S 250S 251S 269S 226S 227S 228S 267S 266S 253S 230S 231S 232
RiverEstuaryCoast
Fig. 2and the. Distri coastalbution of PAHs areas. Stations are ain sand anrranged mud d downstreamfractions from the Siof surface sedimentak tributas fromries ove the r the estuSiak River, estuaryary to the
gion. coastal re the content for each ) was calculated for each station fromA bulk PAH content (PAHBulkfraction 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
concentration within the sand fraction alone. The spatial ghest PAH identified as having the hidistribution of PAHBulk as well as PAHs for the sand and the mud fractions did not show a
ng outh of the estuary area suggestibetween sampling locations towards the river mclear pattern ination was found in the contam2). However, the highest PAHvarious local inputs (Fig Bulkvicinity 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;
Pekanbaru (S42), the capital city of efore, the river sediment around Tolosa et al., 2004). Therthe 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
ver, for a general idea of the PAH level,ekground conditions. Howperformances and the bacrelevant 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
plus its adjacent coastal areas of China (Luo et al., 2006). Higher PAH the Pearl River Estuaryin sediments from this study than in areas from the neighboring countries are assumed to be due
peat burnings. These sources widespread, intense plantation and to greater inputs of PAHs fromproduced 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).

OC Relationship PAH & 4.3.3.The PAHs and the OC content in the sand fraction are generally correlated (R2 = 0.70,
) are treated s correlation, the S253 (coast), S269 (Dumai port), and S142 (estuary thinFig. 3). Iitted for this as outliers due to high PAHs coupled with low OC and vice versa, and thus omud mtent in the and the OC conregression. In contrast, there was no correlation between PAHs fraction. These results suggest that organic matter (OM) associated with the sand fraction has a
stronger affinity for PAHs. On the other hand, in the fine fraction PAHs was independent on
with the OM, or that the OMluctant to associate ethe OC content suggesting that PAHs were rgh for given PAHs content. hicontent was relativelyFurthermore, we figure out that there are actually two groups of the PAH-OC association
correlated (Fig. 4a), and not PAHs with <1% OC was regardless of the fractions. First, the second, PAHs with >1% OC was linearly correlated (R2= 0.78, Fig. 4b). The first type seems
do with the OC oa specific PAH-organic particle interaction which has nothing t to affirmcontent. It might be that PAH-particles came from the same sources entering the aquatic
systems. The second type supports the idea that PAHs in both fractions was controlled by its
OM content and properties. But, the association was in favor of the coarse-attached OM. As no
phasizes that the OM of ne fraction (Fig. 3), this type emcorrelation observed for the fiPAH-OC position which control the PAHs sequestration. The ource and com have different sboth fractionscoarse fraction-OM was most probably attributed to those from combustion-derived particles or
black carbon, vascular plant debris and peat, while the fine fraction-OM was derived mainly
from humification. The reluctance of PAH to associate with the fine fraction-OM is probably
due to less aromatic fraction of the OM structure stemming from highly degraded peatland. As
associations of PAH with the OM of the fine fraction occurs mostly as a direct function of fine

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 (<64μm) 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
yentered the aquatic environment favorablstems. First, the PAH integrated into the aquatic syat) vascular plant debris, or pePAH (i.e. black particles, for binding to the OM with high affinitym econd, the PAH-OM came together fro250, S232. S143, S138, Sas found in S42, S116, Ssimilar 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.
0006

0005

00040003).w.dg g/n (sHAP2000
S253: the Coast
S269: DumaiPort

0001

050

01

Sand Fraction
PAHs = 295.4*OC + 349.1
27.= 0R

Estuarine S142
Sediment
00510152025
)%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

0300A025020000150).w.d g/gs (nHAP500
0100000.

PAH vs OC <1%

0.10.20.3

PAH vs OC >1%

40.

y = 351.24x -128.98
R² = 0.78

5.0

B6000PAH vs OC >1%
050004000300).w.dg g/n (sHAP1000
y = 351.24x -128.98
2000R² = 0.78
00.02.04.06.08.010.012.014.016.0
)%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
position. and comt nconteRelative Composition of PAHs 4.3.4.The relative composition of PAHs was examined by ringed-group PAHs classified as 2
ring (NAPH), 3 rings (ACYN, ACEN, FLU, PHEN, ANTH), 4 rings (FLA, PYR, BaA, CHRY),
5 rings (BbFLA, BkFLA, BaP, DANTH), and 6 rings (BPERY, IPYR). The composition for
both the sand and the mud fractions was largely identical with 3 to 5-ringed PAHs being most
abundant. The 3-ringed PAH dominated the composition for both fractions ranging from 34.3%
to 72.7% in all aquatic environments, followed by 4-ringed and 5-ringed groups. The most
abundant compound of the 3-ringed group is acenaphthylene. On average, it made up to 30.3%,
the the river, position in the sand fraction from28.9%, and 67.7% of the relative individual comestuary and the coasts, respectively. It made up 28.6%, 32.9%, and 68.9% of the relative
eas. ud fraction for the respective arposition in the mmco

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.
the minated byre doHowever, the Siak tributaries of Tapung Kanan and Tapung Kiri Rivers we5-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
ak tributaries, in the estuary pound was particularly pronounced in the Sistations. This com(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
ound. If this is true, increased pmoccurring in the surrounded land could be the source of this cocontents of DANTH and other 5-ring PAHs could become signatures of peat-generated PAHs.
m of peat-generated PAHs froy) on profiles However, further investigations (field and laborator4- and 5-ringed PAH in the areas strongl this area are needed. Widespread distribution of ysuggests invasive pyrogenic non-point sources which were most likely introduced to the aquatic
environments through soil washout and atmospheric deposition.

Source Apportionment 4.3.5.

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
many studies make use of specific characteristics inant, the apportionment for the PAH in is domof low over high molecular weight ratio (LMW/HMW), and specific isomeric ratios such as
979; Budzinski et A/(BaA+CHRY) (Neff 1ANTH/(ANTH + PHEN), FLA/(FLA + PYR), Ba2000). Petrogenic origin from 002; De Luca et al., 2005; Soclo et al., al., 1997; Yunker et al., 2maturation 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
EN and FLU (Requejo et al., 1996). Hsubstances, PThe 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

0.26 and 0.10 (Requeojo et al., 1996). However, the boundaries respective ratios values of 0.03, 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
ean ± 1 ± 0.05 (m 0.the Bengkalis canal. The ratio of ANTH/(ANTH+PHEN) was respectivelystandard 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-
(> 65 ± 0.13, and 0.69 ± 0.17. High values of this ratio 48 ± 0.24, 0. 0.PYR) was respectivelyses, wood, or agricultural debris. The ratio of ass burnings such as gras0.5) indicate typical biomBaA/(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
it 0.35). (upper lim 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
the last severe outbreak of the El Niño. sincee areas particularlyoccurs frequently in thosAccordingly, 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,
rogenic PAHs pyseasons. The widespread signature of high rain and flood intensified during might also reflect the significance of atmospheric (wet/dry) deposition.
estuary However, the signatures of petrogenic PAHs were also observed in the river, theand the coast. The river sediments are to a great extent contaminated by petrogenic sources,
city Siak upper tributaries (S101) and around the capital observable in the which is particularlyouth of nd the m50), Dumai port (S269), a the Siak Kecil River (S2of Pekanbaru (S35, S116),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
also petrogenic signatures were production sites in Sumatra. Strong biggest oil-is one of thereported from estuarine and coastal sediments of the neighboring country, Malaysia (Zakaria et
al., 2002).

81

01.90.80.70.60.50.)YRHC +AaB (/ABa0.2
40.30.10.00.

Petroleum

Biomass Combustion

Combustion

Petroleum

Combustion

70.60.50.noitsubmCo
40.AN)NEHP +HNTA( /HT0.1Petroleum
30.20.00.0.00.10.20.30.40.50.60.70.80.91.0
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 ( ).

Conclusion 4.4. moderate to high level. The sand/coarse fractionments contained PAHs at The sedigenerally contained higher PAHs and OC content than did the mud/fine fraction. A PAH-OC
ylinear correlation was shown onle sand fraction. Enriched PAHs in the high-OC sand h by tmatter with high-fraction plus the linear correlation indicated the existence of particular organic affinity for PAHs, such as black carbon, vascular plant, and peat. The spatial distribution
outh. But, increased content of the PAHs was mshowed no clear pattern in distance to the river inant lecular weight was widespread predomogh mcentered at urban and industrial areas. The hiand the molecular ratios for source apportionment provide further evidences for pyrogenic
sources: biomass and petroleum combustions. PAHs were delivered to those aquatic system by
er transports. both land-water and air-wat

82

ments AcknowledgThis 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
ofour grateful to scientists and students from Universityextent supports. Also, we would like to camRiau, Indonepaigns and discussion. Furthermsia, and to SPICE German colleagues for their contributore, we appreciate the help of our colleaion during samgues Dipl. Epling ng.
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
s. constructive critics and commentnot least, we thank all reviewers for their ReferencesAgarwal, T., River, Delhi, IKhillare, P.S., ndia. EnvirShrionmdhar, V., 2006ental Monitoring a. nPAHs contamd Assessmination ient 123, n 151-166.bank sedim ent of the Yamuna
Ahrens, M.J., Depree, C.V., 2004. Inhomogenous distribution of polycyclic aromatic hydrocarbons in
different size and density fractions of contaminated sediment from Auckland Harbour, New
Zealand: an opportunity for mitigation. Marine Pollution Bulletin 48, 34-350.
Bai, Z., Hu, Y., exposure to Yu, H., Wu, N., You, polycyclic aromatY., 2009. Quic hydrocarbons on citizens antitative health risk assessment of iin Tianjin China. Bulletin nhalation
Balzer, EnW., viroHenmlder, ental CoW., Eppintamng, E., Lination anohsed Toxic, L., Otto, Sology, 83: 1., 1998.51-154. Benthic de nitrification and nitrogen cycling
at the slope and rise of the N.W. European Continental Margin (Goban Spur). Progress in
Oceanography 42, 111-126.
Baumard, P., Budzinski, H., Garrigues, P., 1998. Polycyclic aromatic hydrocarbons in sediments and
mussels of the western Mediterranean sea. Environmental Toxicology and Chemistry 17(5), 765-
6.77Boonyatumanond, R., Wattayakorn, G., Togo, A., Takada, H., 2006. Distribution and origins of
Thailandpolycyclic arom. Marinae Pollutic hydrocation Bulletinrbons 52(PA, 942Hs)-9 in 56. riverine, estuarine, and marine sediments in
Budzinski, H., Jones, I., Bellocq, J., Pierard, C., Garriques, P., 1997. Evaluation of sediment contaminant
by polycyclic aromatic hydrocarbons in the Gironde estuary. Marine Chemistry 58, 85-97.
CharlesMar. Poworth, M., ll. BuServill., 44: 14ce, M., Gibs21-1434. on, C.E., 2002. PAH contamination of western Irish Sea sediments.
Davis, S.J., Unam, L., 1999. Smoke-haze from the 1997 Indonesian forest fires: effects on pollution
and Mlevels, local clanagemiment 124ate, atm, 137-144.ospheric C O2 concentrations, and tree photosynthesis. Forest Ecology
De Luca, G.D., Furesi, A., Leardi, R., Micera, G., Panzanelli, A., Piu, P.C., Sanna, G., 2004. Polycyclic
aromatic hydrocarbons assessment in the sediments of the Porto Torres harbor (northern Sardinia,
Italy). Marine Chemistry 86, 15-32.
De Luca, G.D., Nature, distribution aFuresi, A., Micera, nd origin G., of polycyclic arPanzanelli, A., Piu, omatic hydrP.C., ocarPilobons (PAHs) i, M.I., Spano, N., Sanna., n the sediments of2005.
Olbia harbor (Northern Sardinia, Otaly). Marine Pollution Bulletin 50, 1223-1232.
Evans, K.M., Gill, R.A., Robotham, P.W.J., 1990. The PAH and organic content of sediment particle size
fractions. Water, Air, and Soil Pollution 51, 13-31.
Fang, M., Zheng, M., Wang, F., To, K.L., Jaafar, A.B., Tong, S.L., 1999. The solvent-extractable organic
conpounds in the Indonesia biomass burning aerosols – characterization studies. Atmospheric
Environment 33, 783-795.
Ghosh, U., association ofGillette, J.S., Luthy, R.G., polycyclic aromatic hydrocZare, R.N., arbons on20 har00. Microscale lbor sedimoecationt particles. En, characterization, nvironmental and
Hellou, J., Science & Technology 34, Steller, S., Leonard, J., Langille, M.A., Tre1729-1736. mblay, D., 2005. Partitioning of polycyclic
aromatic hydrocarbons between water and particles compared to bioaccumulation in mussels: a
Holtvoeth, harJ., Kolbour case. Marine Eonic, S., Wagner, nvironmT., 2005. ental Research 59,Soil organic m 101-117.a tter as an important contributor to late
Coquatesmornachimry seicadim Acta e69(8), 203nts of the tropical 1-2041. West African continental margin. Geochimica et

83

Horowitz, A.J., Elrick, K.A., 1987. The relation of stream sediment surface area, grain size and
composition to trace element chemistry. Applied Geochemistry, 2, 437-451.
IARC, 1987. IARC evaluations of Monogracarcinogephs on the enicity: an updating of Ivaluation Aof caRC Monograrcinogenic phs risks to humvolumeas 1 to 42, Lyns, Suppl. 7, on, IAoverall RC
Press. ICES,me 1997. thodsDeterm. In Rienation of port of the ICpolycyclic arES Advisoomryatic Commhydrittee oocarnbons (P the Marine AHs) inEnvi sedironmmeent, 1997. ICEnts: Analytical S
Cooperative Research Report 222, 118-124.
IPCC 2000. Land Use, Land-Use Change and Forestry, A Special Report of the IPCC. Cambridge
KakareUnika, S.V.versity P, Kukharcress, 377 hyk, T.I.pp (ava, 2003. PAilable onliH emission ne: http://www.ifrompcc the open .ch). burning of agricultural debris. The
Science of the Total Environmental, 308: 257-261.
Kalbitz, K.,nitrogen. Geyer, SOrgan., ic ge2002. Diochemiffestry 33, rent eff319-ects of 326.Agarwal, peat degradation T., Khillare, P.S., Shon dissolverid ordhar, V., ganic car2006. PAHs bon and
contamand Assessmination in baent 123,nk se 151-1dim66.e nt of the Yamuna River, Delhi, India. Environmental Monitoring
Karickhoff, S.W., Brown, D.S. and Scott, T.A. (1979). Sorption of hydrophobic pollutants on natural
Kimsedim, G.B., Maruya, ents. WaK.ter A., LeResearce, R.F., h 13, 241-Lee, J.248.-H, Koh, C.-H., Tanabe, S., 1999. Distribution and sources of
Bulletinpolycyclic arom 38(1), 7-a15. tic hydrocarbons in sediments from Kyeonggi Bay, Korea. Marine Pollution
King, A.BrightJ., Reon madmaan, J.W., rina, UK. MarineZhou, J.L., Pollution B2004. Dynamulletin 48, ic behavi229-239. our of polycyclic aromatic hydrocarbon in
Langmann, B., 2007. A model study of smoke-haze influence on clouds and warm precipitation formation
in Indonesia 1997/1998. Atmospheric Environment 41, 6838-6852.
Li, G., Xia, X., Yang, Z., Wang, R., Voulvoulis, N., 2006. Distribution and sources of polycyclic
Envaromironmenatic hydrocarbonstal Pollution in 144, 98the m5 – 993i. ddle and lower reaches of the Yellow River, China.
Luo, X-Jhydroca., Chen, rbons iS-Jn suspe., Mai, B-X., nded matter and sediYang, Q-S., Shmens from the pearl Riveeng G-Y., Fu, J-M., 2006. Polr Estuary anyd adjaccyclic aroment coastalatic
areas, China. Environmental Pollution 139, 9 – 20.
Magi, E., Bianco, R., Ianni, C., Di Carro, M., 2002. Distribution of polycyclic aromatic hydrocarbons in
the sediments of the Adriatic Sea. Environmental Pollution 119, 91-98.
Maruya, K.A., Risebrough, R.W. and Horne, A.J., 1996. Partitioning of polynuclear aromatic
hydrocarbons between sediments from San Fransisco Bay and their porewater. Environmental
Maskaoui, K., Science anZhou, d TechJ.nology 30L., Hong, H.S., Zha, 2942-2947. ng, Z.L., 2002. Contamination by polycyclic aromatic
hPollydrouticoarbonn 118,s 10in9 th-12e Jiu2. long River Estuary and Western Xiamen Sean, China. Environmental
Meyer, P.A., 1994. Preservation of elemental and isotopic source identification of sedimentary organic
matter. Chemical Geology 114, 289-302.
Miguel, A.H., Kirchstetter, T.W., Harley, R.A., 1998. On-road emissions of particulate polycyclic
anaromd Technology, 32atic hydrocarbons and , 450-455. black carbon from gasoline and diesel vahicles. Environmental Science
Neff, J.M.biological effe, 1979. Pocts. Applied Sclycyclic aromience Publisatic hydrocarbon in her Ltd, Essex, the aquatic eUK, 262 pp.nvi ronment: sources, fates and
Oen, A.M.P., Cornelissen, G., Breedveld, G.D., 2006. Relation between PAH and black carbon contents
in size fractions of Norwegian harbor sediments. Environmental Pollution 141, 370-380.
Page, S.E., Siegert, F., Rieley, J.O., Boehm, H-D. V., Jaya, A., Limin, S., 2002. The amount of carbon
Parameswaran,released from K., Nair, S. peat and K., Rajeeforest fires iv, K., n Indone2004. Imsia dupactring 1997. Na of Indonesiature 420, 61-65. n forest fires during the 1997 El
Nino on the aerosol distribution over the Indian Ocean. Advances in Space Research 33, 1098-
. 1031Pillon, P., Jocteur-Monrozier, L., Gonzalez, C., Saliot, A., 1986. Organic geochemistry of recent
equatorial deltaic sediments. Organic Geochemistry, 10, 711-716.
Prahl, F.G., Carpenter, R., 1983. Polycyclic aromatic hydrocarbons (PAH) phase associations in
Quah, E., Was2002. Tranhington Cosboundastal sedimary poellunttions. Ge inoc sohimuthieast ca et CosmAsia. ochimWorld Devieca Acta 47,lopment 3 1013-0(3), 1023.42 9-441.
ReadmaPetrolen, J.W., Fillmum and PAH contamann, G., Tolosa, I., Bination ofa the Blrtocci, ack J., SeaVil. Marileneuve, ne Pollution BJ.-P., Catinni, C., ulletin 44, 48-62.Mee, L.D., 2002.

84

RequePolynuclear aromjo, A.G., Sassen, R., McDonald, atic hydrocarbons (PT., Denoux, AH) as indicators G., Kennicof the source utt II, M.C., Brooks, Jand maturity .M., of marine1996.
crude oils. Organic Geochemistry 24(10/11), 1017-1033.
Ribeiro, C.A.O., Vollaire, Y., Sanchez-Chardi, A., Roche, H., 2005. Bioaccumulation and the effects of
organochlorine pesticides, PAH and heavy metals in the Eel (Anguilla anguilla) at the Camargue
53-69. Toxicology 74, Aquatic Natura Reserve, France. Rockne, K.J., Shor, L.M., Young, L.Y., Taghon, G.L., Kosson, D.S., 2002. Distribution sequestration and
prrelease of Poperties. EAnvironmHs in weatheental Science ared sendimd eTecnt: hnolthe role of ogy 36, 2636-se2dime644. nt structure and organic carbon
Ruttenberg, K.C., Goi, M.A., 1997. Phosphorus distribution, C:N:P ratios, and 13Coc in arctic,
temperate, and tropical coastal sediments: tools for characterizing bulk sedimentary organic
Sauer, T.C., Mmatter. Marinichel, J., Hayee Geology 139s, M.O., , 1Aura23-145. nd, D.V., 1998. Hydrocarbon characterization and weathering
of oiled intertidal sediments along the Saudi Arabian coast two years after the gulf war oil spill.
EnvironmSecco, T., Pellizzato, F., Sfrient International so, A., Pa24(1/2), 43-60.voni, B., 2005. The changing state of contamination in the Lagoon
of Venice. Part 1: organic pollutants. Chemosphere 58, 279-290.
See, S.W., Balsource apportiasubramonmanian, ent of paR., Rianarticulate wati, mE., atter Karthikey 2.5 μma n, S., in SumStreets, atra, Indonesia duriD.G., 2007. Characterization ang a recent peat nd
Simpson, C.Dfire ep.isod, Hare. Envirington, Cronm.ental ScienF. and Cullen,ce an W.R., d Techno1998. Plogy, o41, 34lycyclic aro88-349ma4. tic hydrocarbon contamination
in marine sediments near Kitimat, British Columbia. Environmental Science and Technology 32,
3266-3272.
Soclo, H.H., Garrigues, PH., Ewald, M., 2000. Origin of polycyclic aromatic hydrocarbons (PAHs) in
coastal marine sediments: case studies in Cotonou (Benin) and Aquitaine (France) areas. Marine
Pollution Bulletin 40(5), 387-396.
Tolosa, I., de Mora, S., Sheikholeslami, M.R., Villeneuve, J.-P., Bartocci, J., Cattini, C., 2004. Aliphatic
and aromatic hydrocarbons in coastal Caspian Sea sediments. Marine Pollution Bulletin 48, 44-60.
Wang, X. -C, Zhang, Y.-X., Chen, R.F., 2001. Distribution and partitioning of polycyclic aromatic
Marhydrocaine Pollutirbon (PAHs) on Bulletinin diffe 42r(1ent1), 113 size9-1149 fractions. in sediments from Boston Harbor, United States.
Wang, Z., Fingas, M., Page, D.S., 1999. Oil spill identification. Journal of Chromatography A 843, 369-
1.41Yang, Y., particle-bound Ligouis, B., pies, C., polycyclic aromGrathwohl, atic hydrocarbons P., Hofm(Pann, T., 2008. OccurreAHs) in a river flonce of coal and odplain soil. Environmcoal-deerived ntal
YimPolluti, U.H., Hong, S.H, on 151, 121-1Shi29.m , W.J., Oh, J.R., Chang, M., 2005. Spatio-temporal distribution and
characteristics of PAHs in sediments from Masan Bay, Korea. Marine Pollution Bulletin 50, 319-
6.32Yunker, M.B.,the Fraser Ri Macdonalver d, Rbasin: a .W., Vingarzacritical apprain, R., Mitcsal of PAH ratio as indicahell, H., Goyette, D., Sylvesttors of re, PAH S., 2002. PAHs insource and
composition. Organic Geochemistry 33, 489-515.
Zakaria, M.P., Takada, H., Tsutsumi, S., Ohno, K., Yamada, J., Kouno, E., Kumata, H., 2002.
Distribution of polycyclic aromatic hydrocarbon (PAHs) in rivers and estuaries in Malaysia: a
widespread input of petrogenic PAHs. Environmental Science and Technology 36, 1907-1918.
Zech, W.hum, Senesi, ification aN.n, Gugged minberger,neralization of s oG., Kaiser, K., leil organic mhmaann, J.tter in the tropics. , Miano, T.M., Geoderm1997. Fa 79, actors c117-161. ontrolling
Zhang, Z.L., Hong, H.S., Zhou, J.L., Yu, G., 2004. Phase association of polycyclic aromatic
hydrocarbons in the Minjiang River Estuary, China. The Science of the Total Environment 323,
71-86.
Zhou, J., Wang, T., Huang, Y., Mao, T., Zhong, N., 2005. Size distribution of polycyclic aromatic
hydrocarbons in urban and suburban sites of Beijing, China. Chemosphere 61: 792-799.
Zhou, J.L.sedime, Maskants fromoui, K., 2003. Daya Bay, China.Distribution Environmental of polycyclic aromPollution 121,atic hydr ocar269 – 281. bons in water and surface

85

V.WATERSPOLYCYCLIC OF THE AROMATICSIAK RIVER,HYDRO ITS CARBONSESTUARY IN AND SURFACETHE
COASTAL AREAS OF RIAU PROVINCE, INDONESIA:
DISTRIBUTION AND SOURCES

M. Lukman*, W. Balzer*, I. Becker*, C. Jose**, J. Samiaji**

*Marine Chemistry Working Group, DeLeobener Strasse, 28359 partment of BiBremen, Germany ology/Chemistry, University of Bremen,
** University of Riau, Jl. Simpang Baru Panam, 28293 Pekanbaru, Riau, Indonesia

Abstract

Polycyclic aromatic hydrocarbons (PAHs) were studied both in water solution and in suspended
astal areas of oriver, including its estuary and the cmatter (SPM) of the Siak particulate e EPA selection h dissolved 16 PAHs according to tSumatra, Indonesia. Concentration of(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
cific ent was estimated using speples. PAH source apportionmd particulate samthe water anisomer ratios in combination with the ratio of low and high PAH molecular weights. The
mass stems, but biorogenic sources were found in all water sysignatures of petrogenic and pyburning 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
of Pekanbaru, the industrial area Perawang north of the River, as well as close to the capital city ty. and Dumai ci Keywords: PAHs; Suspended Particulate Matter; Water, Siak River; Estuary; Riau Coast

MANUSCRIPT PREPARED TO BE SUBMITTED

(TABLES MENTIONED IN THIS MANUSCRIPT ARE PROVIDED IN APPENDIX 5: p.134-138)

86

n Introductio5.1.Contamination of polycyclic aromatic hydrocarbons (PAHs) in the river, estuary and
coastal waters has attracted high attention, not only due to their toxic and carcinogenic effects,
but also to their persistence, ubiquity and bioaccumulation. These multiply the potential risks
for human exposure (e.g. Shou et al., 1996; Bofetta et al., 1997; Hussain et al., 1998; Rybicki et
countries allowable concentration of PAHs are nyaal., 2006; Singh et al., 2007). Therefore, in mstrictly regulated for food and drinking water. PAHs refer to a group of arene compounds built
up by two or more fused aromatic benzene rings in various planar configurations of molecular
structures containing no heteroatom (Neff, 1979). These compounds have both natural and
anthropogenic origins. The latter refer to those generated by combustion processes, and are the
most significant due to various possible sources, mainly 1) biomass burning, for example slash-
and-burn agriculture (e.g. Kakareka & Kukharchyk, 2003; Oanh et al., 2005), 2) forest/swamp
fires (e.g. Olivella et al., 2006; Vila-Escalé et al., 2007), and 3) the combustion of fossil fuels
(e.g. de Abrantes et al., 2004, Zielinska et al., 2004). Furthermore, crude oil and its related by-
products (hereafter called petroleum) contain a significant aromatic fraction in which PAHs
equejo et al., 1996). Rion of crude oil (constitute the toxic port the local populationsatra, Indonesia is pivotal forThe Siak River in Riau province, Sum and the adjacent coastal areas, it is a water. Together with its estuary life and drinking for dailypotent fishing ground supporting ca. 2.5 million urban and rural inhabitants along the basin.
They also become a main shipping lane for economic importance mainly oil industry. The Siak
aquatic system significantly discharges humic-enriched blackwater plumes into the Malacca
no2009). There is currentlym et al., 2007; Siegel et al., Strait causing ocean acidification (Bauination, trations and distribution of organic contamavailable on the concenation informparticularly PAHs in these aquatic systems. On the other hand, relatively high level of PAHs
s on agricultural/biomass burningmm be anticipated for this region owing to widespread comayand severe outbreaks of forest/peat swamp fires ever since the El Nino 1997 episode in Sumatra
al. (2007) atra See et in SumDuring a severe fire episode in 2005 (e.g. Page et al., 2002). of Pekanbaru that ai (north of the Siak River) and in Riau the capital cityobserved around Dumthe total 16 PAHs of the US Environmental Protection Agency (the 16 PAHs) priority pollutant
emitted from peatland burnings was ca. 561 ng m-3 and ca. 135 ng m-3, respectively. The latter
was even higher than typical values (ca. 116 ng m-3) of polluted urban areas of Beijing, China
2005).(Zhou et al., ources of PAHs in the ne the concentration, distribution and si aims to examThis studywater solution and in the suspended particulate matter (SPM) of the Siak River, its estuary and
the Riau coastal areas. PAHs are restricted to the 16 PAHs, since these compounds have been
ent. used in the framework of environmental assessm widely

87

Materials and Methods 5.2. Study Areas and Sampling Locations5.2.1., including several tributaries: the Tapung Kanan, ver stretch ca. 300 kmThe Siak Riiak , the S(Fig. 1). Along with its estuaryTapung Kiri (the upstreams) and Mandau Rivers catchment extents of about 1 million hectares, 10% of the total land area of Riau Province
(BPDAS, 2004), draining largely low-laying land characterized by large peatland, palm-oil
plantations and swamp forests. The Siak receives also discharges from many artificial canals.
. infall is usually between October and December (BPDAS, 2004)aThe highest r

amatrSuINDONESIA

317S318SS225S227S229Malacca Strait
DumaiS228
S226S267S324
266SBengkalis
Bukit BatuRiverS233
matraS124S230
15S2ONESIAS132,Siak SK133ecil RiverS316S125
S130, S126S314S231S128
S305S134
231S93S1PaStnrjaaitng
305S 301Sstream SegmentSiakSri Indrapura
PerawangS216S307
S9TapungKiriRiverS291S 115
370S7S1SS102205S10Pekanbaru
105SABSS218272C

Upstream Segment

Fig. 1.Siak Rive Map r wofas sam the sampled fpling loor three secations for gmwaents (ter (triadash-lnglesin)e and s boxeuss): p(Aende) d upstparticreamulate m; (B) Pekaatter (cycles).nbaru; (CThe )
wang.Pera 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
of anthropogenic pressures which follow. First, the Siak River was sampled for (i) the varietyare the Tapung Kanan and Tapung Kiri Rivers, which region of the Siak including upstreamrepresentative of agricultural sections surrounded by large palm-oil plantations, ii) the city
region around the capital Pekanbaru, and (iii) the downstreamal region enclosing the industri zone , the estuarya. Secondly Sri-Indrapurarea of Perawang and the population centre of Siak

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
il-ds, and to Panjang Strait in the south of the Siak river, where several offshore oSumatra Islanridges are located.

Sample Collection and Treatments 5.2.2.circa 1 meter mFive to ten liters of surface water (frodepth) were collected with a Niskin bottle, then poured in a pre-cleaned glass bottle, sealed, and stored until further treatment in the
laboratory. Within 8 hours after sampling, SPM was obtained by filtering one to five liters of
oC for 4 hours) Whatman GF/F filter in busted (at 400 river or estuarine water through pre-comtriple sets of 250-ml glass containers. The water was mixed thoroughly prior to filtration. For
the low SPM concentration. up to 10 L due to reached e of filtration coastal waters, the volumThen, the filters were wrapped in aluminum foil, and stored at -20 oC until further analysis. The
dissolved PAH extraction (see 5.2.4.). filtrate was pre-treated for

Procedures for particulate PAH Extraction & Work-Up 5.2.3. a clean-bench for 24 nPrior to extraction, the filters containing the SPM were air dried ing d10-phenanthrene (PHEN D10), d10-dards includiogate deuterated PAH stanhours. Surrfluoranthene (FLA D10) and d12-perylene (PERY D12) were spiked onto the filter. The filters
were then Soxhlet-extracted with an SoxTec HT6 extraction system using 50 mL of
ary mL with a rots were reduced to ca. 1 for 6 hours. The extractacetone/hexane (1/9; v/v)evaporator, and were subjected to a clean-up process in a 1:2 (w/w) deactivated alumina (10%) /
silica (3%) column. For elution the extract, 40 mL of a degassed 3/7 (v/v)
dichloromethane/hexane mixture was aspirated through the column. The extraction solvents and
e ICES Method (ICES, 1997). The clean extract was thstems are taken fromthe clean-up syagain reduced to ca. 1 mL by the evaporator, and further concentrated until it was dry under a
gentle stream of purified N2. Finally, 500 L of acetonitrile was added to the sample for HPLC
sis. analy

Extraction (SPE) system for dissolved PAH Solid Phase 5.2.4.Dissolved PAHs were obtained from the filtrate, by passing the filtered water through a
SPE cartridge (Chromabond® NH2/C18) obtained from Macherey-Nagel GmbH (Dueren,
filtrate in order of the e) was added to 0.5 to 1 L ). Methanol (2% of the filtrate’s volumGermanystandards (FLA D10 and PERY D12) were spiked to . The surrogate to enhance the recoverydetermine the procedural efficiency and reproducibility, and to enable the data correction from
were losses during extraction and work-up procedure. Prior to extraction, the cartridges anysequentially conditioned with 5 mL hexane and 10 mL methanol, then washed with ca. 100 mL

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
ptied, the cartridge was again washed with Milli-Q emple was er all of the sampressure. Aftwater, 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.
relatively The steps of the work-up procedure for the retained PAHs on the cartridge were 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
atography (HPLC). omliquid chr

Determination of PAH by HPLC UV/FLD 5.2.5.performed using high were aration and quantification of the 16 PAHs Baseline sepperformance liquid chromatography (HPLC LKB 2249 Broma) with a reverse phase RP-C18
HPLC column (Bakerbond 250 x 4.6 mm, 5μm obtained from J.T. Baker Inc, Phillipsburg,
FLD). The 16 d fluorescence detectors ( a couple of ultraviolet (UV) aned byUSA), detectPAHs include naphthalene (NAPH), acenaphtylene (ACYN), acenapthene (ACEN), fluorene
(FLU), phenanthrene (PHEN), anthracene (ANTH), fluoranthene (FLA), pyrene (PYR),
benzo(a)anthracene (BaA), chrysene (CHRY), benzo(b)fluroanthene (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 mobile phase was a
combination of an 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 for 45 minutes.
The quality of the analytical method was tested and confirmed. A mixture of 16 certified
PAH standards and the three surrogate deuterated standards (obtained from Dr. Ehrenstorfer
GmbH, Augsburg, Germany) were used to identify and quantify the analytes. HPLC-grade
acetonitrile and analytical-grade quality solvents (acetone, dichloromethane and hexane)
obtained from Fischer Scientific were used throughout the analytical procedures. Procedural
efficiency experiments for the SPE system were carried out prior to the sampling sequences
using a spiked-mixture of 16 PAHs and Milli-Q quality water. The individual recovery rates
rene (58%).)pywere greater than 74%, except for the naphthalene (47%) and benzo(aProcedural efficiency, reproducibility and data correction from losses during the extraction and
work-up procedures were confirmed by the surrogate deuterated PAHs (PHEN D10, FLA D10,
and PERY D12) which had been spiked into the sample prior to the extraction. The mean
E were 91.7% ± 6.98% (FLA es for the SPd deviation of the surrogat ± standarpercent recovery

90

SPM were 95.3% ± 10.1%, 96.8% ± 9.8%, the while for 8% ± 9.9% (PERY D12), D10) and 88.and 95.7% ± 8.9% for PHEN D10, FLA D10 and PERY D12, respectively.

Results and Discussion5.3.

Dissolved PAHs 5.3.1., riverineAHs) in the dissolved phase of the The concentration of total PAHs (Pestuarine and coastal waters ranged 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 (Table 1). The
PAHs in e concentration ofPAHs decreased about three-folds towards the coastal waters. Ththe rivers were markedly different between the stations, but not in the estuary and the coast. The
highest concentration in river water was detected in confluence of the Siak River and the
of , and of the capital cityMandau River (S301), the industrial area of Perawang (S305)Pekanbaru (S291). The high concentration at S301 was party attributed to the input of the black
gh PAH (unpublished data). The Mandau hidau River which contained relativelywater of ManRiver drains the water mostly from the catchment areas surrounded by large peat and plantation
areas. Increased material transport from surrounding peatland to the Mandau River has been
acknowledged for dissolved organic matter (e.g. Baum et al., 2007). The PAH concentration at
all sampling sites was considered high in comparison to aquatic systems around industrial and
an and European cities (Table 3) such as rivers in Tianjin China (e.g. urban centres in some Asi005), Qiantang River China (e.g. Chen et al., 2007), Seine River France (e.g. Shi et al., 2affectFernandes et ed byal., 1997). These Si PAH after forest fires (e.g. Olivella et al., 2006; Vila-ak concentrations were orders of Escalé et al., magnitude higher than waters 2007), and few-
folds above the concentration of PAHs in waters affected by oil spills (e.g. Gonzáles et al., 2006
and references therein). As to individual PAH, the relative composition of the PAHs in all water systems was
generally dominated by NAPH, ACYN, PHEN and FLA. These compounds are main
constituents of biomass burnings such as wood (e.g. Oanh et al., 2005), agricultural (e.g.
Kakareka, & Kukharchyk, 2003), forest fires (e.g. Vila-Escale et al 2007) and Sumatra peatland
om produced fr FLA is alsoburnings (See et al., 2007). However, high level of NAPH andpetroleum (diesel) combustion (e.g. de Abrantes et al., 2004), and was detected in water
polluted by oil spills (e.g. Baars et al., 2002). The ring composition pattern shows that 2-, 3- and
nificant. NAPH pling stations, while 5- and 6-rings are less sig4-ring are dominant in all samsignificantly enriched in the Pekanbaru (S291) which stem most probably from the city
observed in the waterpicallyPAHs is tywastewater discharges and ports. Increase in 2-ring around industrial areas and ports e.g. Qiantang River in China (Chen et al., 2007).

91

SPM PAHs in the 5.3.2.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
g. 2) taken at the upstream segment in 2004 showed that the contents of PAHs (see: inset Firemained 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
kewise the dissolved PAHs, NAPH, ACYN, attributed to the burnings. Liwas content of PAHs PHEN, FLA and PYR generally dominated the relative composition of individual PAH in all
nts. emseg

70000Upstream
000060000500004g g/ns (AHP).w.d20000
0000300001

0

aM 2004r

Wet SeasonDry Season
70000600005000040000.w.dg g/n (sHAP)
3000020000100000

Mar 04May 04Jun 04Aug 04Sep 04Jul 05

Sep 04Jul 05Mar 06
Upstream TributariesPekanbaruPerawang

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

suggest that land runoffs (lpeatland. The higher content in the wet season (2004) than in the dryand-water interfaces), by which burning residues were flushed out season (2005) might to
the River, were more significant sources of particulate PAHs than atmospheric deposition (air-
position oup comodification of the ring grmwater interfaces). However, there is a clear seasonal in the city of Pekanbaru and the industrial area of Perawang. The 3-ring PAHs (ACYN and
in both segments. ACYN and PHEN contribute season inant in the wet e very domPHEN) werca. 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.

Upstream S205
Pekanbaru S272
Perawang S216

A90The SiakRiver: Dry Season (Jul 2005)
80Upstream S205
70Pekanbaru S272
Perawang S216
6050)%( nioitsopmo CevitlaeR
403020100B90The SiakRiver: Wet Season (Sep 2004)
80Upstream S102
70Pekanbaru S105
60Perawang S115
50nioitsopmo CevitlaeR)%( 10
40302002 rings3 rings4 rings5 rings6 rings
Fig. 3. The relative composition of the ring groups of the PAHs in the Siak River during (a) dry and (b)
roup profiles. lustrate the ring-gdash lines ilwet seasons. The

Upstream S102
Pekanbaru S105
Perawang S115

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.
distribution towards the coast (Fig. 4). As to individual PAHs, the There is no clear trend of 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).
200010000180006000).wg d.g/n (sHA PeatlucitPar0
40002000

S139S140S137S134130 S126 SS132S124S133125 S128 SS225S226S227S228S229S267S266S233S251S230S231S232

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

The Estuary
The Coast
The Malacca Strait
9)22S(

gasoline combustion emit relatively high proportion of high molecular PAHs (e.g. Riddle et al.,
2-ring PAH in nestuarine SPM. Increase ithe 2007). NAPH was higher in the coastal than 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
lis and Dumai Strait) Bengkaouth (including mpronounced along the coast north of the river 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.
A45Dry Season (July 2005)The Estuary
40The Coast
35The Malacca Strait
9)22S(3025eR)%( niotisopmo Cevitla10
201550B45The Coast
40Dry Season (July 2005)Northern part
35Southern part
3025)%( nioitsopmo CevitlaeR5
20151002 rings3 rings4 rings5 rings6 rings
Fig. 5. The relative comprofiles. (a) the profiles in the estuary (mposition of the riedng groups ian valofu e, n=10), the cthe PAHs. The oasdash t (mlines illustrate the riedian value, n=11) and the ng-group
Malacca Strait (at S229), (b) the profiles in northern and southern (of the Siak River mouth) parts of the
coast. ng 62.5 to 694 e basis, the concentration of particulate PAHs ranged fromOn a volumL-1, 25.4 to 293 ng L-1, and 11.7 to 147 ng L-1 in the River, the estuary and the coast,

Northern part
Southern part

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
, China (Luo et al., 2006). were higher than the Pearl River and Estuary

080

060

s (ng/L)PAH040iculate Part

020

0

Siak River

Sak Estuary

CoastuRia

(nFig. 6.=11) C ando conceastal wntration aterof ts (nhe=12) partic. ulate PAHs on volume base (ng/L) in Siak River (n=12), estuarine

PAHs between SPM and Water Solution fDistribution Coefficient o5.3.3. plexlate and dissolved phases is driven by comof PAHs between particuDistribution particle-water interactions which involve physico-chemical properties of individual compounds
and the water properties especially particulate and dissolved organic matter as geosorbents for
hydrophobic pollutants (Schlautmann & Morgan 1993; Christl & Kretzschmar, 2001; Weber Jr.
understand factor controlling PAH phase distribution in the studied et al., 1991). In order to areas, distribution coefficient (KD, mL/g), that refers to as the ratio of PAH content (ng/g) in the
was examined for NAPH, L) water solution,SPM to its corresponding concentration (ng/mPHEN, FLA, BaP, BPERY as these compounds linearly correlated with PAH16, and represent
the ring groups. The KD values generally ranged from 2 to 5 on the logarithmic scale. The KD

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
solution water matter (DOM) in the y. Dissolved organic factors enhancing their solubilitenhances the solubility of PAHs (Liu & Amy, 1993; McGroddy & Farrington, 1995).
a6.0b8.0Samples from Mar 2006 (mean values)
07.5.0DNAPHOC6.0
K4.0PHENKRiver (n=5)
og LFLA Log5.0Estuary (n=3)
BaPCoast (n=3)
3.0BPERY4.0Koc = Kow
03.2.0

b8.0Samples from Mar 2006 (mean values)
07.HNAPPHENKOC6.0River (n=5)
FLA Log5.0Estuary (n=3)
BaPCoast (n=3)
BPERY4.0Koc = Kow
03.RiverEstuaryCoast3.04.05.06.07.0
Kg LoOWc8.07.0Log KOC=R -²0 =.137*D 0.62OC + 6.9
OC6.0Kog 5.0l4.0PBa3.00.05.010.015.020.0
DOC (mg/L)

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.
compound’s 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
was variable, and showed no fraction of organic carbon. The results showed that the KOCcorrelation 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

ans, 2002; Gustafsson et al., 1997). Koelm & black carbon (e.g. Jonkersmatter such as soot orHowever, 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).

Source apportionment 5.3.4.The identification of significant sources for anthropogenic PAH contamination plays a
critical role in water pollution control strategies, but contain a great challenge. This is due to the
fact that PAHs particularly the parent PAHs, have both petroleum and combustion sources,
ore, we applied several ratios which aree aquatic environment. Therefhwhich coincide in tcommonly used to distinguish petroleum from pyrolytic sources for the particulate PAHs. Those
of high-mratios can be classifiolecular weight substances ed in two categories: (i) the ratio of the sum( LMW/HMW); and (is of low-mi) the concentration ratios of olecular to the sum
specific parent isomers namely ANTH/(ANTH+PHEN), FLA/(FLA+PYR),
de Luca et al., nski et al., 1997; Yunker et al., 2002; Budzi1979;BaA/(BaA+CHRY) (Neff 2005; Soclo et al., 2000). Petrogenic origin is typically characterized by a high proportion of
LMW PAHs particularly those of 2-3 ring compounds. Therefore, LMW/HMW >1 indicates
petroleum sources. The specific isomer ratios as mentioned earlier are perceptive to distinguish
different combustion from petroleum sources due to different stability of the isomers with
increasing temperature during pyrolysis. PAHs from combustion processes have typical value of
ANTH/(ANTH+PHEN) > 0.1, FLA/(FLA+PYR) > 0.5, and BaA/(BaA+CHRY) > 0.35. On the
of < ng isomeric ratios cal values of those correspondipiother hand, petrogenic PAHs have ty2002). Any value falling between those nd < 0.2, respectively (Yunker et al., 0.4, a0.1, < determining values is usually considered as mixtures of petroleum and combustion sources.
The LMW/HMW ration ranged from 0.192 to 4.84, 0.137 to 11.4, and 0.26 to 2.54 in
suggest that in all studied . Those ratios clearlyectively and the coast, respthe river, the estuaryareas the PAHs stemmed from both petrogenic and pyrogenic origins. The influence of
petrogenic sources was especially pronounced at Pekanbaru and Perawang in the River, and in
ast including the blue water stations. The signature of petroleum opart of the cthe northern sources in all sampling stations was also detected in the ANTH/(ANTH+PHEN) with the mean
ratio of 0.02 ± 0.01 (mean ± SD), 0.02 ± 0.01, and 0.03 ± 0.01 in the River, the estuary and the
coast. The petrogenic PAHs were assumed to come from vessel discharges, port activities,
industrial and urban runoffs. Thin oil films on the water surface were often observed during the
ling campaigns. psam

98

BaA+CHRY) in all studied and the BaA/(On the other hand, the ratios FLA/(FLA+PYR) and petroleum ass burning rogenic sources, particularly biomportant pyareas show imcombustion. 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. PetroleumBiomass Combustion
01.90.Peat Burning
0.7Agricultural vehicles
SPM after forest debris
0.6firesWeat grasses
50.0.4Rice grasses
AaB( /ABa)YRHC + Enrika"muelortPe
0.3Oil spills "Tanker CharcoalBituminous coal
0.2Estuary S137
0.1Alaskan crude oil
0.8Dumailight-duty diesel notisumboCnotisumboC
0.0Estuary S139
40.Bituminous coal
40.0.3Agricultural
0.3Charcoaldebris
Oil spills
EN)HP +ANTH( /ANTH0.1oilvehicles
0.2"Tanker Enrika"Weat grasses
20.0.1Alaskan crude Dumailight-duty diesel
Peat Burning Rice grassesmuelortPe
00.0.00.10.20.30.40.50.60.70.80.91.0
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

Conclusion 5.4.

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
Hs were dominant in the both dissolved and particulate industrial areas. Two- to four-ring PAphases. 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
. port activities, urban and industry vessel, oil discharges from

ments Acknowledg

This studyFederal German Ministr isy part of the of Education, Science, Research and TechnologyGerman-Indonesian SPICE Project Cluster 3.1., funded by (BMBF, Bonn), a thend
gratitude to supported by the German scientists anAcademd students fric Exom University of Riau, Ichange Service (DAAD). ndonesia, theWe would like to show o crew of RSV ur
paigns Senangin, and to SPICE German colleagues for their contribution during sampling camviewers for their constructive critics and not least, we thank all reand discussion. Last but mments. co

References

ard, P., Budzinski, H., Garrigues, P., Sorbet, J.C., Burgeot, T., Bellocq, J., 1998.mBauorganisms in relation to Concentrations of PAHs (Polthose in sediycyclic Aromentsm and to trophic level. Marine Pollutiatic Hydrocarbons) in various marine on
12): 951-960.Bulletin, 36( C., Garriques, P., 1997. Evaluation of sediment Budzinski, H., Jones, I., Bellocq, J., Pierard,Chemcontamistryinant , 58: 85-by pol97. ycyclic aromatic hydrocarbons in the Gironde estuary. Marine
Countway, R.E., Dickhut, R.M., Canuel, E.A., 2003. Polycyclic aromatic hydrocarbon (PAH)
VA estuarydistributions and associati. Organic Geochemistryons with organic , 34: 209-224.matter i n surface waters of the York River,
Gigliotti, C.L., Totten, L.A., Offenberg, J.H., Dachs, J., Reinfelder, J.R., Nelson, E.D., Glenn aromatic hyIV, T.R., Eisenreich, S.J., 2005. Atmdrocarbons to the Mid-Atlantic east coast region. Enviospheric concentrations and ronmdeposition of ental Science andpolycyclic
Tsapakis, M., Apostolaki, Technology, 39: 5550-5559. M., Eisenreich, S., Stephanou, E.G., 2006. Atmospheric deposition
and marine sediMediterranean basin. Envirmeonmntation fluxes of polental ycyclica arScience and Technologyomatic hy, 40: 4922-drocarbons in the east4927. ern
Baars, B-J., 2002. The wreckage of the oil tanker ‘Erika’ – human health risk assessment of
Baum,beach cleanin A., Rixen, T., Samg, sunbathiiaji, J., 2007. ng and swimmRelevance of ing. Toxicologypeat draining Letters, 128, 55-68. rivers in central Sumatra for
Science 73, 563 – 570. the riverine input of dissolved organic carbon into the ocean. Estuarine, Coastal and Shelf
environmBofetta, P., Jourenkova, ental exposure to polN., Gustavsson, P., ycyclic1997. Cancer risk from aromatic hydrocarbons. Cancer Causes and occupational and
Control, 8: 444-472.BPDAS Indragiri Rokan.,language). Paper presented in the 1 2004. Physstical condition of Siak River water (in Indonesian SPICE Workshop Cluster 3.1., Pekanbaru,
Indonesia.

100

dissolved organic Brunk, B.K., Jirka, G.H., Lion, L.W., ma1997. Effects of salinittter coatings on the sorption of phenanthrene: Imy changes and the formation of plication for
ce and Technology, 31, 119-125. estuaries. Environmental Sciennpollutant trapping i C., Garriques, P., 1997. Evaluation of sediment Budzinski, H., Jones, I., Bellocq, J., Pierard,contaminant by polycyclic aromatic hydrocarbons in the Gironde estuary. Marine
58, 85-97.istryChemChen, Y., Zhu, L., Zhou, R., 2007. Characterization and distribution of polycyclic aromatic
hydrocarbon in surface water and sediment from Qiantang River, China. Journal of
Hazardous Materials, 141: 148-155.Christl, I., Kretzschmar, R., 2001. Relating ion binding by fulvic and humic acids to chemical
composition and molecular size. 1. Proton Binding. Environmental Science and
2511.2505-Technology, 35, hyde Abrantes, R., de drocarbons fromAssu light-dutynção, J.V., Pesquero, C.R., 2004. Em diesel vehicles exhaust. Atmospission of polycyheric Environment 38, clic aromatic
1641631- 0.de Luca, G.D., Furesi, A., Micera, G., Panzanelli, A., Piu, P.C., Pilo, M.I., Spano, N., Sanna.,
2005. Nature, distribution and origin of polycyclic aromatic hydrocarbons (PAHs) in the
sediments of Olbia harbor (Northern Sardinia, Otaly). Marine Pollution Bulletin, 50:
2.1231223-Fernandes, M.B., Sicre, M.-A., Boireau, A., Tronczynski, J., 1997. Polyaromatic hydrocarbon
(PAH) distributions in the Seine river and its estuary. Marine Pollution Bulletin, 34(11):
857-867. González, J.J., Viñas, L., Franco, M.A., Fumega, J., Soriano, J.A., Grueiro, G., Muniatugui, S.,
J.M., Alzaga, R., Albaigés, J., 2006. Spatial and ona, D., BayLópez-Mahía, P., Prada, temarea affected byporal distribution of dissolved/dispersed the Prestige oil spill. Ma aromatrine Pollution Bulletin, 53: ic hydrocarbons in seawater in the 250-259.
Guo, W., He, M., Yang, Z., Lin, C., Quan, X., Wang, H., 2007. Distribution of polycyclic
aromatic hydrocarbons in water, suspended particulate matter and sediment from Daliao
Gustafsson, Ö., Haghseta,River watershed, China. Chem F., Chan, C., Macfarlane, J., Gschosphere, 68: 93-104. wend, P.M., 1997. Quantification
of the dilute sedimentary soot phase: implications for PAH speciation and bioavailability.
203-209.d Technology 31, ental Science anEnvironmHeemkeorganic mn, O.P., satchel, icropollutants in suspended particulate B., Theobald, N., Wenclawiak, B.W., 2000. Temmatter of the River Elbe at Hamporal variability ofburg and
Toxicology, 38: the River Mulde at Dessau, Ger11-31. many. Archieve Environmental Contamination
Hussain, M., Rae, J., Gilman, A., Kauss, P., 1998. Lifetime health rissk assessment from
Environmexposure ofental Contam recreastional users to polination and Toxiycyccolology, 35: lic aromatic hy527-531. drocarbons. Archives of
ICES, 1997. Determination of polycyclic aromatic hydrocarbons (PAHs) in sediments:
AnalyEnvironmtical methods. ent, 1997. ICES In Report of the ICES AdvisorCooperative Research Repyort 222, 118-124. Committee on the Marine
aromatic hyJenkins, B.M., Jones, A.D., Turn, S.Q., Williamdrocarbons from biomass bus, R.rning. EnvironmB., 1996. Emission factors for polental Science and Technolycycogy,lic
9.246462-30, 2Jonker, M.T.O., Koelmans, A.A., 2002. Sorption of polycyclic aromatic hydrocarbons and
polychlorinated biphenyls to soot and soot-like materials in the aqueous environment :
Kakareka, S.V., Kukharchyk, T.I.,mechanistic considerations. Environm 2003. PAH emental Science anission fromd Technology, 36, the open burning of agricult3725-3734. ural
Law, R.J., debris. The SDawes, V.J.,c Woodhead, R.J., Mattience of the Total Environmental, 308: hiessen, P., 1997. Pol257-261. ycyclic aromatic
hy34(5): 306 – 322. drocarbons (PAH) in seawater around England and Wales. Marine Pollution Bulletin,

101

Liu, H., Amy, G., organic matter and polynuclear aro1993. Modeling partitioning and transportmatic hydrocarbons in groundwater. Envi interactions between naturalronmental
Liu, W.X., Dou, H., Wei, Z.C., ChScience and Technology, 27, 1553-1582. ang, B., Qiu, W.X., Liu, Y., Tao, S., 2009. Emission
characteristics of polyresidential coals in North cyclic aromatiChina. Science of the Totalc hydrocarbons from Environm coment 407, 1436-1446.bustion of different
hyLuo, X-J., Chen, S-J., Mai, B-X., drocarbons in suspended mYang, atter and sedimens Q-S., Sheng G-Y., Fu, J-M., 2006. Polfrom the pearl River Eycystuaryclic aromatic and
– 20. adjacent coastal areas, China. Environmental Pollution, 139: 9 McGroddyarom, atic hydrocarbons S.E., Farrington, J.W., 1995. Sedimin three cores from Boston Hent porewater partitioning of polarbor, Massachussetts.ycyclic
1542-1550.d Technology, 29, ental Science anEnvironmNeff, J.M., 1and biol979. Polyogical effects. Appcyclic aromatic lied Science hyPublisher Ltd, Essex, UK, 262 drocarbon in the aquatic environment: sources, fpp. ates
aromatic hyOanh, N.T.K., Albina, D.O., Ping, L., drocarbons from selected cookstove – fWang, X., 2005. Emuissionel systems in Asia. Bio of particulate and polycmass and yclic
Bioenergy, 28, 579-590. de las Heras, F.X.C., 2006. ., Mollet, J.M.,Olivella, M.A., Ribalta, T.G., de Febrer, A.RDistribution of polycyclic aroforest fires. Science of the Total Environment, 355: 156-166.matic hydrocarbons in riverine waters after Mediterranean
Page, S.E., Siegert, F., Rieleycarbon released from peat , J.O., Boehm, and forest fires in IndonesiH-D. V., Jaya during a, A., Limin, S., 2002. The am1997. Nature 420, 61-65.ount of
Reddy, C.M., Quinn,coastal waters and Point J J.G., 2001. Tudith Phe ond. MaNorth Cape oil spill. Hrine Environmydrocarbons iental Research 52, 445-461.n Rhode Isla nd
, M.C., Brooks, J.M., 1996.McDonald, T., Denoux, G., Kennicutt IIRequejo, A.G., Sassen, R., Polymarine crude nuclear aromatic hyoils. Organic Geochemdrocarbons (PAH) istry, 24(10/11): as indicators of the 1017-1033. source and maturity of
2007.an, M.J., Riddle, S.G., Jakober, C.A., Robert, M.A., Cahill, T.M., Charles, M.J., KleemAtmLarge PAHs ospheric Envrionment 41, 8658-detected in fine particulate matter emitted from8668. light-duty gasoline vehicles.
Rybickihy, B.A., Nock, N.Ldrocarbon-DNA adduct formation in ., Savera, A.T., Tang, D.prostate carci, Rundle, A., 2006. Polnogenesis. Cancer Letter, ycyclic arom239: 157-atic
167.Sargenti, S.R., McNair, H.M., 1998. Comfluid extraction for extraction of polycpariysclic aroon of solid-phase matic hydrocarbons fromextraction and supercritical drinking water.
Journal of MicrocolumSchlautman, M.A., Morgan, J.J., 1993. Effects of aqueous chemn Separation 10(1), 125-131. istry on the binding of
polycyclic aromatic hydrocarbons by dissolved humic materials. Environmental Science
and TechnologySee, S.W., Balasubramanian, R., Rianawati, E., Karthikey, 27, 961-969. an, S., Streets, D.G., 2007.
Indonesia durCharacterization and souring a recent ce apporpeat fire tionment of particulate episode. Environmental Scimatter  2.5 μm inence and Technology, 41, Sumatra,
Shi, Z., Tao, 3488-3494. S., Pan, B., Fan, W., He, H.C., Zuo, Q., Wu, S.P., Li, B.G., Cao, J., Liu, W.X., Xu,
China byF.L., Wang, polycy X.J., Shen, clic aromatic hydrocarbonsW.R., Wong, P.K., 2005. . Environmental Pollution, Contamination of rivers in Tianjin,134: 97-111.
Shou, M., Ktausz, K.W., Gonzalez, F.J., Gelboin, H.V., 1996. Metabolic activation of the potent
carcinogen Archives of biocgemistrydibenzo(a,h)anthracene b and biophysicsy, 38(1): cDNA-ex201-207.pressed hu man cytochromes P450.
sySiegel, H., Stottmstem-east Sueister, I., Reißmatra charmaacterisation of sources, estunn, J., Gerth, M., Jose, C., Samarine processes, and discharges into iaji, J., 2009. Siak river
s 77, 148-159. stemthe Malacca Strait. Journal of Marine SySingh, R., Sram, R.J., Binkova, B., Kalina, I., Popov, T.A., Georgieva, T., Garte, S., Taioli, E.,
polFarmycycer, P.B.,lic aromatic hy 2007. The relationship betwdrocarbon DNA adduceen biots, antioxidant status anmarkers of oxidative DNA damd genetic age,

102

susceptibility following exposure to environmental air pollution in humans. Mutation
92.Research, 620: 83-Soclo, H.H., Garrigues, PH., Ewald, M., 2000. Origin of polycyclic aromatic hydrocarbons
(PAHs) in coastal marin(France) areas. Marine Pollution Bulletin, 40(e sediments: case 5): 387-396. studies in Cotonou (Benin) and Aquitaine
Tremblay, L., Kohl, S.D., Rice, J.A., Gagné, J-P., 2005. Effects of temperature, salinity, and
dissolved humic substances on the sorption of polycyclic aromatic hydrocarbons to
estuarine particles. Marine Chemistry, 96: 21-34.
neutral organic on the sorption of e influence of salting out hTurner, A., Rawling, M.C., 2001. Tcompounds in estuaries. Water Research, 35(18), 4379-4389.
Vila-Escalé, M., Vegas-Villarubia, T., Prat, N., 2007. Release of polycyclic aromatic
comResearch, 41: 2171-2179.pounds into a Mediterranean creek (Catalonia, NE Spain) after a forest fire. Water
ena in 1991. Review Paper: Sorption phenomJ., McGinley, P.M., Katz, L.E., .Weber Jr, Wsubsurface systems: concepts, models and effects on contaminant fate and transport.
499-528. ch 25(5), Water ResearWilliamson, K.S., Petty, J.D., Huckins, J.N., Lebo, J.A., Kaiser, E.M., 2002. HPLC-PFD
determination of priority pollutant PAHs in water, sediment, and semipermeable
membrane devices. Chemosphere, 49: 703-715.
Witt, G., 2002. Occurance and transport of polycyclic aromatic hydrocarbons in the water
bodies of the Baltic Sea. Marine Chemistry 79: 49-66.
Yunker, M.B., Macdonald, R.W., Vingarzan, R., Mitchell, H., Goyette, D., Sylvestre, S., 2002.
source and comPAHs in the Fraser River position. Organic Geochemistrybasin: a critical appraisal 33, 489-515. of PAH ratio as indicators of PAH
Zhang, Z.L., Hong, H.S., Zhou, J.L., Yu, G., 2004. Phase association of polycyclic aromatic
hyEnvironmdrocarbons in the Mient, 323: 71-86. njiang River Estuary, China. The Science of the Total
Zhou, J., Wang, T., Huang, Y., Mao, T., Zhong, N., 2005. Size distribution of polycyclic
aromatic hydrocarbons in urban and suburban sites of Beijing, China. Chemosphere 61,
99.792-7Zhou, J.L., Maskaoui, K., 2003. Distribution of polycyclic aromatic hydrocarbons in water and
surface sediments from Daya Bay, China. Environmental Pollution, 121: 269 – 281.
Zhu L., Chen, Y., Zhou, R., 2008. Distribution of polycyclic aromatic hydrocarbons in water,
sediment and soil in driHazardous Materials 150, 308-316. nking water resource of Zhejian Province, China. Journal of
Zielinska, B., Sagebiel, J., Arnott, W.P., Rogers, C.F., Kelly, K.E., Wagner, D.A., Lighty, J.S.,
Sarofim, A.F., Palmer, G., 2004. Phase and size distribution of polycyclic aromatic
hydrocarbons in diesel and gasoline vehicle emissions. Environmental Science and
2567.2557-Technology, 38:

103

A COMPARISON OF POLYCYCLIC AROMATIC HYDROCARBONS VI. PEATLAND AQUATIC SYSTEM(PAHs) IN PEATLAND AND NON- SURFACE SEDIMENTS: A STUDY OF THE SIAK ESTUARY,SUMATRA, INDONESIA AND OF THE WENCHANG AND WANQUAN ESTUARIES, HAINAN ISLAND, CHINA

er*, Xiaoliang Tang*, zMuhammad Lukman*, Wolfgang Balang*** hChristine Jose**, Jing Z *Marine Chemistry Working Group, Department of Biology/Chemistry, University of Bremen,
Leobener Strasse, 28359 Bremen, Germany
**Department of Chemistry, University of Riau, Jl. Simpang Baru Panam, 28293 Pekanbaru, Riau,
a Indonesi***Institute of Estuarine and Coastal Research, East China Normal University, 3663 Zhongshan Road
North, Shanghai 200062, China

AbstractThe distribution of polycyclic aromatic hydrocarbons (PAHs) in two grain-size fractions
(coarse: 2 mm - 63μm) and fine: < 63μm) of sediments from peatland aquatic systems of the
Siak Estuary and Coast, Sumatra, Indonesia, was compared with those from non-peatland
The uaries, Hainan, China. Wenchang and Wanquan (WW/WQ) coastal eststems of sysediments were sampled in September 2004 and July 2005 for the Siak Estuary and Coast and in
December 2006 and July 2007 for the WW/WQ estuary, and analyzed for the PAHs of the US
ors. The PAHs in the peatland imetric detectPLC with UV and fluory list using HEPA prioritsystem are characterized by high contents of PAHs and organic matter in the coarse fraction.
The level of the US EPA priority pollutants (PAH) ranged from 125 ng/g d.w. to 1828 ng/g
d.w. (median m = 689 ng/g d.w.) in the coarse fraction, and from 88 ng/g d.w. to 426 ng/g d.w.
(m = 202 ng/g d.w.) in the fine fraction of the Siak sediments, while it ranged from 94.3 ng/g to
386 ng/g d.w. (m = 138 ng/g d.w.), and from 93.8 to 575 ng/g d.w. (m = 430 ng/g d.w.) in the
coarse and the fine fractions of the WW/WQ sediments, respectively. The concentration of
dissolved PAHs in WW/WQ coastal estuary was relatively low; the PAHs ranged from 7.36 to
and the coast ranged ed in the Siak estuarycontrast, the level of the PAHs dissolvng/l. In 16.2 from 121 to 619 ng/l. The sediment-water distribution coefficients (KD) values of the individual
PAH in the Siak estuary ranged in logarithmic value from 2.22 to 5.58 (median m = 3.37) for
= 3.01) for the fine fraction. On the other hand, in the coarse fraction, and from 1.53 to 5.03 (m3) in the coarse from 1.12 to 5.89 (m = 3.9 and coast it ranged greatlythe WW/WQ estuaryfraction, and from 2.58 to 5.85 (m = 4.40) in the fine fraction. It suggests that the high DOC
contents in the Siak water may sustain the PAHs in the water column impeding their sorption
onto suspended particles with subsequent sedimentation and incorporation into the sediments.
Keywords: PAHs; Sediment; Siak Sumatra, Wenchang/Wanquan Hainan, Estuary

MANUSCRIPT PREPARED TO BE SUBMITTED

(TABLES MENTIONED IN THIS MANUSCRIPT ARE PROVIDED IN APPENDIX 6: p.139-140)

104

n Introductio6.1.Studies of land-water interactions with respect to organic pollutants such as polycyclic
aromatic hydrocarbons (PAHs) are important in providing researchers with a better
understanding of how pollutants are transferred and distributed in aquatic compartments. This is
particularly true for very dynamic, transitional environments such as rivers, estuaries and coasts.
One of the most effective ways of understanding such systems is to evaluate sedimentary
pollution as the capacity of sediments to concentrate and retain heavy metals and organic
compounds results from complex geochemical factors such as grain size and organic matter
. hy et al. 1997), 1987; Lutcontent (Horowitz & ElrickPAHs are one class of organic contaminants that are relevant worldwide owing to their sources such as thropogenic on anies, their widespread and commtoxic/carcinogenic propertbiomass burning and fossil fuel combustion (Neff, 1979; IARC, 1987). This is particularly
important for Asia, which annually contributes more than 50% of the global PAH emissions
(520 Gigagrams in 2004), with PAHs stemming mainly from biomass burnings (Zhang & Tao,
2009). Since PAHs constitute up to 13% (by mass) of oils (Requejo et al., 1996), we can expect
that oil discharges into water bodies add significant amounts of PAHs into these systems (e.g.
to Signs of petrogenic PAH contamination dueMutairi, 2000; Wang et al., 2004). Saeed & Al- been recognized for the Malacca Strait, where the Siak product spills have alreadypetroleum 2000). ends (Zakaria et al.,estuary the context of estuaries draining nd to PAHs ile attention has been paiHowever, littpeatland which enhances its degradation such as that found in the Siak River estuary. Most
stems have focused on the land-aquatic syrticular peataland-water interaction studies of these pincreasing levels of dissolved organic matter exported into the sea due to land-use changes (e.g.
Baum et al., 2007; Siegel et al., 2009). Simultaneously, however, Sumatra's peatlands are
.g. Fang et al., 1999; See ete PAH sources due to widespread fires (considered to be potentialal., 2007). The degradation of Sumatran peatland (e.g. Page et al., 2002) has been of great
concern, not only for climate changes associated with the emission of up to 2.57 Gt of carbon
its al., 2002), but also due to Nino event of 1997/1998 (Page et e El recorded during fires in ths peatland al., (2007) revealed that Sumatra'utant. See et portance for the distribution of pollimburning events observed in the haze around Dumai and Pekanbaru, created ca. 100 to 600 ng m-3
of 16 PAHs from the list of US EPA priority compounds. This was even higher than levels
observed (ca. 116 ng m-3) for the polluted urban areas around Beijing, China (Zhou et al., 2005).
Baum et al (2007) estimated that peat-draining along the Siak River may cause levels of
-1. High DOC flux into rhigh as 0.3 Tg C ydissolved organic carbon (DOC) export reaching as aquatic systems can facilitate the water-borne transport of PAHs (e.g. Liu & Amy, 1993;
McGroddy & Farrington, 1995) and can hypothetically determine their fate in these aquatic

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
ental management. environmThis study aims to compare the PAH distributions in surface sediments for two
Wentworth size fractions: coarse (2mm – 63μm) and fine (<63μm). 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
(SPICE) program, a cooperative stemfor the Protection of Indonesian Coastal Marine Ecosy ch effort. The second is the “Land-Sea Interactions along Coastalman-Indonesian researGerEcosystems of Tropical China: Hainan (LANCET) program, a German-Chinese cooperative
content, their PAH ed were examined for their total PAH collectresearch project. The sediments 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
mn and prevent it content stabilize the PAHs in the water coluic humwhether a high dissolved to the sediment. ansfer trfrom

Materials and Methods 6.2.

Sample Collection and Fractionation Study areas, 6.2.1.The Siak estuary is one of the most pertinent peat-draining rivers in Sumatra. Comprising
of the Siak River and its tributaries, the Siak basin stretches over 300 km and drains a large area -oil plantations, ous landscapes, including huge palmlowland and peat swamps with varieas outh (Fig. 1a). In terms of PAH relevance, the ard oil refinery near the Siak mrainforests annt dense smog events caused both by the que decades-long records showing frestudied havecommon practice of agricultural/biomass burning and by naturally occurring forest and swamp
fires. In addition, oil discharges from routine river-boat transports as well as from oil industry
observable. yposals of residues) are readilation and disrelated activities (production, transportnan bodies on Haiatland water pical, non-peThe Wenchang and Wanquan coastal estuaries are tyIsland, China (Fig. 1b). These two aquatic systems are both surrounded by large agricultural
landscapes and human settlements. Although having relatively high PAH content in the
sediment, the two Hainan estuaries are not characterized by intense biomass burning events.
As part of the SPICE program, sediment samples were taken during 2004-2005 from a
. 1a). A full report on the and the coast (Figng the Siak estuarytotal of eight stations alo and the coastline was presenteds estuarytdistribution and sources of PAHs in the Siak River, iin a previous study (Lukman et al., manuscript being prepared for journal publication). Samples
from the Wenchang and Wanquan coastal estuaries were collected during the December 2006

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 (< 63μm) was collected by centrifuging the
remaining sample.

A

amatrSu

INDONESIA

35S2230S 250S231134SS138S232S

143S

107

ANICH

B

Wenchang

quannaW

anHain

TYI CAOBOCC02-1/07

074/BB

6WRB/0

nquanaWCoastal Estuary

Aquaculture

60K/70/8WW60H/WENCHANG WW10/07
CITYhangcneWCoastal Estuary

the WFig. 1enc. The mhaang and Wps of the samanquan Estuaries (black pling stations: (A) the Siak estuary (ccycles), Hainan, Chinaros. sed cycles), Sumatra, Indonesia; (B)

Determination of PAHs 6.2.2.Up Extraction and Working-6.2.2.1.fractions were spiked with three surrogate perdeuterated PAH ent the sedimUp to 10g of standards: d10-phenanthrene (PHEN D10), d10-fluoranthene (FLA D10) and d12-perylene
odified extractors (SoxTec) with solvents suggested t-m(PERY D12), then extracted in a Soxhleby 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-
During the cleanup process the extracts were to clean up the extract. er, was used extracted watvent in the clean of degassed 3/7 (v/v) dichloromethane/hexane. Excess solLeluted with 40 mextracts was removed by the evaporator, resulting in sample volumes of ca. 1 mL. Then, the
ance solvent exchange into acetonitrile (ACN) to allow high performextracts were subjected to sis. atography (HPLC) analyomliquid chrples with GF/F, and the filtrate e water samhng tDissolved PAHs were obtained by filteriwas 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 filtrate’s 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
up any losses during extraction and work-ity from and reproducibilprocedural efficiencyprocedure. The SPE cartridges were sequentially conditioned with 5 mL hexane and 10 mL
was ple Milli-Q water before using. After all of the samLmethanol, then washed with ca. 100 maspirated, 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.
has been suggested (e.g. Sargenti &stemyThe use of DCM for elution of PAH for SPE sMcNair, 1998). The elutes were reduced to a dry state by gently dried by N2 blow down, then
sis. LC analyACN for HPchanged into matrix was

HPLC Analysis6.2.2.2.The samples were analyzed for 15 out of the 16 PAHs priority pollutants listed by the US
ne uorene (FLU), phenanthrene (ACEN), flacenaphtheEPA, including naphthalene (NAPH), rene (PYR), benzo(a)anthracene (BaA),py(PHEN), anthracene (ANTH), fluoranthene (FLA), ne (BkFLA), sene (CHRY), benzo(b)fluoranthene (BbFLA), benzo(k)fluoranthechrybenzo(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.
rformed using a reverse phase pounds was peBaseline separation and quantification of those comRP-C18 column (250 x 4.6 mm, 5μm) 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),
min, and 100% ACN for 10 in.) for 20 ACN (a linear gradient at 2.25% ACN/m55% to 100%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. hexane) were used throughout the analyHPLC grade acetonitrile and analytical-gradetical procedures. A certified solvents (acetone, dichlorommietxture of 16 PAHs hane and
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)
e perdeuterated surrogate PAHs were used to achievfor fluorescence detection. The three 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).

Determination of Sedimentary Organic Matter 6.2.3.Sedimentary organic carbon and nitrogen contents and were analyzed at the Leibniz
Center for Tropical Marine Ecology (ZMT), Bremen, Germany. The content of the elements
was measured using a C/N elemental analyzer (Carlo Erba NA 2100, Milan, Italy) operating at
1100oC (during combustion under supplied oxygen). 30 mg of each homogenized sediment
fraction was placed in a silver cup, treated with 200 L of 1 N HCl to remove inorganic carbon.
This process was repeated twice (when necessary) to ensure all carbonates were transformed
into carbon dioxide, then subsequently dried at 40oC overnight. The method reproducibility was
Joseph, MI) with 1.30 ± 0.04 use of a sediment standard (LECO 1012, Leco, St. measured byple. The fifth samafter everyand 0.13 ± 0.04 wt.-% N wt.-% C (mean ± standard deviation) reproducibility (by relative standard deviation) was 2.71% for C and 4.0% for N for the LECO
of ple 43% for C and 6.52% for N applied for the fine fraction sam.standards (n=5), and was 0WR-B (n=3).

Results 6.3.

ctions e Fratary SizPAHs and Organic Matter in Sedimen6.3.1.mmarized in Table 1 (p. 139) and Table 2. (p. 140). The total PAH are suThe results content (PAH15) in the sediment samples from the Siak estuary varied from 125 ng/g d.w. to
to m = 689 ng/g d.w.) in the coarse fraction, and from 88 ng/g d.w.w. (median, 1828 ng/g d.426 ng/g d.w. (m = 202 ng/g d.w.) in the fine fraction. For the Wenchang/Wanquan estuaries,
the recorded values varied from 94.3 ng/g to 386 ng/g d.w. (m = 138 ng/g d.w.), and from 93.8
to 575 ng/g d.w. (m = 430 ng/g d.w.) in the coarse and in the fine fraction, respectively. The
OC content of the coarse sediment ranged from 0.05% to 9.07% (m = 4.41%) and from 1.29%
/WQ estuaryW. For the Wto 3.31% (m = 1.66%) in the fine fraction of the Siak estuarysamples, the values ranged from 0.13% to 3.87% (m = 0.46%) in the coarse fraction and from
dual PAH in the = 1.98%) for the fine fraction. The content of the indivi 1.21% to 4.11% (mSiak sediments ranged from below instrumental detection limits to 1061 ng/g d.w. for DANTH
ANTH in the fine fraction. Likewise, the r Dng/g d.w. foin the coarse fraction and to 206 individual PAH in the WW/WQ sediment varied from below detection limits to 97 ng/g d.w. for
rene in the fine fractions. The g d.w. for pyfraction and to 178 ng/H in the coarse DANTdistribution of individual PAHs between the fractions was generally very distinct when
comparing the Siak sediments to the WW/WQ sediments. In the sediments taken from the Siak,
PAHs were enriched in the coarse fractions in most cases, whereas the WW/WQ sediments
mainly showed PAH enrichment mainly in the fine fraction. However, individual PAHs which

110

Y ween the stations. BPERe pattern emerged, showing variation bethdid not exactly follow twas 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.
for the Siak pares the distributionstal PAH content, Fig. 2 comoWith respect to tsediments and the WW/WQ sediments. In general, there was a large difference in PAH
of PAHs tended settings. The total content entaldistributions between the two distinct environmto 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
1997). ,inated by marine-originated organic matter (Ruttenberg & Goidom

esraConeFi

A2000Siak-SUMATRA
01801600Coarse
0140neFi).w.g dg/n(1000
012015080HA060P0400200S 143S 138S 134S 250S 253S 230S 231S 232
B700WenchangWanquan
600NANHAI500.)g d.wg/n(300
40015HA200P1000

(A) aFig. 2.nd the DistWencharibution ng apatterns nd Wanquan seof PAHs (as PAHdiments (B).15) i n the coarse and fine fractions of the Siak sediments

111

Relative Composition of PAHs 6.3.2.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
the ons between significant difference in the proporti(Fig. 4 and Fig. 5). However, there was a 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,
n. For the WW 30% in the coarse fractio position of DANTH reached up tothe relative comestuary 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,
ngs (BbFLA, BkFLA, BaP, DANTH), FLA, PYR, BaA, CHRY), 5 riH), 4 rings (PHEN, ANT weenPERY, IPYR) also showed a distinct pattern. The significant difference betBand 6 rings (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
= > 30%). ng structures (m 3- and 4-riby

A40353025)(% nioitsopmo CetivlaeR5
2015100

Siak-Sumatra
(median values)
neFiesoarC

B40Wenchangand Wanquan–Hainan
35(median values)
3025( nitiosompo CetivlaeR)%5
2015100

coarseFig. 4. and t Comhpe fine arisons of the fractions relative comfor the Sumatra and Haiposition of thnan este indivuary anidual PAH to d coasts. the to the PAH15 between the

112

Siak-Sumatra
(median values)
enFieoarsC

A60Siak-Sumatra
50(median values)
40enFieoarsC30evitalRe)%( noitisomp Co0
20102 rings3 rings4 rings5 rings6 rings

B60Wenchangand Wanquan–Hainan
50(median values)
4030) (%nitiosopmo CetivlaeR0
20102 rings3 rings4 rings5 rings6 rings
fine Fig. 5.fractions Compof (arison A)of Siak the sedime contribution nts and of(B the PA) WencHhang ring grand Woup taonqua thn e sePdiAHme15 nts. between the coarse and the

Source Apportionment 6.3.3.Ratio of isomers for PAHs with the molecular weights 178 (ANTH, PHEN), 202 (FLA,
combustion PYR) and 228 (BaA, CHRY) have or petroleum origins (Neff 1979; Budzinski et al., been widely employed to apporti1997; Yunker on et al., 2002; sources to either 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
molanthracene iecular ratncreases as ios of ANTH/(ANTH + Pburning procHesses involve higher tempEN), FLA/(FLA + PYR), BaA/(BaA+CHRY) were eratures. In this study, the
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 respectivelyAlaskan Crude Oil has values of 0.03, 0.26 and 0.10 for these three ratios (Requeojo et (Yunker et al., 2002). For instance, al.,
ue valver, the boundaries between the assigned values are not set in stone. Any1996). Howefalling 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
14 ± 0.07 in the coarse and fine fractions,n = 8) and 0.ean ± standard deviation, ± 0.18 (m± 0.13 and 0.59 Likewise, the coarse and fine ratios of FLA/(FLA-PYR) were 0.59 . respectivelycalculated as 0.48 ± 0.15 and 0.36 ± 0.08. These CHRY) was ± 0.22, and that of BaA/(BaA + m s fro stemination found in Siak River sediments generallyratios suggest that the PAH contampyrogenic sources. On the other hand, the WW/WQ coarse sediment samples yielded ratios of
N), FLA/(FLA-PYR) and BaA/(BaA + CHRY) with values of 0.01 ± 0.01, H+PHEANTANTH/(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.

tion Coefficient Sediment-Water Distribu6.3.4.Sediment-water distribution coefficient (KD, ml/g) was evaluated to get insight into
underlying processes that control the transport and fates of the PAHs in those different aquatic
systems, in particular the role of the dissolved humic substances which may stabilize the PAHs
in the water column and inhibit it from association with the sediment. The KD value is defined
ent to that in water solution, and calculated for here as the ratio of PAH concentration in sedimindividual compound for both sediment fractions at three stations (S143, S138, S134) from the
Siak estuary, and four stations (BB4, CC02, WW8, WW10) from the WW/WQ estuary and
coast. The concentration of dissolved PAHs in WW/WQ coastal estuary was relatively low. The
undetected to 4.15 ng/l. The PAHs ranged from 7.36 to 16.2 mextended frodual PAH indiving/l. This range of concentration was considered low in comparison to aquatic systems around
industrial and intense urban centres in China such as rivers in Tianjin China (45.8 – 1272 ng/l)
ina (70.3 – 1844 ng/l) (Chen et al., 2007). On the other (Shi et al., 2005) and Qiantang River Chous and the coast was reported in our previhand, the level of dissolved PAHs in the Siak estuarynuscript being prepared for journal publication), which the PAHs amwork (Lukman et al., 619 ng/l. o121 t ranged fromThe KD values are then plotted in the Fig. 7, which show that in general the KD values of
and coast. In uarythose of the WW/WQ est are lower than individual PAH in the Siak estuarythe Siak estuary, it ranged in logarithmic value from 2.22 to 5.58 with a median value of 3.37
fraction. On the m = 3.01) for the fine edian for the coarse fraction, and from 1.53 to 5.03 (mother hand, in the WW/WQ estuary and coast it ranged greatly from 1.12 to 5.89 (m = 3.93) in
= 4.40) in the fine fraction. 2.58 to 5.85 (mthe coarse fraction, and from

114

Discussion 6.4.

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.
r PAH contents e, with higheexact oppositents was the The situation for the WW/WQ sedimfound 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
t. DANTH andpling areas were differensuggest that the PAH sources located in these two samNAPH significantly contributed to the relative composition of the total PAHs analyzed in the
Siak sediments. During Sumatran peatland burnings, the resulting smoke contained DANTH
e. Riau provinc of mmensurate with the values observed for Pekanbaru, the capital citylevels coNAPH levels for this area, however, remained low (See et al., 2007). Therefore, high DANTH m burnings. However, further ing fro be a strong indicator stemmmayin the sediments 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
de crude oil. High NAPH contents in the cruother sources than biomass burnings, specificallyoil 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
ments are on. On the other hand, PAHs in the WW/WQ sedipolluti high characterized bycontents 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
The ratios for FLA/(FLA+PYR) andal., 1998). coal emissions (e.g. Yang et BaA/(BaA+CHRY) are in agreement with those calculated for coal and petroleum combustion
al., 1999). t(e.g. Marr et al., 1999; Li eSedimentary organic matter is a pivotal factor affecting PAH distribution in the coarser,
gher PAH contents generally correspond to higher OC hi,s studygrain-size fractions. In thiof the OC content between the grain-size stems. The distribution both aquatic sycontents for ng PAH contents. The higher OC contents ilar patterns to their correspondifractions showed simean value = 23) found in the coarse fraction of Siak d.w. ) and the C/N ratios (m%edian = 4(msediments 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

in can conclude that the high PAH levels erefore, we h(Holtvoeth, 2004, Pillon et al., 1985). Tthe 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 &
004; Gustafsson et al, 1997; Grathwohl, 1990). Black carbon is also co-produced Gustafsson, 2with 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
stem via both landto enter the aquatic syare then free the burning residues. These substances drainage and atmospheric deposition. High erosion rates have been recognized in much of the
in the suspended particulate increases and the along the coast as evidenced by Siak estuarymatter 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
be ments can also solution. The higher PAH levels in the fine fraction of these sedisorption fromrresponding coarse fraction. opared to that of the cthe larger OC content as comattributed to 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
ined for the an = 13) determediN ratio (mmedian values of ca. 2% d.w.. The relatively low C/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
er PAH partitioning rates, which occurred whenever soot-partitioning ment-porewatelevated sedi

116

concluded that black carbon (BC) emerges as the was included in calculating the hydrophobic partition mmost important overall geosorbent constitodel. Cornelissen & Gustafsson (2004)ute
our studies siin the case of low aqueousnce the PAH concentration existing in PAH (concentrations below ng/l). That would be in solution was in the rangeagreement wi of 121 to 619 th

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-

ount ing water. Siak estuary and the coast contained significant amand overlyorganic porewater data). npublished mpared to the Wenchang and Wanquan coastal estuaries (Balzer, uof DOC coThe calculation of the sediment-water distribution coefficient showed that the KD values in the
lower than those of the non-peatland water of Hainan suggesting are the generallySiak estuary

that high DOC in the Siak water may sustain the PAHs in the water column impeding their
role of colloid or DOC in sustaining the association onto the sediment organic matter. Such r instance, Chin & Gschwend (1992) observed een recognized. FoPAHs in the water has bincreased PAH sorption levels onto porewater colloids in heavily contaminated Boston Harbor
be released from seents. Yu et al. (2009) found that PAHs tend tosediments into porewater dim

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
However, these insights also need further Hs by the fine fraction. sorption/desorption of PA are. accurate these suggestions reallyto show how investigation

117

dexMisecurSoPetroleum

Combustion

Petroleum
CombustionGrass/Wood/Coal
PetroleumCombustion
01.90.Peat Burning
0.8Dumailightve-dhuticley disesel Combustion
0.7Agricultural
SPM after forest debris
0.6firesWeat grasses
)RYHC + AaB( A /aBSources
0.5Oil spills Rice grasses
0.4"Tanker Enrika"
0.3CharcoalBituminous coalMixed
20.0.1Alaskan crude oilPetroleum
00.40.0.4Bituminous coal
0.3Agricultural Combustion
0.3debris
Oil spills "Tanker Charcoal
20.NEHP H +TNA(H / TNA)0.1WW8oilvehiclesPetroleum
Enrika"Peat Burning Weat grasses
0.2DumaiRice grasses
0.1Alaskan crude light-duty diesel
01WW00.0.00.10.20.30.40.50.60.70.80.91.0
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 fromoils (light grey cycles) are Yunker et al. (2002additionally ). For compresented parison, vatori illustrate how the determous literature data of PAHs emissions and crude ining 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
ai (See et al., ng-Dumatra peatland burniAbrantes et al 2004); Sumal.,1996); light-duty diesel vehicle (de 2007); SPM after forest fire (grey cycle with black outline: Vila-Escale et al 2007).

118

kaSiSUMATRA

Wenchangand Wanquan
NANIAH

6.00SiakWenchangand Wanquan
SUMATRAHAINAN
HNAP505.NEACUFLNEPH005.HANTAFL504.RPYABa004.RYCHDKALFBb glo3.50BkFLA
PBaHDANT3.00BPERY
RYIP2.50SIAK, MEDIAN
SIAK, MEDIAN
HAINAN, MEDIAN
2.00HAINAN, MEDIAN
1.50CoarseFineCoarseFine
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.
Conclusion 6.5.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
als such as biomass burning residues, peat and true in the presence of carbonaceous materifragmented 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
the Siak River nents associated with the organic matter imsorption of PAHs onto fine sedisystems could be due to the existence of high levels of DOC found in the water column, which
However, in non-peatland areas of Hainan, on PAHs. can increase the partitioning effect 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
m mixture of coal and petroleud from a m Hainan Island stemmeWW/WQ sediments frocombustion. For the total content of PAHs not only the sources of PAHs are important
ment fraction size, PAH ring size, but also other factors such as sedior petrogenic), rogenic (py

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,
als. peat, and fragmented plant materi

ments Acknowledg

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
ore, we FurthermAcademic Exchange Service (DAAD). We acknowledge all their supports. would like to extent our grateful to scientists and students from University of Riau, Indonesia,
y, China, and to Research, East China Normal Universitthe Institute of Estuarine and Coastal paigns and discussion. pling camduring samon SPICE German colleagues for their contributiwe appreciate our colleagues at Leibniz Centre for Tropical Marine Ecology ZMT ore, Furtherment and measureDipl. Ing. Matthias Birkicht, Ms. Dorothee Dasbach, for the organic mMs. Sonia Tambou (Marine Chemistry Working Group, Uni-Bremen) for laboratory assistance.
s. constructive critics and comment, we thank all reviewers for theirFinally Referencesnic bined roles of natural orga2002. Assessing the com, A., Gschwend, P.M., Accardi-Deymatter and black carbon as sorbents in sediments. Environmental Science and
21-29.Technology, 36, Baars, B-J., 2002. The wreckage of the oil tanker ‘Erika’ – human health risk assessment of
beach cleaning, sunbathing and swimming. Toxicology Letters, 128, 55-68.
Baum, A., Rixen, T., Samiaji, J., 2007. Relevance of peat draining rivers in central Sumatra for
Science 73, 563 – 570. the riverine input of dissolved organic carbon into the ocean. Estuarine, Coastal and Shelf
C., Garriques, P., 1997. Evaluation of sediment Budzinski, H., Jones, I., Bellocq, J., Pierard,contaminant by polycyclic aromatic hydrocarbons in the Gironde estuary. Marine
58, 85-97.istryChemChen, Y., Zhu, L., Zhou, R., 2007. Characterization and distribution of polycyclic aromatic
hydrocarbon in surface water and sediment from Qiantang River, China. Journal of
Hazardous Materials, 141: 148-155.Chin, Y-P., Gschwend, P.M., 1992. Partitioning of polycyclic aromatic hydrocarbons to marine
porewater organic colloids. Environmental Science and Technology, 26, 1621-1626.
on ental black carbof phenanthrene to environmSorption Cornelissen, G., Gustafsson, Ö., 2004. in sediment with and without organic matter and native sorbates. Environmental Science
, 38, 148-155.and Technologyde Abrantes, R., de Assunção, J.V., Pesquero, C.R., 2004. Emission of polycyclic aromatic
hydrocarbons from light-duty diesel vehicles exhaust. Atmospheric Environment 38,
De Luca, G.1631-1640. D., Furesi, A., Micera, G., Panzanelli, A., Piu, P.C., Pilo, M.I., Spano, N., Sanna.,
2005. Nature, distribution and origin of polycyclic aromatic hydrocarbons (PAHs) in the
sediments of Olbia harbor (Northern Sardinia, Otaly). Marine Pollution Bulletin 50,
2.1231223-

120

extractable Fang, M., Zheng, M., Wang, F., To, K.L., Jaafar, A.B., Toorganic conpounds in the Indonesia biomass burning aerosols –ng, S.L., 1999. The solvent-
characterization studies. Atmospheric Environment 33, 783-795.
Fernandes, M.B., Sicre, M.-A., Boireau, A., Tronczynski, J., 1997. Polyaromatic hydrocarbon
(PAH) distributions in the Seine river and its estuary. Marine Pollution Bulletin, 34(11):
Gauthier, T.D., Seltz, 857-867. W.R., Grant, C.L., 1987. Effects of structural and compositional
variations of dissolved humic materials on pyrene Koc values. Environmental Science and
248.Technology, 21(3), 243-Ghosh, U., Gand associatiillette, J.S., Luthyon of polycyclic aromatic hydr, R.G., Zare, R.N., 2000. Microscale location, cocarbons on harbor sediment particles. haracterization,
& Technology 34, 1729-1736. ental Science EnvironmGhosh, U., Zimmerman, J.R., Luthy, R.G., 2003. PCB and PAH speciation among particle types
in contaminated harbor sediments and effects on PAH bioavailability. Environmental
Science & Technology 37, Grathwohl, P., 1990. Influence of organic 2209-2217.m atter from soils and sediments from various origins
on the sorption of some chlorinated aliphatic hydrocarbons: iplication on Koc correlations.
Gustafsson, EnvironmÖ., Haghseta,ental Science and Technology 24, F., Chan, C., Macfarlane, J., Gsch1687-1693. wend, P.M., 1997. Quantification
of the dilute sedimentary soot phase: implications for PAH speciation and bioavailability.
Gustafsson, EnvironmÖ., Haghseta,ental Science and Technology 31, F., Chan, C., Macfarlane, J., Gsch203-209. wend, P.M., 1997. Quantification
of the dilute sedimentary soot phase: implications for PAH speciation and bioavailability.
203-209.d Technology 31, ental Science anEnvironmHoltvoeth, J., 2004. Terrigeneous organic matter in sediments of the eastern equatorial Atlantic
– distribution, reactivity, and relation to Late Quaternary climate -. PhD Dissertation,
y. r Universität Bremen, GermanGeowissenschaften, deFachberiech Holtvoeth, J., Kolonic, S., Wagner, T., 2005. Soil organic matter as an important contributor to
Cosmlate quaternarochimy sedimica Acta 69(8), 2031-2041. ents of the tropical West African continental margin. Geochimica et
ea, grain size and arment surface Horowitz, A.J., Elrick, K.A., 1987. The relation of stream sedicomposition to trace element chemistry. Applied Geochemistry, 2, 437-451.
IARC Monographs on the evaluation of carcinogenic risks to humans, Suppl. 7, IARC, 1987.overall evaluations of carcinogenicity: an updating of IARC Monographs volumes 1 to
RC Press.yon, IA42, LICES, 1997. Determination of polycyclic aromatic hydrocarbons (PAHs) in sediments:
AnalyEnvironment, 1997. ICES tical methods. In Report of the ICES AdvisorCooperative Research Repyort 222, 118-124. Committee on the Marine
aromatic hyJenkins, B.M., Jones, A.D., Turn, S.Q., Williamdrocarbons from biomass bus, R.rning. EnvironmB., 1996. Emission factors for polental Science and Technolycycogy,lic
9.246462-30, 2polychlorinated biphenyJonker, M.T.O., Koelmans, A.A., 2002. Sorptiols to soot and soot-like materials in the n of polycyclic aromaqueous environmatic hydrocarbons and ent :
mechanistic considerations. Environmental Science and Technology, 36, 3725-3734.
debris. The SKakareka, S.V., Kukharchyk, T.I.,cience of the Total Environmental, 308, 2003. PAH emission from257-261. the open burning of agricultural
ng, Y-F., 1999. PAH emission from the industrial H-H., Lee, W-J., You, W-C., WaLi, C-T., Mi, Liu, H., Amy, G., boilers. Journal of Hazardous Materials, 1993. Modeling partitioning and transportA69, 1-11. interactions between natural
organic matter and polynuclear aromatic hydrocarbons in groundwater. Environmental
Liu, W.X., Dou, H., Wei, Z.C., ChScience and Technology, 27, 1553-1582. ang, B., Qiu, W.X., Liu, Y., Tao, S., 2009. Emission
characteristics of polycyclic aromatic hydrocarbons from combustion of different
residential coals in North China. Science of the Total Environment 407, 1436-1446.

121

LuthyJ.J., Reinhard, M., Traina, , R. G., Aiken, G.R., Brusseau, S.J., 1997. SeM.L., Cunniquestration ofngham, S.D., hydrophobic Gschwend, P.M., Pignat organic contaminants ello,
by geosorbents. Environmental Science and Technology, 31, 3341-3347.
guel, A.H., Hering, S.V., Hammond, S.K., 1999., R.A., MiMarr, LC., Kirchstetter, T.W., HarleyemCharacterizatissions. Environmion of polyental cyclic aromatic Science and Technology, hydrocarbons in 33, 3091-motor veh3099. icle fuels and exhaust
McGroddyarom, atic hydrocarbons S.E., Farrington, J.W., 1995. Sedimin three cores from Boston Hent porewater partitioning of polarbor, Massachussetts.ycyclic
Meyer, P.A., Environmental Science an1994. Preservation of elemental and isotd Technology, 29, 1542-1550.opic source i dentification of sedimentary
Neff, J.M., 1organic matter. Chem979. Polycyclic aroical matic Geologyhy 114, 289-302. drocarbon in the aquatic environment: sources, fates
pp. Publisher Ltd, Essex, UK, 262 lied Science ogical effects. Appand biolaromatic hyOanh, N.T.K., Albina, D.O., Ping, Ldrocarbons from selected cookstove – f., Wang, X., 2005. Emuissionel systems in Asia. Bio of particulate and polycmass and yclic
Bioenergy, 28, 579-590.Page, S.E., Siegert, F., Rieley, J.O., Boehm, H-D. V., Jaya, A., Limin, S., 2002. The amount of
Pillon, P., Joccarbon released fromteur-Monrozi peat er, L., Gonzalez, C., Saand forest fires in Indonesiliot, A., 1986. Ora during ganic geochemistry1997. Nature 420, 61-65. of recent
equatorial deltaic sediments. Organic Geochemistry, 10, 711-716.
Prahl, F.G., Washington Carpenter, R., 1983. PolCoastal sediments. Geochycyclic aromimatiica et Cosmochimica c hydrocarbons (PAH) phase associations in Acta 47, 1013-1023.
, M.C., Brooks, J.M., 1996.McDonald, T., Denoux, G., Kennicutt IIRequejo, A.G., Sassen, R., Polymarine crude nuclear aromatic hyoils. Organic Geochemdrocarbons (PAH) istry 24(10/11), as indicators of the 1017-1033. source and maturity of
Rockne, K.J., Shor,sequestration and release L.M., Young, L.of PAHs in weatherY., Taghon,ed G.L., Kosson, D.S., sediment: the role of sediment structure 2002. Distribution
and organic carbon properties. Environmental Science and Technology 36, 2636-2644.
Ruttenberg, K.C., arctic, tempGoi, M.A., erate, and tropical coastal 1997. Phosphorsedimentus distribution, C:N:P s: tools for characteriratios, and 13Coczing bulk in
organic matter. Marine Geology 139, 123-145.entarysedimSaeed, T., Al(PAHs) in th-Mutairi, M., 2000. Comparative coe sea water-soluble fractions of different Kuwaiti crmposition of polycyclic aromatude oils. Advances in ic hydrocarbons
145.ental Research 4, 141-EnvironmSargenti, S.R., McNair, H.M., 1998. Comfluid extraction for extraction of polycpariysclic aroon of solid-phase matic hydrocarbons fromextraction and supercritical drinking water.
Journal of MicrocolumSee, S.W., Balasubramanian, R., Rianawati, E., Karthikeyn Separation 10(1), 125-131. an, S., Streets, D.G., 2007.
Indonesia durCharacterization and souring a recent ce apporpeat fire tionment of particulate episode. Environmental Scimatter  2.5 μm inence and Technology, 41, Sumatra,
Shi, Z., Tao, 3488-3494. S., Pan, B., Fan, W., He, H.C., Zuo, Q., Wu, S.P., Li, B.G., Cao, J., Liu, W.X., Xu,
China byF.L., Wang, polycy X.J., Shen, clic aromatic hydrocarbonsW.R., Wong, P.K., 2005. . Environmental Pollution, Contamination of rivers in Tianjin,134: 97-111.
sySiegel, H., Stottmstem-east Sueister, I., Reißmatra charmaacterisation of sources, estunn, J., Gerth, M., Jose, C., Samarine processes, and discharges into iaji, J., 2009. Siak river
s 77, 148-159. stemthe Malacca Strait. Journal of Marine SySoclo, H.H.,(PAHs) in coastal Garrigues, PH., Ewald, marine sediments: case M., 2000. Origin of polycystudies in Cotonou (Benin) and Aquitaine clic aromatic hydrocarbons
396., 387-(France) areas. Marine Pollution Bulletin 40(5)Vila-Escalé,compounds into a Mediterranean creek M., Vegas-Villarubia, T., Prat, N., 2007. Rel (Catalonia, ease of polyNE Spain) after a forest fire. Water cyclic aromatic
Research, 41: 2171-2179.

122

ert, P., Zeng, G., Yang, C., Hollebone, B., 2004. Characterization bWang, Z., Fingas, M., Lamand identifiChromatography A 1038,cation of the Detroit 201-214. River mystery oil spill (2002). Journal of
Wang, Z., Fi843, 369-411. ngas, M., Page, D.S., 1999. Oil spill identification. Journal of Chromatography A
stacks. Journal of HazardoYang, H-H., Lee, W-J., Chen, S-J., Lai, S-O., 1998. PAH emus Materials 60, 159-174. ission from various industrial
Yu, Y., Xu, aromatic hydrocarbons (PAHs) froJ., Wang, P., Sun, H., Dai, S., 2009. Smediment-porewater p Lanzhou Reach of Yellow River China. Journal ofartition of polycyclic
Hazardous Materials 165, 494-500.Yunker, M.B., Macdonald, R.W., Vingarzan, R., Mitchell, H., Goyette, D., Sylvestre, S., 2002.
of PAH ratio as indicators of PAH basin: a critical appraisal PAHs in the Fraser River Zakaria, M.P., Horinouchisource and composition. Organic Geochemistry, A., Tsutsumi, S., Takada, H., Tanabe, S., Ism 33, 489-515. ail, A., 2000. Oil
pollution in the source identification. EnvirStraits of Malacca,onm Malayental Science and Technologysia: Application of , 34, mo1189-lecular1196. markers for
hyZhang, Y., Tao, S., 2009. Global atmdrocarbons (PAHs) for 2004. Atmospheric emission inventorospheric Environment, 43, 812-819.y of pol ycyclic aromatic
Zhou, J., Waromaatic hyng, T., Huang, Y., Mao,drocarbons in urban and suburban T., Zhong, sites N., 2005. Siof Beijing, China. Chemze distribution of polyosphere 61: cyclic
99.792-7

123

38 1--05827 3--76829 2--8382-8 08-96223 0--219 a,bS CA0022-3263. ebez; Toropov, Andrey.1139/v74-087; IAarzenb= Schwc n3 0--7352-5 3993-1 of the US EPA priority pollutants. 16 PAHsical properties ofPhysical & chem .Appendix 1

number2a,bpotswood,T.M.; JCSOA9; Journal of ,G.M.; Surnal; Badger7; Jo 15967,f. 2e: Ral; Studt; JLACBF; Justus Li 4623412; Journ f. 1e: R
tMol. ol) (g/m 718,124,15 12 328,17 622,20 928,22 232,25 232,25 436,27
Weigha FormulCCCCCCCCCCCCCCCCurnal; Aronson; 4276855; Jo,: Ref. 9
820 ,25 181022 ,66 1101023 ,87 11010 622, 20101228, 22 91212,25 232 121234 ,67 2121235 ,87 214
ar e enlery)pd-c acene)anthrFieser; Novello; JHershberg bei 18469; Journal; 17,. 2: RefEdstrom; JOCEAH; Journal ofLewis; 67311; Journal; 44,. 1: Ref
e enryp)kel PerMayez, rnal; Gonzal: Ref. 3, 6482028; Jou
H10H12H12H13H14H14H16H16H18H18H20H20H20H22H22H22
Molecul)P(M .No 1.2.3.4.5.6.7.8.9..10.11.12.13.14.15.16= Bojes & Pope, 2007; available; a = Weast & Astle, 1985; b= data not n.a. llows: o as fences refersiou var= Beilstein Database from* (MP)Fluoranthene02-7863. a061; ISSN: 0010.1021/ja01864Benz(BP)reneo(a)py DOI: 10; 557;; 1974 52;y ChemistrJournal ofCHAG; Canadian et al.; CJMurray(MP)ntheneo(b)fluoraBenz368-1769. 04420; ISSN: 010.1039/jr96000P)(Bleneo(g,h,i)peryzBen3049.; 33; ISSN: 1420- 102004; 1019 -902. 1902(79)80180-3; ISSN: 0022-1(BP)reneIndeno(1,2,3-cd)py50,2053; ISSN: 28; 1963; 20;yemistrOrganic Ch Edstrom; JOCEAH; Journal of
spoundCom )anthraceneane yre)pa antheneor)flub antheneor)flukh,ig,ha,
Naphthalenelene yhphtcenaA theneaphAcen Fluorene Phenanthrene eneAnthrac antheneFluor Pyrene yseneChr(Benzo(Benzo(Benzo(Benzo(Benzo.3.2(1Indenoo(Dibenz

dWater ownt 453. 224. 464. 205. 615.6. 35 206. 516.16/0022-
e 9; 12; K85084 91303Partitiong 7975.....Coefficie5.5.46654LoOctanol-.10les; English; K n.a. n.a.al; . 9, 4258666; Journ: Ref
; DOI: 10a)P(Mal; Lewis; 4467311; Journ : Ref. 3
ol) 5 I:e9 7 6 0605/m Henry’s LawConstant mmt(a 03E-504. 04E-402. 04E-702. 03E-951. 05E-407. 07E-702. 9 Anm. 23; DOI:
E-0E-0E-0E-03Ha. E-E-; 1579 .0000n20304008.da983. n.a. 02E-90 2.., 200al., 2004; et ez 2; e = Martin
LEFW; Molecu...1.1.72214420 - 4427; DO 41; 1979 3 1 0 8 5 )55,1850706P;OE-0yE-1E-1E-0E-0E-E-(M porVaPressure(mm Hg) 02E-898. 03E-753. 04E-806. 06E-138. 09E-807. 09E-894. 11E-599. 10E-401.
; M40065emistr5425.21005.....ish; 1960; 1.4.3SSN: 0022-3263.; 21824617.; ardo A; 62; 1940; 18 Nuclear Ch, Edu ; Engl15005 003 140 76 0.1Watermg/L .230 933. 181. 0260.015 0.0038 0.0080 0.0005 0.0
9; I0113Solubility0.6stro000.130; ISSN: 0075-1...0.0.0a000= Williamson et al Chemical Societyemical Societynorganic and63; 2050,2053Pablo R.; C* * ; 5C)a117 3 270 216 o27916526Melting (MP256 55-2
Point .580 .29601 151* 1 *46.1717 260* 1
I-9h 161516-2cz, 69-14-77-62-9the C 28; 191993; d erican1Chemie; 19782221SSN: 0008-4042. ;AO; Journal ofyA.; Duchowie Amistr et al. a295 der emC) 79 a. 56-275 18 oachh60* a. 5Boiling 42* 80 95* 48 375 40 40 ..Point433993-(BPigs Annalen Organic CCSAT; Journal of thKatlowitz; JINCpotswood,T.M.; JCSOA9; Journal of

124

5-2 2491-14-9 0807-2n-2 9905-248 2--305 3-55-564-9 0118-2 0-00-9123-00 4406-3-7 1220-1

Appendix 2. Emission factors and isomeric ratios of PAHs from various pyrogenic ture data) and petrogenic sources (literaAppendix 2.1. Emission factors of PAHs (mg/kg fuel) from various coal, biomass, and petroleum combustions Emission Sources Factor Remarks References
g fuel) (mg/koalCBituminous Coal 121 Cu addition at 800oC Yan et al 2004
Bituminous Coal 248 Cupric oxide, CuoO, addition at Yan et al 2004
C 1000Coal 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 the Jinxi coal mine in Beijing Liu et al 2009
al Datong coCoal source: the Bituminous Coal 1096 mine in Shanxi province
Anthracite Coal 77,8 coal source: the Jinxi coal mine in
Beijingal Datong coCoal source: the Anthracite Coal 151 mine in Shanxi province
al Datong coCoal source: the Honeycomb Briquette 812 mine in Shanxi province
Bituminous Coal 152 Samples from Elmsworth Willsch & Radke, 1995 cited in
gasfield, Canada Achten & Hofmann, 2009
ada Elmsworth gasfield, Can137 Bituminous Coal Bituminous Coal 153 Ruhr basin, Osterfeld Germany
Bituminous Coal 124 Ruhr basin, Hugo Germany
y Ruhr basin, Westerholt German164 Bituminous Coal Bituminous Coal 155 Ruhr basin, Blumenthal Germany
sesBiomasWoodsAlmond 14,1 Wind tunnel simulation of open 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 chips Vietnam traditional wood 56,4 Oanh et al., 2005
Eucalyptus wood 110 Open burning in Southeast Asia Oanh et al., 1999
Paper 68,8 Joss paper furnace Yang et al., 2005
isbrs / deGrasseRice grasses 15,1 Wind tunnel simulation of open Jenkins et al.,1996
burning Corn grasses 45,3 Jenkins et al.,1996
Agricultural debris 410 Open burning Kakareka & Kukharchyk, 2003
eum PetrolNatural 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

LMW/HMW MW 178 MW 202 MW 228 MW 276 References
Coal and Petroleum combustions
18 0,10 0,24 0,58 0,65 Yang et al., 1998
10 7,3 0,120,21 0,210,33 0,350,37 0,31 Yang et al., 199Oanh et al., 1998 9
5,115 0,400,55 0,930,32 0,490,15 0,36 Lee et al., 2005Oanh et al., 199 9
1,1 0,28 0,91 0,61 0,28 Li et al., 1999
6,0 0,14 0,24 0,35 0,35 Yang et al., 1998
1,0 0,43 0,56 Marr et al., 1999
6,5 0,25 0,52 0,53 0,70 Li et al., 1999
1,7 0,04 0,93 0,87 2004 de Abrantes et al.,
ingss BurnBiomasWoods/Bamboo8,68,3 0,160,14 0,540,57 0,510,43 Jenkins et al.,19Jenkins et al.,1996 96
4,3 0,25 0,79 0,56 0,59 Oanh et al., 2005
8,8 0,14 0,56 0,53 Jenkins et al.,1996
6,12,4 0,160,18 0,550,56 0,540,48 0,000,49 Schauer Jenkins et al.,19et al., 296 001
2,6 0,20 0,52 0,53 0,57 Yang et al., 2005
2,5 0,19 0,57 0,45 Schauer et al., 2001
2,4 0,26 0,77 0,51 0,64 Oanh et al., 2005
4,0 0,28 0,79 0,39 0,82 Oanh et al., 2005
2,9 0,24 0,81 0,53 0,77 Oanh et al., 2005
4,2 0,21 0,80 0,40 0,88 Oanh et al., 2005
7,4 0,29 0,67 0,48 0,69 Oanh et al., 1999
0,214 0,040,30 0,650,53 0,500,11 0,561,00 Oros et Yang et al., 200al., 20065
Grasses/debris/peats0,20,4 0,160,23 0,530,43 0,52 0,42 1,00 Oros Oros et et al., al., 20062006
0,7 0,21 0,44 0,68 Oros et al., 2006
0,310 0,040,15 0,500,59 0,0,4740 0,940,50 Jenkins et al.,19Jenkins et al.,1996 96
3,4 0,23 0,71 0,69 0,26 KukharchKakareka & yk, 2003
0,7 0,16 0,38 0,73 0,62 See et al 2007
0,7 0,79 0,49 0,90 0,68 See et al 2007

Appendix 2.2. The isomeric ratios for source apportionment from various organic matter burnings combustion/ Sources LMW/HMW MW 178 MW 202 MW 228 MW 276 References
Coal and Petroleum combustions
IndustrCoal- Cy ement 18 0,10 0,24 0,58 0,65 Yang et al., 199
Bituminous Coal 10 0,12 0,21 0,35 0,31 Yang et al., 199
Coal BrCharcoal iquette 15 7,3 0,550,21 0,32 0,33 0,150,37 Oanh et al., 199Oanh et al., 199
Bituminous Coal Diesel, Industrial 5,1 0,40 0,93 0,49 0,36 Lee et al., 2005
Boiler 1,1 0,28 0,91 0,61 0,28 Li et al., 1999
Plant Fuel Oil, Heavy-oil 6,0 0,14 0,24 0,35 0,35 Yang et al., 199
DiesVehiclel –es Heavy-duty 1,0 0,43 0,56 Marr et al., 1999
HeavBoilery oil, Industrial 6,5 0,25 0,52 0,53 0,70 Li et al., 1999
vehiclesLight-duty Diesel 1,7 0,04 0,93 0,87 2004 de Abrantes et
ingss BurnBiomasWoods/BambooWalnut Almond 8,68,3 0,160,14 0,540,57 0,510,43 Jenkins et al.,19Jenkins et al.,19
Chinese clawoodstoves y 4,3 0,25 0,79 0,56 0,59 Oanh et al., 200
heating Pine-domestic 8,8 0,14 0,56 0,53 Jenkins et al.,19
Fir Eucalyptus wood 6,12,4 0,160,18 0,550,56 0,540,48 0,000,49 Schauer Jenkins et al.,19et al., 2
Heating Wood, Domestic 2,6 0,20 0,52 0,53 0,57 Yang et al., 200
Oak Wood 2,5 0,19 0,57 0,45 Schauer et al., 2
Lao traditional wood 2,4 0,26 0,77 0,51 0,64 Oanh et al., 200
chips chips Thai bucket wood 4,0 0,28 0,79 0,39 0,82 Oanh et al., 200
Cambodian traditchips ional wood 2,9 0,24 0,81 0,53 0,77 Oanh et al., 200
Vietnamwood chips tr aditional 4,2 0,21 0,80 0,40 0,88 Oanh et al., 200
EucalyJoss Paper ptus wood 7,414 0,040,29 0,650,67 0,480,11 0,560,69 Yang et al., 200Oanh et al., 199
Bamboo 0,2 0,30 0,53 0,50 1,00 Oros et al., 2006
Grasses/debris/peats2006Sugarcane 0,4 0,23 0,53 0,42 1,00 Oros et al.,
Mixed rPampas grass yegrass 0,70,2 0,210,16 0,440,43 0,520,68 Oros et Oros et al., 2006al., 2006
Corn grasses Rice grasses 0,310 0,040,15 0,500,59 0,0,4740 0,940,50 Jenkins et al.,19Jenkins et al.,19
Agricultural Debris 3,4 0,23 0,71 0,69 0,26 KukharchKakareka & yk, 20
(ng/mPeat Burn3) ing Dumai 0,7 0,16 0,38 0,73 0,62 See et al 2007
Peat Smoke Pekanbaru (ng/m3) 0,7 0,79 0,49 0,90 0,68 See et al 2007

126

Appendix 2.2.

1,0

0,7

0,4

0,150,15

0,110,13

0,090,14

0,10 0,18 Requojo et al. 1996

0,37 0,21 Baars et al., 2002

0,31 0,37

0,470,31

Sources LMW/HMW MW 178 MW 202 MW 228 MW 276 References
Spillsoil / OilCrude Crude (ppm) Alaskan North Slope 10 0,03 0,26 0,10 0,18 Requojo et al. 1996
Oil spills "Oil Tanker 1,0 0,15 0,15 0,37 0,21 Baars et al., 2002
Enrika" (mg/kg) BeachOil spills Samp "Enrikle1 a" 0,7 0,13 0,11 0,31 0,37
a" "EnrikOil spillsBeach Sample2 0,4 0,14 0,09 0,31 0,47
(μg/g TSEM*) Detroil Oil Spill_1 1,3 0,10 0,57 0,51 0,47 Wang et al 2004
Detroil Oil Spill_3 Detroil Oil Spill_2 1,01,5 0,050,11 0,610,57 0,510,50 0,490,47
LMW/HMW = sigma low molecular weight compounds (2-3 rings) / sigma high molecular weight compounds (4-6
rings)MW 178= the ratio of anthracene /( anthracene + phenanthrene)
MW 202 = the ratio of fluoranthene /( fluoranthene + pyrene)
MW 228 = the ratio of benzo(a)anthracene/( benzo(a)anthracene + chrysene)
MW 276 = the ratio of indeno(1,2,3-cd)pyrene /( indeno(1,2,3-cd)pyrene + benzo(g,h,i)perylene)
*TSEM = total solvent-extractable materials

127

3800 3600 300 200 200 4e standaum 20 20or uS mor fedar 0, 50, 10-,3,2(1node0, 1 )pg,h,izo(0,1 20ha,(nzo0,05 ,0 0azo(0, 50, 10oulf)kzo(0, 1 uo)flbzo(0, 50, 100,05 ,0 0)aazo(0, 50, 10 0, 1 nenthera0, 50, 10 nehrace0,05 ,0 0 enhrenant0,1 20 nere,05 00 enthehp 128

Dilution Fractor (DF) Acetonitrile (μL) Dilution FactMaking a Chrysene PyreneAcenaAcenaDibeComFluoFluoBenBenAntPheVolBenBenBenInN

)rd (μL

10 e en ene neyrnthraceneheheylen)pon ntntic,dnthraceneer rara)adilut)pyrenephthylene Dilution Fractor (DF)

ny ards for calibrationem of 16 PAH reference standAppendix 3.1. Dilution systbH, Augsburg, GermaDr. Ehrenstorfer Gm nol (1:1) obtained fromthaem= 16 PAH Mix 61 (US EPA 16) in 1 mL acetone/ k Standard Stoc(HPLC grade) = acetonitrile Dilution solvent = ng/μl Concentration unit

Stock000 11000 2000 1100 200 1100 1 2002000 100 1100 1 2002000 100 1100 2 2002000 1

00 000 1

2 001 1 00 1 202111121
1 1 22211

eprP 1000 4600 3

80 5 805950 33
k cot 00 900 S40-1b3

25 25 25 55252525 200 8 52, 250, 5120, 5120, 5120, 5120, 250, 5120,
24 111,,,,0,0,0,,11000 5555 5 55522 00 45 50, 250, 250, 250, 250, 50, 250,
23 ,,,,0,0,0,,22000

L-2 CA 00 m600 10o4r3 fedareprP00 200

5555 5 1110000 2 10, 050, 050, 050, 050, 10, 050,
00,1,,0,0,0,,,00000ardandton satiCalibr-#) (CAL
1 1 5 6 1 2221 000 1 20, 10, 10, 10, 10, 20, 10,
1 ,2,,0,0,0,000

5 5 555 25 25 25 5505050505000 7 8 0550220220202020,

800

555025 025 25 25 025 0 0004 050, 5000,025 0,0025 0,0,0025 0025 0,0 5000,025 0,0
0 00000000100,,00,0,,,0,,00000 05 05 05 550101010 000210, 010, 5000, 5000, 5000, 5000, 010, 5000,
009 00,,00,0,,,0,,00000 1111 1 0202020 0001 20, 020, 010, 010, 010, 010, 020, 010,
00,,0,,,000,0,0,000

10 00 4600 3
L-7 CA 200 00 m58o3r fedareprP 52.600 1400 2

,05 00 e alenthpha400 2 102 Sub-Stock pound

Appendix 3.2.1. procedural efficiency and reproducibility in suPercent recovery of surrogate standards used for comrface sediment fractions. pensating the

SampleStationSedimentd10-phenanthrened10-fluoranthene d12-perylene
Fraction (μm)River S 24 > 63< 63 74,179,5 98,5109 90,8100
S 101 > 63 83,2 117 90,5
S 20 < 63> 63 74,199,2 94,0113 94,995,0
S 104 > 63< 63 81,186,9 105 10310188,5
S 105 > 63< 63 40,6 117 85,0
< 63S 35 > 63 72,5 82,3 88,5
< 63S 116 > 63 78,1 105 87,3
S 42 > 63< 63 94,169,7 84,299,4 11973,9
< 63 10910599,7
S 145 < 63> 63 81,276,3 108102 83,992,4
Estuary S 143 < > 6363 64,577,0 93,9105 94,382,5
S 142 > 63 86,3 11996,7
< 63 75,7 93,0 94,5
S 138 < > 6363 92,266,5 93,672,9 86,275,8
S 134 < > 6363 83,293,4 10876,7 104106
S 252 < > 6363 82,882,8 97,597,5 109 95,1
S 125 < > 6363 69,582,4 77,8103 89,682,7
S 250 > 63 113109121
< 63 99,1 87 119
S 251 < 63> 63 82,881,2 115109 87,5107
CoastS 269 > 63 73,1 70,2 102
S 226 > 63< 63 82,868,0 69,492,0 10375,6
< 63 82,8 141120
S 227 < 63> 63 82,882,8 88,499,9 81,5104
S 228 > 63 77,2 94,9 99,7
< 63 79,4 87,3 86,7
S 267 > 63< 63 70,394,2 86,4104 87,388,8
S 266 < 63> 63 97,384,0 90,5117 107 118
S 253 > 63 82,8 114 91,6
S 230 > 63< 63 82,8114 89,087,0 90,479,8
S 231 > 63< 63 95,296,8 81,197,1 83,283,2
< 63 82,6 97,9 99,4
S 232 < 63> 63 78,483,6 74,791,3 84,995,5

129

procedural efficiency aAppendix 3.2.2. Percent recovery ofnd reproducibility in SPM and SPE. surrogate standards used for compensating the

SampleStation d10-phenanthrened10-fluoranthened12-perylene
SPMRiver S10275,6 93,3 79,4
S105 S115118 80,2 91,185,1 99,579,4
S205 84,2 114 87,7
S218 S272103 10196,1102 92,295,4
92,2103109S216 S 291 85,5 103 88,4
96,6103103S 301 Estuary S 139 103 73,5 92,3
S 140 10888,8 90,3
S 137 102 85,2 82,4
113118 93,9S 134 S 133 89,2 86,8 101
S S 132 124 98,579,0 84,898,1 93,497,4
115112102125 126 12810191,0 86,392,0 95,593,7
104 105 87,2 130 CoastS 225 10694,7 106
S S 227 226 10788,2 96,5105 10596,1
S 228 89,7 95,7 98,4
S S 267 266 87,2104 102 90,9 96,1105
101107101S 233 S S 231 230 88,596,1 108 88,5 101 76,0
S S 229 232 86,285,2 95,990,0 10194,8
S 251 93,3 104 93,2
SPES 291 85,4 85,3
S S 370 301 87,8 97,1
S S 305 307 98,296,7 88,477,2
101 88,0S 312 S S 316 314 88,095,9 81,297,9
S 317 94,6 91,5
96,8103S 318 S 324 79,9 71,5

130

Appendix 4. Tables for the Manuscript in the Chapter IV Table 1. Sampling stations and properties of the sediment fractions Sand Mud Station Percentage Organic Total C/N Percentage Organic Total C/N
of total Carbon Nitrogen (mol/mol) of total Carbon Nitrogen (mol/mol)
sediment (%) (%) sediment (%) (%)
River
S 2S 101 4 1745.5 .2 2.1.71 34 0.0.25 30 9.8.1112 45.3 77.8 3.2.39 08 0.75 0.40 6.91 4.82
S 20 76.6 0.29 0.01 41.7 16.8 2.98 0.29 11.8
S 104 99.0 0.05 0.003 18.5 0.40 n.a. n.a. n.a.
S 105 98.4 0.14 0.008 19.4 1.11 n.a. n.a. n.a.
S 35 87.3 0.22 0.01 24.3 2.22 n.a. n.a. n.a.
S 4S 116 2 6.34.1 06 143.52 .0 0.0.34 62 2611.2 .9 62.6 63.3 3.3.70 24 0.0.26 38 9.16.4 89
S 145 69.0 2.08 0.11 22.5 28.4 1.41 0.20 8.32
S 143 Estuary 33.0 4.04 0.36 12.9 60.4 2.25 0.13 20.4
S 142 24.2 24.0 1.14 24.6 70.3 1.27 0.16 9.53
S 138 12.3 9.07 0.64 16.5 70.3 1.46 0.19 8.85
S 252 S 134 59.1 16.3 4.78 1.25 0.45 0.11 1212.7 .4 72.3 37.4 2.04 1.61 0.0.11 27 8.67 17.6
S 125 33.5 1.96 0.21 10.7 59.7 1.13 0.09 14.7
S 250 20.8 7.29 0.55 15.5 55.4 3.31 0.35 10.9
CoastS 251 91.8 0.22 0.03 9.08 4.14 1.82 0.08 27.2
S 269 6.78 0.11 0.01 24.0 84.3 1.05 0.09 13.4
S 226 18.8 0.23 0.01 28.1 72.8 0.41 0.04 12.2
S 228 S 227 18.0 28.5 2.37 2.66 0.06 0.07 4342.2 .8 75.8 65.9 0.34 0.46 0.0.05 04 9.80 11.7
S 267 64.7 0.01 0.001 11.1 29.0 1.19 0.10 13.8
S 266 55.0 0.30 0.01 49.2 26.9 1.15 0.09 14.8
S 230 S 253 3.75 24.1 0.05 0.28 0.004 0.01 1732.4 65.5 .9 69.5 1.29 1.44 0.09 0.09 16.2 18.7
S 231 7.25 1.13 0.04 30.6 69.2 2.18 0.14 18.8
S 232 4.58 6.72 0.16 47.9 83.0 1.71 0.11 18.6
n.a. = data not available due to insufficient sediment
131

Table 2. Median and range of PAH contents (ng g-1 d.w.) in the global sediment fractions from
following their elutione ordered by and the coastal areas. The PAHs arthe Siak River, estuarytime. PAHs Bulk was calculated from the fraction contents
Compound River Estuary Coast
MedianRange MedianRange Median Range
SANDNaphthalene 48,8 14.2 – 310 45,8 13.0 – 221 42,0 3.24 - 84.0
AcenAcenaphaphththene ylene 21308 ,5 19..9638 –42 – 155 35 21304 ,3 78.024.7 –20 - 83.5 85 18405 ,5 54.2560 - 17 - 133 80
FlPhuoenreanneth rene 27,096,2 91..0925 - 8 – 321 9.0 17,819,8 12.083 -.3 - 78 26..0 6 71,,7873 30..5681 - - 31 4.9.6 9
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
BenBenzo(zo(kb)f)flluuooraranntthheennee 14,497,9 21..0356 - 3 – 278 4.3 2105,4,3 61..7475 - 7 – 137 6.7 12,722,9 00..8074 - 5 - 179 0.5
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
FluoAcenarepneh thene 3,1884,4 1.3.9082 - - 1 450..19 3,2454,9 1.2.5723 - - 4 6.58.21 2,1083,7 1.1.0860 - - 3 7.09.37
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
BenChryzo(sebne)fl uoranthene 8,1760,8 2.3.5991 - - 7 592..70 8,1429,9 5.2.5637 - - 3 182..98 8,5,8651 2.0.8967 - - 5 519..81
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 Locations Sampling PAH range Reference
year
AsiaIndonesia, Riau Province 2004 - 2006 16 837 164 - 5474 Sand fraction, this
studycoastal areas Siak river, estuary and the 16 493 126 - 1314 Mud fraction, tstudy his
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 2003, 2004 17 Boonyatumanond et al.,
2006 y tuaresRiver 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 PChina earl River and Estuary, 2002 18 279 189 - 637 Luo et al., 2006
Middle and lower Yellow 2004 13 91 31 - 133 Li et al., 2006
River, China Daya Bay, China 1999 16 481** 115 – 1134 Zhou & Maskaoui, 2003
Jiulong River Estuary, China 1999 16 238 59 - 1177 Maskaoui et al. 2002
Korea Mouth of Han river,
Kyeonngi Bay, Korea 1995 18 83* 29 – 230 Kim et al, 1999
Masan Bay, Korea 1997 18 680** 207 – 2670 Yim, et al, 2005
India, Yamuna River, Delhi, (river 2003 16 9490 4500 - Agarwal et al., 2006
23530 bank sediment) Europe
Italy, PortoSardinia Torres harbor, Northern 1999 16 740 70 – 1210 De Luca et al, 2004
Olbia hSardiniaa, Italy rbor, Northern n.a 16 315 160 - 770 De Luca et al., 2005
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

34 1

006 56102° 00, astCo
901° 53, 576 01° 53, 549 01° 37, 506 01° 14, 6 5701° 11, 8 6001° 07, 1 7700° 49, 06 700° 45, 48 600° 42, 75800° 35. 531, 33°000 41102° 00, 8 98101° 53, 5 24102° 10, 6 86102° 09, 80 5102° 08, 66 5102° 03, 58 6101° 47, 22 1101° 40, 014101° 35. 217,3 21°10
etuditLa 37.0 53.0 ND ND 55.3 ND ND NDND 68.1 29.7e neryp)
acene r)anth 10.9 DN DN D 39.2 NDN3.71 22.5 2.16 45.512.7 81.0<DL <DL D24.5 N2.65 D1.19 N1.95 32.710.4 enelyerp)
vince ProuaiRs of aear laasto the cdn ayestuar River, the akim the Sfroin the water )
g LnAHs (P of notincentra. Co 61.7 01.8 40.6 97.86 5.82 4.358.5 1.03 5.33 .31125.9 acene hrtna)anluorf) 02.6 91.5<DL 96.84 6.65 2.8<DL 29.0 4.28 .11545.2 ethen 90.1 20.3 60.2 21.60 3.94 0.7<DL 0.26 1.32 53.813.5 enehtnarluof) 30.120.2<DL30.77.211.47 0.9310.82.66116.5 4.7yrenep)ha,
V ter Chapript in the e Manuschtfor 5. Tables Appendix ble 1Ta 18 3S7 1 3S24 3S6 1 3S4 S 312 S 317 S 301 S 305 S 3070 3S1 S 29 dnoupmCo 29.818.7 25.257.631.5 8.86 49.9 21289.1 .557 553phthalene aNDNDNDN76.7140.176.8 DN133918 ND231ecenaphthylenA ND ND ND ND ND 4.4 3ND 9.2 9ND DN ND neehthpaneAc 82.3 83.6<DL 728.8 13.3 9.3<DL 72.4 23.0 13.99.26 e enorFlu 25.242.9 31.055.7 831 02164.9 6212 538 .35266.3 anthrenePhen7 3.57 6.93 1.76 18.7 3.99 8.7 2.60 1111.4 7 4.010.5 acene rthnA 49.439.8 54.980.3 651 DN28.9 0525 527 .75891.8 ethenanorFlu 11.211.5 8 7.117.433.2 16.2 28.1 20441.6 .82225.5 ne erPyzo(Ben 31.7 71.6 70.4 57.86 11.8 5.048.9 2.15 4.43 35.410.8 enesyrChzo(Benzo(Benzo(Ben(onzebDizo(Beneno(1,2,3-Ind0 30 1311 20 1239 165 89 321 0415 53010 524 28 sHAPction e = below det; <DLedt detectoND = n timli
Estuary River-1e Longitudc,dg,h,iakba

35 1

5 601 36.8PRW 195283S 8146 782 ND ND ND 124.0 0.8 365 7012 521 6. 1250.9 8 149732 5 171927 6 18122 2 35117.2 5167 724 ..3 610.7 1.2 212 ND 545.1 4460 7 ND ND
.3r-06449 0 7645, °00 135, 33°005 6746, °00 58, 67101° 4 21,73101° 2 46, 36 4°110
182 S291 PKU 82a6 M 1316157 282 ND 44.2584 11.6471 319 21.3 37.3 59.5 6.95 21.2257 124 17.1
144 59.8PRW 224S

0 , 77° 320061 11° 28, 01
36.5 16.5 1168 1.46 .4.0
22 °101 ´´101° 28, 121 , 9908101° 11° 35,319 01 ´´,759 ´
p-04 eS 40r-Ma Jul-05 .342 38.9152 79.2 40.5 28.8 23.0 17.5.11262 81 647 85 1 101529 2 36715 694
S218 2S27 502S 151S 051S 2S10S9 S10 17SniotaSt
° 300 ´´5,6´ 435 °0098 6,2° 400 615,° 3200 '',70' 4° 360053 , 7° 32006 , 79° 360046 8,5° 300 ´´,923 ´35,43 ´8 1°110 40,105 °101 101° 26,118' '5,50' 1° 1901
g gent (ntHs con PA.019 112 111512 512 093185 0acene 3r)anth 271356 .987278 78.613.4 .293 .845.6 34 825 348enelyerp)
.826 .130 .696.11 94 .07 768 1773 518138 12acene hrtna) .116 .149 .9087.54 58. 137 8037 533209 32 ethenanluorf) 0.81 216. <DL 736. 3.48 5.17 152 59 3enethnaorulf) 89.6 .321 .019 16.51.46 76.1 .348.0 92 642 rene 182yp)ha,
.ble 2.aTa U KPUpstream PRW U KPUpstream PRW PKUam erstp U dnoupmCo .215 .729313 911 .709835 8171 27117 047phthalene 1aN .966125 269 0011 8101724 6513 93210 477e 1cenaphthylenA NDND ND DNND ND DN 78.2 .7 96ecenaphthenA 5.13 2.32 9.12 2.52 0.56 3.74 1.69 122 48 2neeruolF 369333 199 368 5531335 1153 6008350 6anthrenePhen 15.6 5.00 51.53.95 65.7 .422.7 13 79.2 .9acene 85rthnA 261252 8199 914 7318845 4190 5658 654ethenanorFlu 217501 310550.8 7253897 52916 07117 501ne 1erPyzo(Ben .143 .550140 5.69 .1531062 7107 094226 8 2enesyrChzo(Benzo(Benzo(Ben(onzebDizo(Beneno(1,2,3-Ind475 1 6208 2426 3023 4250 37381 401573 74390 9055s HAPSPM (mg/L) )Lg/n (sAHPg wana= Per WRbaru; PkaneP= KU it; Pmliction e = below det; <DLedt detectoND = n
f SPM eth n) i ters. River wa aki Smor
itLaetud.5 10 DN35.6 .1 32yrenep)
-1eLongitudc,dg,h,iakba

36 1

92 ,9a 6.72 4.27 3. 26
psu) 25 >(h Hig srteestuarine wa min the SPM fro)
-18 S 12 S 125 S 133 S 124 S 132126 S0 3 1S4 S 13 S 137140 S39 1S62.2 6 2.35 220.810.9 5.0 0 .3 1.3141 48.3 51.3135 625 74.269.2 38.2280262 129 107 51.2179 69.7 95.2 97.325.4293 128127 233
0301° 14,354 01° 13,539 01° 15, 47414, 01° 85701° 15, 01° 15,591 915,7 0°10 84501° 07, 47201° 07, 616, 04°01 999, 13°10 3 112°10 981102° 11, 072102° 10, 022102° 10,6 1610, 2°01 256102° 10, 2 10,21°102 336,9 02°100 15102° 09, 397102° 07, 859, 072°10
psu)itude Long10.0 ND ND .00163 .1 ND 5 1.9DN 72.2 3.18 23.7 reneyp)
– 25 gntent (ngos c PAH86.2 137 .471 .948.1 0 382. 116.552.3 526254 991acene r)anth 40.6 42.649 . 421. 296.4 DN .961 .013 17.5 enelyerp)31.3 ND
12.5 .632 18.5 20.704 .9 20.4 0 2.500 342.1 2.55 37.7acene hrtna) 6.92 6.32 7.11 7.31 7. 114. 17.374 8.47 5.15 7.21 .581 enehtnaroulf)3.71 .771<DL 93.279 . 079. 050.414.0 .611 .711 10.2 enehtnarluof) 84.5 373. 1.20 987. 7. 1160 5.97.5 0.11 915. 42.5 72.9 eneryp)ha,
(10 b..ble 2Ta dnoupmCo75.1 337 218 .351 127 .524 71.7 0312 .352 .110 96aphthalene 1N28.9 ND 0276124 346ND ND 3225ND .633 De NcenaphthylenAND <DL ND ND DN 63.<DL 2 DNND ND DN ecenaphthenA 3.51 DN 9.18 806. 2. 1895 3.78.5 3.13 975. 59.5 .822 neeruoFl 971144 202 .957 416 .662 77.041 8.374 .840 312 anthrenePhen3.12 74.2 65.3 03.227 . 373. 001.718.3 84.1 1.32 15.7acene rthnA 615 141 251 0.58 132 1.22 .41 73 813.11 1.04 421 neehntaruoFl 710 891 2.59 6.76 3. 614. 20.105 4931 2.35 6.83 184 enrePyzo(Ben 4.41 4.22 568. 107. 281. 965. 57. 82 414.11 21.9 .367ne esyChrzo(Benzo(Benzo(Ben(onzebDizo(Beneno(1,2,3-Ind 857 9105 3348516 2128156 36769 76745482 8081 s HAPSPM (mg/L) )Lg/n (sAHPa timn litectio below ded; <DL = not detecte; ND = valuetedam = esti
Medium psu) – 100( Low Latitude)us (ptyniilSac,d
g,h,iaakb

37 1

ofyit5 , 83 03°10 02, 65
2° 13100 , 932° 1310 4051,48 , 7
232 S31 2S0 S 23 S 251233 S6 6 2S7 S 26
-1
658 38.7279 105 215 804 638 611 2342 241 271 18 3ND ND 65.0ND 530 3105 283 ND .578337 62 4ND ND <DLND ND7 25.7 86.137 ND5 22. <DL <DL ND 1.61 13.0 4.206.74 15.1 NDND LD<7.08 ND <DL15.8 172 26.149.7 98.1943 342 55 878.9 .689 68 70.91250 0.87 7.50 1.402.23 1.89 54 7. 39.2 2.4542. 4 3.555.32 2.28 37.2279 77.0134 335 106 870 1138 206 166 55 2122 45.0724 77.4163 897 263 054 2321 209 185 18 3343 6.46 24.9 17.619.5 20.4 76.101 4 23.7.20 5 24.548.5 40.5 8.17 86.0 13.317.0 38.9 79.407 2 21.3.58 3 28.545.0 46.7 19.7156 25.177.3 40.3 183.342 8 59.2.33 2 82.383.1 76.5 3.79 3.53 5.554.19 2.78 25 4. 36.0 3.6252. 4 0.964.68 5.19 2.84 11.3 2.8811.9 9.06 732.39 2 8.0492. 5 11.221.0 14.1116 359 51.877.6144 578 64 7 70.0.49 883.467 1109 17.2 31.2 43.094.9 14.4 25.979 1 81.4.14 96.3385 1 4.3590 1. ND ND09 5. ND NDND25 7. NDND NDND 125.5 22.7 58.558.3 15.6 12.5 14.4 9.25.43 1 22.912.5 16.6 40.8 48.7 31.584.9 35.4 82.347 1 11.7.85 1 33.126.1 28.0
sastline o cauiRe ht fort ap htrone ht morlled febare las tion staehstal waters. T coamorf SPM n) icl riastduthe in t agnartit
S 2259S 2228 2S27 2S6 S 22
01° 15 , 67° 2010 350° 16,01 095 ,62 01°40 , 2° 31100 , 38° 3710 497,35° 0170 0 ,83 01° 20''0 ° 41'010 97° 39,10 745,14° 01, 142° 06100 931° 59,10 990,35° 10195 3 ,002° 01 10''1 ° 51'101' '01 4'34 01°1 150,43 °10159 8 ,01° 2711° 10218 1 ,90 02°10
c..ble 2Ta gnaj Pan Selatfuth path o soeh to tnwod uingintnod cni aamDu dnoupmCophthalene aNe cenaphthylenA ecenaphthenA neeruolF anthrenePhenacene rthnA neehntaruolFrene Pyzo(Ben enesyrChzo(Benzo(Benzo(Ben(onzebDizo(Beneno(1,2,3-Ind326 1462 935 7 2263 1455596 43102 212682 11 494 18220 7168 s HAPSPM (mg/L) )Lg/n (sAHPa tmi detection li = belowt detected; <DL = noDrait; NStacca lat to the Mcenajions ad= stat
a eudg g (ntnetAHs conP enelyerp)
Station acene Longitude ) reneyp
Latitrc,d)anthacene thrna)a ethenanluorf)bl)fe nehtranoukrene yp)ag,h,i
ha,

38 1 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.
Locations Sampling PAHs Median* Content Reference
e rang yearDissolved PAHs (ng L-1)
Indonesia, Riau Province
Siak river 2006 16 824 129 – 5140 This study
Siak estuary 16 385 320 – 619 This study
Riau coastal areas 16 130 121 – 130 This study
China
Rivers in Tianjin 16 119** 45.8 – 1272 Shi et al., 2005
Daya Bay 1999 16 10984*** 4228 – 29325 Zhou & Maskaoui,
2003Minjiang 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
Seine River, France 1993 10 2 4 – 36 Fernandes et al.,
1997Baltic 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 SpillThe Prestige, NW & northern 2002 16 270*** 60 – 2090 Gonzáles et al.,
2006Spanish coast, NY,The No * rth Cape, Point Judith Pond, 4 days after n.a 13700 – 497000 Reddy &2001 Quinn,
32 days after n.a ~ 300
Forest Fire
The Llobregat river, Catalonia, 1994 12 70 2 – 336 Olivella et al., 2006
ain northern SpMeSpain diterranean creek, Catalonia, 2003 16 2.29 0.34 – 4.29 Vila-Es2007calé et al.,
Particulate PAHs (ng g-1 d.w.)
Indonesia, Riau Province 2004-2006
Siak river 16 5286 1475 – 59050 This study
Siak estuary 16 758 156 – 7669 This study
Riau coastal areas 16 1572 326 – 10234 This study
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
Seine River, France1993 10 + 1 5000 1000 – 14000 Fernandes et al.,
alkyl 1997
Elbe River, Germany
At Hamburg 1994 - 1995 18 + 4 4150 2540 – 8980 Heemken et al.,
alkyl 2000
At Dessau 11850 6300 – 16570 Heemken et al.,
2000*) own calculation from the literature data
**) median of the mean values of the sum PAHs
luea***) mean vn.a = unavailable data from the given literature for median calculation

Appendix 6. Tables for the Manuscript in the Chapter VI and properties of the sediment fractionsSampling stationsTable 1. Station FineCoarse)) Perceof total ntage* OrgaCarbon nic Nitrogen Total (molC/N /mol) Perceof total ntage* OrgaCarbon nic Nitrogen Total (molC/N /mol)
sediment (%) (%) sediment (%) (%)
Siak SumatraS 138 S 143 12.3 33.0 9.07 4.04 0.36 0.64 1216.5 .9 60.4 70.3 1.46 2.25 0.0.13 19 8.85 20.4
S 134 16.3 4.78 0.45 12.4 72.3 1.61 0.11 17.6
S 253 S 250 20.8 24.1 7.29 0.28 0.55 0.01 1532.5 55.4 .9 69.5 3.31 1.44 0.35 0.09 10.9 18.7
S 230 3.75 0.05 0.004 17.4 65.5 1.29 0.09 16.2
S 231 S 232 7.25 4.58 1.13 6.72 0.04 30.6 0.11 47.9 69.2 83.0 1.2.71 0.11 18 0.14 18.6 18.8

Wenchang and Wanquan HainanWR-B/06 41.2 0.52 0.04 17.2 58.8 1.21 0.12 12.1
K/06 60.4 0.46 0.02 22.9 39.6 2.84 0.24 14.0
H/0BB4/076 1968.3.8 0. 1.1324 0.0.0201 8110.3.1 3180.2.7 1. 1.9198 0.0.1918 1112.6.6
WW8/07 32.6 0.39 0.01 33.8 67.4 2.14 0.15 16.7
WW10/07 40.6 0.37 0.02 18.4 59.4 1.80 0.16 13.5
2-CC01/07 85.7 3.87 0.05 88.2 14.3 4.11 0.09 52.3


*) 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
e. elution tim following their ordered byWenchang and SiakCompoundWanquan Median Range Median Range
CoarseNaphthalene 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
ChryBenzo(seneb )fluoranthene 18.9 14.6 7.67 2.51 – - 137 49.8 25.8 4.61 9.17 – 2.62 – 63.0 32.1
Benzo(k)fluoranthene 7.76 0.73 – 76.7 1.77 0.01 – 7.90
Benzo(Dibenzo(a)pya,hrene )anthracene 17.0 522 11.2 4.85 - 249 - 1061 1.21 4.61 0.17 – 1.15 – 11.9 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
FineNaphthalene 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
ted c= not deteND

140