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ALIPHATIC BIOMAKER OF CRUDE OIL OF BUNYU ISLAND, BULUNGAN DISTRICT,

NORTH KALIMANTAN (BN 20)


Zjahra Vianita Nugraheni, M.D. Ari Rahman, Endah Mutiara M.P., Yulfi Zetra, Agus
Wahyudi and R.Y. Perry Burhan*
Department of Chemistry, Institut Teknologi Sepuluh Nopember (ITS)
Jl. Arief Rahman Hakim, Kampus Sukolilo, Surabaya 60111
* Corresponding author, tel/fax: +62-8113442558, email: pburhan@gmail.com
Co-author 1, email: rharha.vianita@gmail.com
Co-author 2, email: mdedyarirahman@gmail.com
Co-author 3, email: endah_mutiara@hotmail.lcom
Co-author 4, email: yzetra@chem.its.ac.id
Co-author 5, email: agus@chem.its.ac.id

ABSTRACT
Organic geochemical characteristics (biomarkers) provides information about the
environment and the maturity of crude oil. The crude oil was separated to produce pure oil
and then extracted using n-hexane : crude oil (50: 2) as a solvent for 24 hours and
centrifuged at 2400 rpm for 20 minutes to separate the crude oil and aspaltan. The extract
obtained was fractionated using McChharty column chromatography methods. The
obtained extracts are neutral, acidic and polar fractions. Neutral fraction separated by
KLTP method to produce aliphatic compounds. Aliphatic compounds obtained from the
neutral fraction was analyzed using GCMS. GCMS results showed the presence of nalkanes, alkyl cycloalkanes and sesqueterpen bicyclic compounds.
Keywords: Biomarkers; Hydrocarbons; Bulungan District; Bunyu island; crude oil; GCMS;
Organic Geochemistry
ABSTRAK
Karakteristik geokimia organik (biomarker) memberikan informasi tentang lingkungan
dan juga kematangan minyak mentah. Minyak mentah yang masih tercampur dipisahkan
untuk menghasilkan minyk murni lalu diekstraksi menggunakan pelarut n-heksan : minyak
mentah (50:2) selama 24 jam kemudian disentrifugasi dengan putaran 2400 rpm selama
20 menit untuk memisahkan minyak mentah dan juga aspaltan. Ekstrak yang diperoleh
difraksinasi dengan menggunakan metode McChharty yaitu kromatografi kolom. Hasil
ekstrak dari kromatografi didapatkan fraksi netral, fraksi asam dan fraksi polar. Fraksi
netral dipisahkan dengan metode KLTP untuk menghasilkan senyawa alifatik. Senyawa
alifatik yang diperoleh dari fraksi netral dianalisis menggunakan GCMS. Hasil GCMS
menunnukkan kehadiran n-alkana, alkil sikloalkana, dan senyawa bisiklik seskuerterpen.
Kata Kunci: Biomarker; Hidrokarbon; kabupaten Bulungan; pulau bunyu; minyak mentah;
GCMS; geokimia Organik

INTRODUCTION
Petroleum is a mixture of gas, liquid and solid hydrocarbons with smaller amounts of
nitrogen, oxygen and sulphur. Petroleum is formed through two phases, diagenesis (the
formation process of karogen) and katagenesis (the convertion process of karogen into gas
and petroleum) [1].
Molecular characterization of petroleum is very important to determine the thermal
maturity, depositional environment, rock sources, type of material source and estimated
age of rocks. All of molecular characterization can be obtained by knowing the type of
petroleum biomarker. Biomarker is a complex compound derived from a living organism.
Biomarker generally found in crude oil, rocks and sediments that are stable and showed
any change or without any change in the structure of organic molecules derived from main
source [2].
According to Burhan et al. (2002) [3], the classification of biomarker depend on their
fractions can be divided into three groups that is neutral fraction, acidic fraction and polar
fraction. Tarakan-Bunyu basin is one of the basins located on the Borneo Island
(Kalimantan). Basically, the NE basin in Kalimantan is divided into 4 groups, Tidung basin,
Berau basin, Muara basin and Tarakan basin. One of basin that is located in Tarakan called
Bunyu basin [4].
Geological and geophysical data regarding Bunyu exploration wells has been
obtained through the early survey on the Bunyu well. Bunyu Island Subdistrict located in
the Bulungan District, North Kalimantan province has great potential as oil producer in
because of its located in flat areas with some plateau and has a moderate slope. The oil
wells located in North Kalimantan had one sub basin that is Tarakan sub-basin located in
Tarakan city and Bunyu Island. The formation of petroleum is derived from quartenery era
dating from about 2 million years ago [5].
EXPERIMENTAL SECTION
Materials
Crude oil from Bunyu Island, Bulungan District, North Kalimantan, nitrogen, filter
paper, aluminum foil, cotton, sea sand, cellite, aquabidest, diethyl ether (C 4H10O) p.a,
dichloromethane (CH2Cl2) p.a, acetone (C3H6O) p.a, chloroform (CHCl3) p.a, methanol
(MeOH) p.a, n-hexane p.a, 2% KOH solution, formic acid, silica gel GF254 for column
chromatography, diazomethane, sodium periodate (NaIO4), 1,2,5, 6-dibenzantrasen (DBA),

BF3, isopropyl alcohol (IPA), acetonitrile, carbon tetrachloride (CCl4) and ruthenium
tetroxide (RuCl3.XH2O).
Instrumentation
A set of reflux apparatus, soxhlet apparatus, column chromatography apparatus,
rotary evaporator, vials, analytical balance (digital), oven, chamber, Thin Layer
Chromatography (TLC) preparative plate, GC-MS and other supporting glasse equipments.
Procedure
Preparation of Oil
The sample of oil was separated using separating funnel to obtain the mixture of
crude oil and asphalt. Four grams of crude oil was mixed with 90 mL of n-hexane and
precipitated for 24 hours at room temperature. A mixture then centrifuged to ensure
separation between crude oil and asphalt. The crude oil was evaporated using a vacuum
rotary evaporator to obtain pure oil (free n-hexane), then stored in vials and dried using N 2
gas. The pure oil was weighed and stored for further analysis.
Drained pure oil then separated using column liquid chromatography to obtain a
neutral, acid and polar fractions. To separate the acid fraction, diethyl eter was used as
solvent. The neutral fraction obtained was re-fractionate using preparative TLC method for
separating hydrocarbon, alcohols and ketones fractions. Fractionation process was done
by dissolving the neutral fraction in dichloromethane (DCM). Furthermore, the extract
spotted on the TLC plate. The plates were eluted in the chamber using dichloromethane
(DCM) as eluent.
The

hydrocarbon

fraction

was

separated

using

Preparative

Thin

Layer

Chromatography (PTLC) method and n-hexane as the mobile phase. This separation aims
to get a fraction of aliphatic and aromatic hydrocarbons. Elution process of hydrocarbon
fraction as same as with elution process of neutral fraction. After the elution process is
complete, the silica gel containing aliphatic and aromatic fraction was extracted using
funnel tulip with n-hexane as solvent. This extraction process produces dry fraction of
aliphatic, aromatic, n-hexane and dried using N2 gas to produce purified fractions.
Characterization
One mililitre of the results of fractionation (aliphatic and aromatic fractions) injected
into Gas Chromatography-Mass Spectroscopy (GC-MS) apparatus. The operating
conditions are 50 C of oven temperature (5 minutes on hold) with 10 C/min of rate, and

isothermal temperature at 290 C for 25 minutes. The results of GC-MS subsequently be


interpreted as biomarker compound from petroleum.

RESULTS AND DISCUSSION


Gas Chromatography Analysis
The resultof GC-MS analysis of aliphatic fractions of crude oil from Bunyu Islands,
Bulungan District, North Kalimantan can be showed in Figure 1.
Biomarker of n-alkanes
The presence of n-alkanes compounds in the aliphatic fractions of sample was
identified by fragmentogram m/z 57, which is the base peak of alkanes compound. The
base peak at m/z 57 was identified as a result of the release of the buthyl group (-C 4H9)..
Fragmentogram m / z 57 aliphatic fraction hydrocarbon shown in Figure 2.
The mass spectrum of n-alkanes the hydrocarbon follow a distinctive pattern that
decreases linearly from the peak at m/ 57 as the base peak to m/z 71, 85, 99 and so on
with the addition of 14 ( as the loss of a methylene group (-CH2-) [6].
N-alkane compounds are widely distributed in various plants and organisms so that it
can be the most common biomarker exploited as geological mark. Distribution of n-alkane
can be used to determine the source of organic material and the maturity level of sediment
[7]. The distribution of short-chain n-alkane with carbon atom number of C <20 derived from
marine organisms such as algae. Short-chain n-alkanes are usually derived from aquatic
autothrops photosynthetic organisms, and C16, C17, C18 are the type of strains of bacteria
and algae [8].
N-alkanes compounds in the sample contain compound that have carbon atom
beetween C15 to C32 which is an indicator of terrestrial (land) plant derived from higher
plants [9]. However, the compounds with the number of atoms C <20 are less dominating.
If at any sediment identified homologous n-alkanes with number of atoms carbon range
between C15 to C20 and C17 at the maximum peak, the source of the sediment organic
matter derived from marine phytoplankton and algae [8][10]. The contribution of marine
phytoplankton and algae as a source of organic matter on Bunyu crude oil is very possible
because the geological of Bunyu Island is a small island surrounded by the sea.
Distribution of long-chain n-alkanes are dominated by C21-C25, show that the source of
the sediment organic matter derived from vascular plants, microalgae, cyanobacteria,
sphagnum and aquatic microorganisms, especially macrophytes. Tissot and Welte (1984)
[11] also stated that the homologous compounds of n-alkanes C25-C35 is a marker
compound for sedimentary organic matter source derived from the wax coat of higher

plants. The same thing also expressed by Eglinton and Hamilton (1967) [12] that the nalkanes hydrocarbon C29-C31 is a marker compound for terrestrial plants.
The distribution pattern of n-alkane compounds can also demonstrate the maturity of a
sediment. These sediments generally have a dominated distribution of short chain nalkanes. Extracts from immature sediments usually have less amount of even carbon, but
with the increasing of maturity level, the even carbon atoms can be formed. The formation
of carbon through a diagenetic process of aliphatic hydrocarbon contained in kerogen or
alcohols, esters and other alkanes [13]. The crude oil of Bunyu island has n-alkanes in the
range of C15-C31 dominated by long chains of carbon atoms in which the odd carbon
dominant to even carbon [11]. From the results, it can be concluded that crude oil is the oil
that has a low level of maturity.
Biomarker of alkyl cycloalkanes
Identification of alkyl cycloalkanes biomarker compounds in in the sample has been
done by interpretation of mass spectra at the peak of m/z 83. The fragmetogram of
aliphatic alkanes can be shown in Figure 3.
Alkyl cycloalkanes biomarker compound was identified from total chromatogram of
aliphatic fraction. The founded compound is alkyl cycloalkanes that have C 15-C22. The
presence of alkyl cycloalkanes of range C16-C19 have identified as the presence of bacteria.
This is because the precursors of alkyl cycloalkanes is a fatty acid derived from bacteria.
This results is similar with the previous research from Fowler et al. (1986) [14] which stated
that alkyl cyclohexane with total amount of carbon C 16-C19 in Nonesusch Seep oil has 13cyclohexyl tridekanoat acid derived from bacteria as precursors. Rodrigues et al. (2005)
[15] also said that alkyl cycloalkane compound with total amount of carbon C 14-C33 shows
that the crude oil is derived from the cell membrane of Bacteriallicyclobacillus sp.
The high temperature and pressure used in the liquefaction process allow the
formation reaction of alkyl cycloalkanes. These compound can be derived from alkyl nalkanes, mono- and substituted cycloalkanes resulting from radical cyclization reaction of
olefins during thermolysis process of n-alkanes [16].
Bicyclic sesquiterpene compound
Identification of bicyclic sesquiterpene biomarker compound in the sample has been
done by intrepretation of mass spectra at the peak of m/z 123. The fragmentogram of
bicyclic sesquiterpene compound can be shown in Figure 4.

The fragmentogram of m/z 109 is indication of kadinan compound. Distribution of


kadinan compound confirmed as a result of pyrolysis products derived from resin that
appear on the earth in the Miocene age. The resin is derived from Dipterocarpeceae [17].
(Widodo et al, 2009). Kadinan compound biomarker indicate that filling material derived
from biological materials from Angeospermae family and shown the contribution of organic
matter derived from terrestrial. It is also supported by -concha kerala shore research in
west India that had been done by Dutta and Mallick (2010) [18]. This research reported
that Dipterocarpaceae is a productive plant vegetation in tropical rain forest with warm
conditions during the Miocene age. From the previous explanation, it can be conclude that
Dipterocarpaceace contribute the formation of crude oil in

Bunyu Island, Bulungan

Dstrict,North Kalimantan.
Ion fragmen at m/z 123 is a drimane and homodrimane compounds belongs to
sesquiterpene compound. Some sesquiterpene and diterpene can be synthesized by
bacteria and seaweed [19]. Simoneit, 1986).
Bicyclic sesquiterpene compound with C15 called driman. Driman derived from the
reduction of drimanol derived from microbial and formed from petroleum. Driman presence
in sediments and crude oil derived from microbes [21].While the presence of bicyclic
sesquiterpene compound with C16 indicate that crude oil from Bunyu island has undergone
a hopanoid microbial degradation in the rock source during diagenesis process. The
diagenesis process form functionalization bicyclic compound that had rearrangements
reaction to form drimane.
CONCLUSION
Based on the results of the analysis of crude oil samples from Bunyu island, Bulungan
District, North Kalimantan, there was a distribution of n-alkanes C15-C32 compounds.
Distribution of n-alkanes C15-C32 compounds showed the contributions of terresterial plants
derived from higher plants. The distribution of n-alkanes C15-C20 and C17 at maximum peak
indicated the contribution of marine phytoplankton and algae. The distribution of n-alkanes
in the range of C15-C31 dominated by long chains of carbon atoms in which the presence of
odd carbon is more dominant than even carbon indicate that crude oil is the oil that has a
low level of maturity.

ACKNOWLEDGEMENTS
Authors say thanks to the Laboratory of Molecular Geochemistry, Department of
Chemistry ITS that has provided the opportunity to do research.
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Figure 1 The total chromatograms aliphatic hydrocarbon fraction of crude oil Bunyu
Islands, Bulungan district North Borneo

Figure 2 Fragmentogram m/z 57 n-alkane aliphatic fractions hydrocarbon compound of


crude oil Bunyu Island, Bulungan District, North Borneo

Figure 3 Fragmentogram m / z 83 cyclealkane fractions hydrocarbon compound of crude oil


Bunyu Island, Bulungan District, North Borneo.

Figure 4 Fragmentogram m/z 123 bicyclic sesquiterpene hydrocarbon compounds


aliphatic fractions of crude oil Bunyu Island,Bulungan District, North Borneo.