Bourdet 2014 GCA

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Geochimica et Cosmochimica Acta 142 (2014) 362–385
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Evidence for a palaeo-oil column and alteration of residual oil

in a gas-condensate field: Integrated oil inclusion
and experimental results
Julien Bourdet a,⇑, Robert C. Burruss b,1, I.-Ming Chou b,2, Richard Kempton a,3,
Keyu Liu a,4, Nguyen Viet Hung c
a
CSIRO Energy Flagship, ARRC, 26 Dick Perry Ave., Kensington, 6151 WA, Australia
b
U.S. Geological Survey, 954 National Center, Reston, VA 20192, United States
c
Japan Vietnam Petroleum Company Limited, Exploration Group – JX Nippon Oil & Gas Consulting Services,
Green Power Building, 35 Ton Duc Thang Street, Ben Nghe Ward, Dist. 1, Ho Chi Minh City, Viet Nam
Received 18 December 2013; accepted in revised form 21 July 2014; available online 1 August 2014
Abstract
In the Phuong Dong gas condensate field, Cuu Long Basin, Vietnam, hydrocarbon inclusions in quartz trapped a variety of
petroleum fluids in the gas zone. Based on the attributes of the oil inclusion assemblages (fluorescence colour of the oil, bubble
size, presence of bitumen), the presence of a palaeo-oil column is inferred prior to migration of gas into the reservoir. When a
palaeo-oil column is displaced by gas, a residual volume fraction of oil remains in pores. If the gas does not completely mix
with the oil, molecular partitioning between the residual oil and the new gas charge may change the composition and prop-
erties of the residual oil (gas stripping or gas washing). To simulate this phenomenon in the laboratory, we sealed small
amounts of crude oil (42 and 30 °API) and excess pure gas (methane, ethane, or propane) in fused silica capillary capsules
(FSCCs), with and without water. These mixtures were characterized with the same methods used to characterize the fluid
inclusions, heating and cooling stage microscopy, fluorescence spectroscopy, synchrotron FT-IR, and Raman spectroscopy.
At room temperature, mixtures of ethane and propane with the 30 °API oil formed a new immiscible fluorescent liquid phase
with colour that is visually more blue than the initial oil. The fluorescence of the original oil phase shifted to yellow or
disappeared with formation of semi-solid residues. The blue-shift of the fluorescence of the immiscible phases and strong
CH stretching bands in FT-IR spectra are consistent with stripping of hydrocarbon molecules from the oil. In experiments
in FSCCs with water solid residues are common. At elevated temperature, reproducing geologic reservoir conditions, the fluo-
rescence changes and therefore the molecular fractionation are enhanced. However, the precipitation of solid residues is
responsible of more complex changes. Mixing experiments with the 42 °API oil do not form a new immiscible hydrocarbon
liquid although the fluorescence displays a similar yellow shift when gas is added. Solid residues rarely form in mixtures with
42 °API oil. FT-IR spectra suggest that the decrease of fluorescence intensity of the original oil at short wavelengths to be due
to the partitioning of low molecular weight aromatic molecules into the vapour phase and/or the new immiscible liquid phase.
The decrease of fluorescence intensity at long wavelengths appears to be due to loss of high molecular weight aromatics during
⇑ Corresponding author. Tel.: +61 8 643 687 67; fax: +61 8 633 685 55.
E-mail addresses: julien.bourdet@csiro.au (J. Bourdet), burruss@usgs.gov (R.C. Burruss), imchou@usgs.gov (I.-Ming Chou), richard.
kempton@csiro.au (R. Kempton), keyu.liu@csiro.au (K. Liu), hung.nv@jvpc.com.vn (N.V. Hung).
1
Tel.: +1 703 648 6144; fax: +1 703 648 6419.
2
Tel.: +1 703 648 6169; fax: +1 703 648 6252.
3
Tel.: +61 8 643 687 37; fax: +61 8 633 685 55.
4
Tel.: +61 8 643 687 83; fax: +61 8 643 685 55.
http://dx.doi.org/10.1016/j.gca.2014.07.022
0016-7037/Ó 2014 Elsevier Ltd. All rights reserved.
J. Bourdet et al. / Geochimica et Cosmochimica Acta 142 (2014) 362–385 363
precipitation of solid residues by desorption of aromatics and resins from asphaltenes. Desorption of low molecular weight
aromatics and resins from asphaltenes during precipitation can also increase the fluorescence intensity at short wavelengths of
the residual oil. Water clearly affects the precipitation of semi-solid residues from the oil phase of the lowest API gravity oil.
The change of hydrocarbon phase(s) in UV–visible fluorescence and FT-IR enclosed within the FSCCs were compared
with the fluorescence patterns of natural fluid inclusions at Phuong Dong gas condensate field. The experimental results sup-
port the concept of gas-washing of residual oil and are consistent with the oil inclusion attributes from the current gas zone at
Phuong Dong field. The hydrocarbon charge history of the fractured granite reservoir is interpreted to result from the trap-
ping of residual oil after drainage of a palaeo-oil column by gas.
Ó 2014 Elsevier Ltd. All rights reserved.
1. INTRODUCTION assemblages (OIAs, Eadington and Kempton, 2008) can

be more difficult. OIAs in a single petroleum reservoir
Complex histories of petroleum charge to reservoirs are may have a wide range of fluorescence colours, suggesting
well documented by geochemical studies of produced oils that the reservoir was filled with a number of different
and gases (for example Thompson, 2004; George et al., hydrocarbon charges, while appearing to be trapped at
2004; Volk et al., 2005). Mixtures can form as charges of about the same time in basin history. Furthermore, some
progressively more thermally mature oils and gases are OIAs in a uniform petrographic setting may have variable
released from a source rock during burial (Larter and liquid–vapour ratios indicating trapping in the presence of
Aplin, 1995; George et al., 1997; Zumberge et al., 2005), multiple hydrocarbon phases or necking down phenomena
or migration pathways from different sources converge (Teinturier et al., 2002). Recently, petrographic and spec-
toward a single trapping structure (Wilhelms and Larter, troscopic studies of the attributes of oil inclusion assem-
2004). The oil and gas initially expelled from the source blages demonstrated that some of the variance in the
can be altered in the reservoir through microbial activity attributes of oil inclusion assemblages is a consequence of
(Milner et al., 1977; Volkman et al., 1983; Peters and in-reservoir fluid interactions (Bourdet et al., 2012). Conse-
Moldowan, 1991; Blanc and Connan, 1994), water-washing quently, to accurately understand the charge history of a
(Lafargue and Barker, 1988), asphaltene and bitumen pre- petroleum system using fluid inclusion techniques, it
cipitation (Evans et al., 1971; Bailey et al., 1974; appears necessary to separate the attributes derived from
Wilhelms and Larter, 1994), in-situ cracking of oil to gas in-reservoir fluid interactions from those acquired from
(Schenk et al., 1997; Dahl et al., 1999), and in some cases, generation-migration processes.
several processes may happen simultaneously. As part of a study of the petroleum charge to the Phu-
The concept of progressive displacement of oil by addi- ong Dong gas condensate field, Cuu Long Basin, Vietnam,
tion of gas, initially known as Gussow’s hypothesis oil inclusion assemblages from the current gas zone and oil
(Gussow, 1954), has been part of petroleum geology for leg were systematically characterised using CSIRO’s
60 years. The effects of multiphase flow during displace- Frequency of Oil Inclusion technique (FOI, Eadington
ment of oil by gas during basin history, referred to as et al., 1996, 2000; Lisk et al., 2002). Although the FOI tech-
deasphalting (Evans et al., 1971; Milner et al., 1977), or nique documents the abundance of oil inclusions it also
gas-washing (Su et al., 2001; Losh et al., 2002; Losh and records selected attributes of oil inclusions in assemblages
Cathles, 2010) can profoundly affect the composition of such as the petrographic location, variance in the propor-
the reservoir fluid (Thompson, 2004), shifting it to a gas- tion of vapour, and variability of the fluorescence colour
condensate and causing precipitation of solid or semi-solid of the oil. The resulting data can reveal covariances
phases like asphaltenes or bitumen. These changes can between attributes that are useful interpreting the fluid his-
profoundly affect production of hydrocarbons due to the tory of the reservoir. At Phuong Dong, the OIAs observed
near-critical phase behaviour of gas-condensates and the range from uniform to highly variable fluorescence colour
presence of solids that plug pores and pore-throats decreas- and liquid–vapour ratios suggesting a complex charge his-
ing the permeability and producibility of reservoirs. Better tory involving multiple episodes of oil charge and gas
understanding of the history of the petroleum fluids in charge.
gas-condensates fields can improve exploration and produc- In this paper we report the results of a series of mixing
tion models for such resources. experiments in fused silica capillary capsules (FSCCs;
Modern fluid inclusion studies based on the concept of Chou et al., 2008) between oils, gases, and water to test
fluid inclusion assemblages (FIAs) identify groups of petro- the origin of variability in attributes of OIAs in the Phuong
graphically associated fluid inclusions that formed at about Dong Field that may result from in-reservoir fluid interac-
the same time, or during the same set of diagenetic conditions. We have used the same spectroscopic methods to
tions (Goldstein and Reynolds, 1994). This allows identifi- characterise the products of these experiments in FSCCs
cation of distinct compositions of fluids present during as those used to characterise the OIAs in samples from
the pressure–temperature-history of rocks. The approach the Phuong Dong Field. The characteristics of the inclu-
works well for aqueous fluid inclusions (Goldstein, 2001), sions in the Phuong Dong Field are described in detail
but similar approaches to analysis of oil inclusion and then compared with the results of the experiments.
364 J. Bourdet et al. / Geochimica et Cosmochimica Acta 142 (2014) 362–385
Fluorescence and infrared spectroscopy are widely Table 1

employed as non destructive methods for characterisation API gravities and fluorescence data of the calibration set of crude
of crude oil (Mattson et al., 1970; Tissot et al., 1974; oils.
Leythaeuser et al., 1980; Van Gijzel, 1981; Hagemann and Field name Fluorescence data °API
Hollerbach, 1986; Bertrand et al., 1986; McLimans, 1987; CIE x CIE y QG/B QR/G kmax
Khorasani, 1987; Pradier et al., 1990; Stasiuk and
Vincent 0.32 0.37 1.80 0.48 515 19.4
Snowdon, 1997; Ellingsen and Fery-Forgues, 1998;
Arab Mediuma 0.33 0.36 1.61 0.65 515 30.3
Ryder, 2004) and hydrocarbon fluid inclusions (Barrès Cliffhead 0.30 0.35 1.45 0.41 505 33
et al., 1987; Videtich et al., 1988; Bodnar, 1990; Tsui, Blina 0.30 0.34 1.32 0.44 505 36
1990; Guilhaumou et al., 1990; Wopenka et al., 1990; Dongara 0.28 0.33 1.22 0.31 495 35
Pironon and Barrès, 1990, 2001; Pironon and Pradier, Challis 0.26 0.31 1.18 0.24 480 39
1992; Kihle, 1995; Stasiuk and Snowdon, 1997; Blamey Watson South 0.25 0.30 1.00 0.22 470 46.4
and Ryder, 2007). The techniques are based on the Enfield 0.24 0.28 0.97 0.17 460 43.3
behaviour of covalent bonds in molecules excited by an Barrow 0.24 0.29 0.96 0.20 460 37.7
electromagnetic radiation to deduce compositional infor- Jackson 0.26 0.29 0.95 0.24 450 40.7
mation. Unsaturated organic structures which contain p Goodwyn 0.24 0.27 0.87 0.18 460 34
Jabiru 1A 0.24 0.28 0.86 0.19 450 42.1
electrons such as aromatics and conjugated polyenes are
Tirrawarra 0.23 0.27 0.83 0.15 450 46.5
primarily responsible for oil fluorescence (Hagemann and Wanaea 0.24 0.27 0.82 0.20 445 46.7
Hollerbach, 1986; Khorasani, 1987). Polar compounds (res- Skua 0.21 0.24 0.75 0.11 450 43.3
ins and asphaltenes) also fluoresce but the absolute inten- Yammaderry 0.22 0.23 0.63 0.14 440 54
sity is low relative to emissions from the aromatic systems Blackback 0.21 0.23 0.61 0.14 440 50
(Hagemann and Hollerbach, 1986; Khorasani, 1987). The Corallina 0.20 0.21 0.60 0.10 440 58
fluorescence properties of crude oils are thus primarily con- Saladin 0.21 0.22 0.59 0.12 440 51
trolled by the type and concentration of aromatic molecules Laminaria 0.20 0.21 0.58 0.09 440 57
relative to the concentration of aliphatic compounds Swallow 0.18 0.15 0.33 0.06 425 59
a
(Khorasani, 1987; Stasiuk and Snowdon, 1997). Visually, Arab Medium is a blended oil from Saudi Arabia.
the UV–visible fluorescence of oil is perceived by human
eye as a colour that can be measured and plotted in a of sixteen fused silica capillary cells (FSCCs) were prepared
CIE chromaticity diagram (Blanchet et al., 2003). Alter- containing crude oil only, crude oil + water, crude oil + gas,
ation of fluorescence is also a major factor influencing the and crude oil + water + gas (Table 3). Conventional
colour of petroleum mixtures under UV illumination deionized water was used for the water phase and the gases
(Pradier et al., 1990; Pironon and Pradier, 1992). In most were either pure methane, ethane, or propane.
cases fluorescence of petroleum is used to give a fingerprint The methods for the preparation of FSCCs and gas
of the composition of hydrocarbon mixtures. In this work loading are described in Chou et al. (2008). Square cross-
we used an empirical relationship between fluorescence of section micro-capillaries with a 96 lm internal width were
oils and API (American Petroleum Institute) gravity used to enclose a small volume of oil and a large volume
(Hagemann and Hollerbach, 1986; Bodnar, 1990; Tsui, of pure methane, ethane or propane. The following
1990; Stasiuk and Snowdon, 1997; Blanchet et al., 2003) procedure was used to fill the micro-capillaries:
and applied it to petroleum inclusions. Changes in fluores-
cence were also used to track the partitioning of hydrocar- - One end of about 8 cm of open capillary is immersed in
bon molecules between phases (oil, gas and water) that can water and/or oil. The liquid(s) moves into the tubes by
occur during the interaction between oil and gas. In con- capillary action. The oil in the tube is then pushed fur-
trast to fluorescence spectroscopy infrared spectroscopy ther from the open end by slightly heating the air in
provides more detailed information on molecular bond the tube using a soldering iron. That end of the capillary
types in organic compounds and mixtures. It is used in this is then sealed with a hydrogen–oxygen micro-torch. The
study to characterise the partitioning between phases of lar- oil in the tube is protected from the heat by a wet tissue
gely non-fluorescent alkane hydrocarbons. wrapped around the tube.
- The capillary is centrifuged for 90 s to push the oil and
2. METHODOLOGY water to the sealed end.
- The open end of the capillary is inserted into about 4 cm
2.1. Fused silica capillary cells (FSCCs) of polyethylene tubing. The tubing and capillary are
fused together by melting 2 mm of the polyethylene tub-
Crude oil from the Jabiru oil field, Timor Sea, Australia ing in contact with the silica capillary.
(Jabiru-1A) and Arab Medium were chosen as the oil phase - The plastic tubing is connected to a gas delivery and vac-
for experiments in capillary cells. Their SARA composi- uum system. The gas line and the capillary are evacuated
tions, API gravity, and sulphur contents are shown in and then flushed with the fill gas (methane, ethane or
Table 2. Jabiru is a light crude (42 °API) that is rich in sat- propane).
urates and has a low sulphur and asphaltene content. Arab - The sealed end of the capillary tube containing oil and/
Medium is a blended crude oil (30 °API) that is rich in or water is immersed in liquid nitrogen up to the top of
aromatic hydrocarbons, resins, and asphaltenes. A total the oil. The capillary is then pressurized with the fill gas
Table 2
Crude oil SARA compositions, API and sulphur content.
Crude oil °API Saturates Mono-aromatics Total aromatics Resins Asphaltenes Sulphur
(wt%)
Arab Medium 30 55 6 33 15 7 2.59
Jabiru 42 80 6 14 4 <1 0.04
Table 3
Sample numbers for fluid loadings in the FSCCs.
Crude oil No Gas Methane Ethane Propane
No water Water No water Water No water Water No water Water
Arab Medium A1 A2 A3 A4 A5 A6 A7 A8
Jabiru J1 J2 J3 J4 J5 J6 J7 J8
and immersed a few millimetres further in the liquid assessment, the filter cube is changed for a U-MWU model
nitrogen in order to freeze or condense methane, ethane combining a BP330–385 excitation filter, a DM400 dichroic
or propane. The gas line is then evacuated. When the mirror and a BA420 long pass barrier filter. This
pressure decreases to below 0.01 MPa the capillary is configuration creates a brighter fluorescence and a UV-safe
sealed with a torch while the bottom part is still in the observation while having minor impact on the colour
liquid nitrogen bath. perception.
The infrared spectra of inclusions were recorded with a
With this procedure it is difficult to control the oil/gas BrukerÒ V80v FT-IR spectrometer and Hyperion 2000 IR
volume ratios and the final pressure in the capillaries. microscope on the IR beamline at the Australian Synchro-
However, only the cells with the minimum oil volume were tron. The aperture is adjusted manually to fit to the inclu-
retained in order to maximise the effect of gas-washing on sion size using 4 orthogonal blades that can be rotated
oil. The initial oil/gas volume ratios are often not (5 5 lm minimum spot size). A background spectrum
measurable due to mixing of the crude with liquid ethane was measured in the silica glass. The detector is a liquid
and propane at 20 °C or complete liquid crude oil vaporisa- nitrogen cooled mercury cadmium telluride (MCT) detector
tion into the gas phase. and using the IR beamline of the Australian Synchrotron as
The evolution in the fluorescence of oil in FSCCs with the radiation source. OPUS 6.5 (BrukerÒ) software was
temperatures was observed and measured using a Linkam used to process the spectra to obtain a flat baseline and then
MDS 600 stage on an Olympus BX 50 microscope equipped to calculate the area ratios. Maps of the FT-IR signal were
with a 100 Olympus long-working distance objective lens. created using CytoSpec (v.1.4.0.2) software. Mapping of
The stage was calibrated using a Linkam CO2 synthetic inclusions was used to detect variability in composition
inclusion reference plate and a pure water fluid inclusion within the same inclusion. FT-IR spectra of inclusions
plate at critical density from Bubbles IncÒsynthetic fluid trapped in quartz or in the FSCCs are limited to the mid-
inclusion reference set (Blacksburg, VA, USA). Tempera- infrared range above 2000 cm 1 due to the absorption of
tures of the CO2 triple point, and ice melting point, and the infrared light by silica at lower wavenumbers.
H2O critical point at 56.6, 0.0 and 374 °C respectively, Functional groups that can be detected are –CH, –CH2
were used as reference temperatures for stage calibration. and –CH3 radicals, mainly contained in aliphatic molecules,
The precision and accuracy on temperatures is ±0.1 °C. CH4, CO2 and liquid water. Differentiation of functional
groups attached to aromatic rings from those attached to
2.2. Spectrophotometry alkanes is not possible due limitation of spectra above
2000 cm 1. Details of procedures for semi-quantitative
Fluorescence spectra were measured over the range of measurements of CH2/CH3, H2O/alkanes, and quantitative
400–900 nm with an Avantes spectrometer (Anglia Instru- measurements of the concentration of methane, alkane, and
ment, model Avaspec-2048TEC) equipped with a thermo- CO2 can be found in Pironon et al. (2000, 2001).
electric cooled Sony CCD detector. The spectrometer was Hydrocarbon gases in the vapour phase of FSCCs were
coupled to an Olympus AX70 microscope equipped with a identified with Raman microspectrophotometry. Raman
100W high pressure mercury-vapour light source (Olympus spectra were acquired with a Horiba Jobin-Yvon Labram
BH2-RFL-T3 and mercury short arc Osram HBO 103W/2 HR Raman microscope using a 25 mW frequency doubled
lamp). The filter cube (11004v2-Narrow-UV from Chroma Nd:YAG 532 nm laser. The grating used was 1800 gr/mm.
Technology) combines a D365/10 excitation filter (355– The methane peak position was checked with reference to
375 nm), a 380dclp dichroic mirror and an E400lpv2 long FSCC containing a low pressure of methane (<0.1 bar).
pass barrier filter transmitting wavelength of 400 nm and
above. Manipulation of the microscope diaphragm enabled 2.3. Phuong Dong Field sample preparation
the incident light to be focused on single inclusions or single
phases in FSCCs using a 100 air UMPlanFI objective. Samples are cuttings fragments of granite and consist
During visual observation and fluorescence colour mainly of free angular quartz and feldspar. Excess drilling
mud was removed by water washing, followed by magnetic Temperatures of phase changes in fluid inclusions were
mineral separation to concentrate the silicate and recorded with standard methods of microthermometry
non-magnetic fractions. Concentrates were cleaned in (Roedder, 1984). The same microthermometric equipment
dichloromethane in an ultrasonic bath for 10 min to remove described in the Section 2.1 was used for fluid inclusion
soluble hydrocarbons or drilling additives around frag- homogenisation temperature measurements.
ments. Samples were oven dried at 60 °C and then digested
in 10% H2O2 at room temperature for 1 h in an ultrasonic 3. GEOLOGICAL SETTING
bath to degrade and remove reactive organic compounds
and clay particles adhering to the grain surfaces. The clean The Phuong Dong Field is located off the south coast of
fragments were mounted in epoxy resin with Irgalite Vietnam within the Tertiary Cuu Long (Mekong) Basin, a
BlueÒ pigment and then prepared as double-polished 250 km long rift basin trending NE-SW (Fig. 1A). White
100-micron-thick fluid inclusion sections. Tiger (Bach Ho) and Sunrise (Rang Dong) are the largest
fields in the area (Fig. 1B) and Phuong Dong is considered
2.4. Fluid inclusion investigation as a NE satellite of Sunrise. The Cuu Long Basin is one of a
series of basins resulting from crustal extension in the
In the fluid inclusion investigation, oil inclusions, water proto-South China Sea prior to sea floor spreading (Lee
inclusions and gas inclusions were grouped into the same et al., 2001). The basin contains syn-rift and post-rift
assemblage providing they were trapped along the same sediments separated by a major unconformity. The base-
fracture in quartz. The assemblages are described as uni- ment is fractured and heavily weathered Mesozoic granite
form when the fluorescence colour and the bubble size, at and granodiorite.
room temperature, are visually similar in all the petroleum Organic-rich lacustrine deposits and coals are the main
inclusions. They are described as variable when the fluores- source rocks in the terrigenous Paleogene (Eocene–
cence colours or the bubble sizes are different. The fluores- Oligocene) syn-rift series (Boejesen-Koefoed et al., 2009).
cence colour of the oil may appear to co-vary with the Lacustrine source rocks are in contact with the fractured
bubble size amongst the petroleum inclusions in the same basement either by onlap or faulting. Depocentres in local
assemblage (i.e., blue fluorescence associates with larger grabens developed during the rifting phase and a regional
bubbles and yellow fluorescence with smaller ones). Assem- latest Oligocene unconformity characterises the beginning
blages were visually assessed and named according to the of the subsidence phase (Lee et al., 2001). Neogene post-rift
characteristic attributes of that assemblage. sediments, consisting of shales (Bach Ho Formation) and
Attributes, such as the variability in the size of the paralic or shallow marine sediments (Con Son, Dong Nai
vapour phase (bubble) and the visual fluorescence colour, and Bien Dong Formations), are organised in thick pro-
were assigned to each assemblage during Frequency of grading clinoforms. Sedimentary thickness can reach 8 km
Oil Inclusion (FOI; Eadington et al., 2000) analysis (not in depressions (Areshev et al., 1992).
presented in this paper). The fluorescence colours of oil The Phuong Dong reservoir is fractured and weathered
inclusions were visually discriminated into blue, white and granite basement on a fault-block high. The origin of the
yellow (George et al., 2001). To further characterize the fractures is not well understood, but may have resulted
variability in the visual fluorescence colour of the oil inclu- from a compressional event that reactivated pre-existing
sions, and to reduce bias in colour perception, visible spec- faults (Schmidt et al., 2003). Weathering and erosion of
tra were recorded and converted into CIE parameters as the granitoid bodies took place from the end of the Creta-
defined by the “Commission Internationale de l’Eclairage” ceous to the Palaeogene. The main stage of oil formation
(McLimans, 1987; Blanchet et al., 2003; Alderton et al., took place during the Late Miocene to Early Pliocene
2004) using a 1931 standard observer chromaticity diagram post-rift stage (Areshev et al., 1992). Gas generation began
(Deaton, 1987). The colour functions of the CIE coordinate during Early Pliocene. Oil is stored in micro- and macro-
were computed over the 415–780 nm wavelength range. fractures, and in vuggy pores. Structurally, the Phuong
A green–blue fluorescence intensity ratio (QG/B ratio, Dong Field is shallower in the northeast where it produces
Bourdet et al., 2012) was calculated from the fluorescence gas and condensate. Oil is produced from the deeper south-
spectra and used to estimate a density of the oil, expressed west part of the field (Fig. 1C). PD3X and PD4X are both
as API gravity, by comparison to a calibration set of crude horizontal wells that penetrate the Phuong Dong reservoir
oils (Table 1). Most of the crude oil compositions and API in the gas condensate zone and the oil zone, respectively.
gravities are reported in Edwards et al. (2002) open access
reports. Crude oils are mostly Australian examples from 4. OBSERVATIONS
the Northern Carnarvon Basin (Barrow, Goodwyn, Sala-
din, Vincent, Wanaea and Yammaderry), Bonaparte Basin 4.1. Phuong Dong fluid inclusions
(Challis, Corallina, Jabiru and Laminaria), Cooper and
Eromanga basins (Jackson, Tirrawarra and 4.1.1. Petrography of the OIAs
Watson-South), Canning Basin (Blina), Gippsland Basin The granitic rock samples comprise disaggregated quartz
(Blackback) and Perth Basin (Dongara). Arab Medium is and feldspar fragments and inter-grown quartz-feldspar.
a British Petroleum blend from Saudi Arabia crude Oil and gas inclusions are observed only in fracture trails
oils. Barrow, Goodwyn and Vincent crude oils are in quartz and feldspar, often in association with bitumen.
biodegraded. In feldspar, identification of individual fracture trails was
Fig. 1. (A) Map of the main sedimentary basins along the South China Sea showing the Cuu Long Basin (offshore Vietnam). (B) Location of
the Bach Ho, Rang Dong and Phuong Dong Fields. (C) Location of the PD3X and PD4X horizontal wells in the Phuong Dong reservoir.
difficult and only inclusions in microfractures in quartz - Oil in transmitted light, has a yellowish colour (Fig. 2A–C)
grains were studied. and fluorescences yellow. Inclusions contain bitumen,
Oil inclusion assemblages (OIAs) from the present-day wax and occasionally a small amount of water. The
oil leg are characterised by a uniform gas/liquid ratio and amount of bitumen is variable between the inclusions
fluorescence colour of the oil. Two groups of OIAs are of the same assemblage, but the amount of wax particles
distinguished: seems to always be in proportion to the oil volume. The
Fig. 2. Photomicrographs of oil inclusions from the Yellow group of assemblages (A–C) and the White group of assemblages (D–F) present in
the current oil zone in PD4X, Phuong Dong reservoir. Chromaticity diagrams show the CIE x–y location of the fluorescence colour for oil
inclusions of each group. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
bitumen particles partly coat the walls of inclusions, or – Oil inclusions with uniform medium gas/liquid ratio,
occur at the boundary between oil and water (when the oil appears to be colourless in transmitted light.
water is present). Some oil inclusions have water and Bitumen is rare or absent and water is not observed in
no bitumen and vice and versa. The wax, present as par- these inclusions. This assemblage has uniform visual
ticles in the oil, always melts at about 65 °C, whereas pale yellow fluorescence of the oil (Fig. 3B). This
bitumen is stable over a wide range of temperatures. assemblage is referred as Yellow-2.
The oil inclusions have low gas/liquid ratio. This group – Oil inclusions with uniform medium gas/liquid ratio
of assemblages is referred to as Yellow. and under transmitted light colourless oil. Bitumen
- Oil in transmitted light is colourless with white fluores- particles are rare or absent and water is not observed
cence. Bitumen is absent, wax particles are rare and in these inclusions. This assemblage has uniform white
water is not observed. The inclusions have medium– visual fluorescence of the oil (Fig. 3C). This assemblage
low uniform gas/liquid ratios and white visual fluores- is referred as White.
cence of the oil (Fig. 2D–F). This group of assemblages – Oil inclusions with uniform low gas/liquid ratio
is referred to as White. co-trapping bitumen, wax and a small amount of water
(Fig. 3D). The oil, as observed under transmitted light,
White and Yellow assemblages have visually uniform has a yellowish colouration, and uniform white visual
fluorescence, but for the Yellow OIA especially, the CIE fluorescence. The characteristics of this assemblage are
x–y chromaticity diagrams (Fig. 2) show a continuous the same as those from the Yellow OIA, except that
spread of CIE indexes. the fluorescence of the oil appears to be visually more
The fluid inclusion assemblages from the current gas white. This assemblage is referred as White-2.
zone fall into two categories characterized either by uni- – Oil inclusions with uniform high gas/liquid ratio, a
form or variable properties regarding the gas/liquid ratio colourless oil in transmitted light (Fig. 3E) and a dull
and fluorescence colour of the oil. to bright blue fluorescence colour. This assemblage is
referred as Blue.
Uniform groups of OIAs:
– Oil inclusions with uniform low gas/liquid ratio Variable OIAs:
co-trapping bitumen, wax and a low amount of water – The oil inclusions trap variable amounts of bitumen
(Fig. 3A). This assemblage has uniform yellow visual and an amount of solid wax at room temperature that
fluorescence of the oil, referred as Yellow, is strictly the appears to be proportional to the volume of oil. Water
same as the previously described assemblage from the is present in some inclusions. The assemblages have
oil leg. white and yellow fluorescing oil inclusions with
Fig. 3. Paired bright light and UV photomicrographs of oil inclusions from the different uniform fluorescence OIA (A–E) and variable
fluorescence OIA (F–I) present in the current gas zone in PD3X, Phuong Dong reservoir. Chromaticity diagrams show the CIE x–y location
of the fluorescence colour for oil inclusions of each group. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
medium and low gas/liquid ratio, respectively. A

co-variance of the gas/liquid ratio and the visual
fluorescence of the oil is observed (Fig. 3F). This
assemblage is referred as White to Yellow.
– assemblages of large vapour phase inclusions, with a
blue fluorescing rim of oil, and medium to small
vapour phase (low gas/liquid ratio) yellow fluorescence
inclusions with (Fig. 3G). This assemblage is referred as
Blue to Yellow.
– Assemblages with large vapour phase inclusions, with
blue fluorescing rim of oil, and low gas/liquid ratio
(small vapour phase) inclusions, with white fluores-
cence. There appears to be co-variance of the gas/liquid
ratio and the visual fluorescence of the oil (Fig. 3I) in
which inclusions with a larger volume fraction of liquid
have more whitish fluorescence colour. Inclusions often
trap a variable amount of bitumen (Fig. 3H) in narrow
throats, without a relationship to the gas/liquid ratio or
the volume the inclusions. This assemblage is referred
as Blue to White.
On the CIE chromaticity diagram the fluorescence col-

ours of variable assemblages cover the entire graduation
from the yellow to the blue domain (Fig. 3).
4.1.2. Estimated API gravity of inclusion oils

Stasiuk and Snowdon (1997) used fluorescence spectra Fig. 4. Diagrams plotting the °API of the calibration set crude oils
to estimate °API gravity using correlation equations calcu- against their QR/G (A) and QG/B (B) values. The data set from
lated from a calibration set of crude oils. Those correlations Stasiuk and Snowdon (1997) are also plotted in diagram A.
are based on a Red/Green ratio (Q = Intensity 650 nm/
Intensity 500 nm) and the wavelength at maximum spec-
trum intensity (Lmax). Applying the Stasiuk and Snowdon 4.1.3. Microthermometry
(1997) correlations to light oil or condensate inclusions, like 4.1.3.1. Current gas zone. In the gas zone the Th measure-
those of the Phuong Dong Field is difficult because the ments (Fig. 6 and Table 4) for the uniform and the variable
fluorescence signal at 650 nm is often weak with a low sig- fluorescence OIAs are separated into two different histo-
nal-to-noise ratio, making the Q values imprecise. There- grams. In the uniform OIAs, oil inclusions from the Yellow
fore, correlations based on a new set of crude oils with assemblage homogenise in liquid with a Th range between
°API between 30.3 and 59 and a different definition of Q 92.1 and 136.2 °C and an average Th of 114.0 °C and a
(intensities at 510 and 430 nm, Bourdet et al., 2012) were mode in the 115–120 °C class. The oil inclusions from the
used in this study (Table 1). This data set contains Austra- Yellow-2 assemblage homogenise in liquid with a Th range
lian crude oils and one Middle East crude oil (Arab Med- from 113.2 to 132.6 °C, an average Th of 121.8 °C and a
ium). The Q and °API values of this set of crude oils are mode in the 120–125 °C class. The oil inclusions from the
shown in Fig. 4A, together with the data from Stasiuk White assemblages have Th between 123.6 and 128.8 °C,
and Snowdon (1997). with the exception of one inclusion that had a lower Th
The correlation equation (°API = 24.824 QG/B + of 104.2 °C. The oil inclusions from the White-2 assem-
66.434, R2 = 0.84) is used to calculate the °API of inclusion blages have Th between 108.3 and 114.0 °C. Both of the
oils from their measured QG/B values. We included white fluorescence OIAs homogenise in liquid. The uniform
90% confidence interval curves which result in a precision blue assemblages have Th between 109.4 and 123.7 °C and
of ±6 °API for a QG/B of 0.4 and ±2 °API for a QG/B homogenise in gas, liquid, or with critical phenomena
of 1.8. (disappearance of the interface between liquid and vapour).
The calculated API gravities of petroleum inclusions In the variable OIAs, oil inclusions from the Blue to
from the Phuong Dong Field are presented in Fig. 5. white assemblage have a left-skewed Th histogram with val-
Table 4 summarizes the average °API for each OIA in ues ranging from 130.3 to 166.2 °C (n = 20 inclusions).
both zones. Derived °API gravity values from hydrocar- Three Th were measured lower than this, at 82.1, 110.7,
bon inclusions from the current gas zone range between and 120.5 °C, and five Th higher than 170 °C were not
8 and 58, and in the current oil leg they are between 17 cycled to avoid damage to the other fluid inclusions. The
and 44. High °API values between 45 and 58 are only blue fluorescing inclusions in this assemblage with large
found in the current gas-zone based on blue fluorescing vapour phase homogenised into gas while the white inclu-
inclusions. sions, with smaller vapour phase, homogenised into liquid.
Fig. 5. Histograms of the derived °API calculated from the QG/B ratio acquired from the fluorescence spectra of petroleum inclusions in the
different OIAs in the gas zone and the oil-leg at Phuong Dong Field.
The inclusions belonging to the Blue to yellow The inclusions from the uniform White assemblages
assemblage have Th ranging from 111.5 to 156.6 °C without homogenise in liquid. The Th values range from 90.2 to
mode in the histogram. The blue fluorescing inclusions with 128.2 °C, with a mode in the 120–125 °C class. Only one
large vapour phase homogenised in liquid, gas, or critical inclusion has Th below 110 °C and three have Th higher
phenomena while the yellow inclusions with smaller vapour than 140 °C (not cycled to preserve other inclusions from
phase homogenised in liquid. overheating damage).
The inclusions belonging to the White to yellow assem-
blage have Th ranging from 74.9 to 139.4 °C without a clear 4.1.3.3. Synchrotron FT-IR. FT-IR spectra of individual
mode in the histogram. All the inclusions homogenise in inclusions (Fig. 7), from each of the uniform and variable
liquid. OIAs, were used to quantify methane concentrations,
CH2/CH3 ratios (low for short n-alkane and high for long
4.1.3.2. Current oil zone. In the current oil zone, the inclu- n-alkanes) and water–hydrocarbon ratios (Table 4). In the
sions of the uniform Yellow fluorescing OIAs have Th of current oil leg, inclusion oil from the uniform White fluo-
between 77.6 and 155.2 °C with a mode in the 120–125 °C rescing OIA is enriched in methane (average of 33 mol%)
class. They all homogenise in liquid. Of a total sample size and has lower CH2/CH3 ratios (average value of 1.3)
of 41 inclusions, five inclusions had Th below 110 °C and compared to the oil in the uniform Yellow fluorescing OIAs
one higher than 130 °C. that have average methane concentration of 26 mol% and
Table 4
Fluid inclusion results summary acquired on the Phuong Dong petroleum reservoir samples from the current gas zone and the current oil leg.
V, C and L stand for vapour, critic and liquid phase state. Th: homogenisation temperature; W/Hc: water/hydrocarbon mid-IR band area
ratio; wax and bitumen: none, + present, ++ frequent, +++ abundant.
Current Assemblage name Attributes Phase Number of Averaged data Bitumen Wax
hydrocarbon at Th inclusions
Oil Visual Variance Th Derived CH2/ W/ CH4
zone fluorescence bubble (°C) °API CH3 Hc (mol%)
colour size
Gas zone Blue Blue Large Uniform V–C–L 8 118.1 49 1.3 6 49 +
White-2 White Small Uniform L 4 111.6 28 1.3 0.3 33 +++ +++
White White Medium Uniform L 6 121.1 31 1.3 12.2 27
Yellow-2 Yellow Medium Uniform L 16 121.8 22 1.3 0.2 26 +
Yellow Yellow Small Uniform L 45 114.0 23 1.7 2.1 25 + ++
Blue to White Blue Large Co-variance V–L 22 144.0 52 1.0 0.1 58 +
White Medium V–L 6 151.2 40 1.6 1.4 43 +
Blue to Yellow Blue Large Co-variance V–C–L 8 138.3 48 1.1 5.5 53
Yellow Small L 10 127.9 28 1.4 2.2 37 +
White to yellow White Medium Co-variance L 2 122.5 31 1.4 0.1 34 ++ ++
Yellow Small L 16 109.6 23 + +++
Oil zone White White Medium Uniform L 28 119.6 35 1.3 0.2 33 +
Yellow Yellow Small Uniform L 41 116.3 25 1.5 0.1 26 ++ +++
average CH2/CH3 ratio of 1.5. Water contents are low for and ethane at elevated temperature, while propane had a
both assemblages. lesser effect. This change is characterised by a red-shift of
In the current gas zone, the average methane content the fluorescence colour (Fig. 12C). Increasing the tempera-
varies from 25 mol% (Yellow OIA) to 58 mol% in blue flu- ture from 20 and 100 °C enhances this change, which corre-
orescing inclusions belonging to the Blue to white OIA. sponds to a relative decrease in the intensity of the signal in
Overall, blue fluorescing inclusions are enriched in methane the 400–480 nm range and increase in the 480–750 nm
and have lower CH2/CH3 ratios compared to white fluo- range (Fig. 13). Minor amounts of solid residues were
rescing and yellow fluorescing inclusions. Water within observed and are often associated with water in the FSCCs
petroleum inclusions (quantified by the Water/HC ratio) (Fig. 11A). The presence of water with gas slightly reduces
varies from high to low in the gas zone, while in the oil the change in fluorescence of the oil (Figs. 13 and 14).
leg they are only low. Maps of the FT-IR signal of inclu- For the Arab Medium crude oil (30 °API) the change of
sions from the Yellow assemblage in the gas zone and the fluorescence of the oil phase is subtle with methane and eth-
oil leg, and of one large oil inclusion from the White assem- ane, corresponding to either a blue or a red shift, depending
blage in the oil leg are shown in Fig. 8. The maps indicate on the presence or absence of water. With ethane only, a
that methane is concentrated in the vapour phase and CH2/ new immiscible ethane-rich liquid phase appears which
CH3 ratios are higher in the area occupied by the brown does not have detectable fluorescence with our equipment.
solid matter, consistent with long chain hydrocarbon mole- With ethane and water, a large volume of solid residue
cules. On map a2, wax particles in the oil phase give an and a new blue fluorescing liquid phase appears. With pro-
intense CH signal, consistent with n-alkanes. The white flu- pane only, the initial oil disappears and new blue fluoresc-
orescing oil inclusion from the oil leg has a more uniform ing liquid and semi-solid residues form. With propane and
CH2/CH3 ratio throughout the entire inclusion except in water, most of the initial oil disappeared while new blue flu-
the vapour phase where there are low CH2/CH3 ratios con- orescing liquid and semi-solid residues form. The remaining
sistent with a high concentration of methane in the vapour. initial oil has fluorescence that is shifted to blue. The
amount of semi-solid residues is negligible with methane
4.2. Experimental gas-washing of crude oil in FSCCs while it is high in the capsules containing ethane and pro-
pane. More residues form when water is associated with
Images of the FSCCs with enclosed mixtures of oil, gas ethane than with ethane only. All residues have similar
and water are shown in Figs. 9–11. Fluorescence colour, low intensity, dark orange visual fluorescence. Temperature
measured by CIE x–y chromaticity, is shown in Fig. 12 change from 20 to 100 °C has a small effect on the fluores-
for the reference oil and on oil mixed with gas and water cence spectra of the oil phase with methane. With ethane
at different temperatures. Changes in the shape of the fluo- only, the temperature effect is small. With propane, the
rescence spectra of the oil, due to the presence of gas and fluorescence of the oil phase shows a red-shift with an
water at different temperatures, are illustrated in Figs. 14 increase in the fluorescence signal in the 500–740 nm range.
and 15. In FSCC with Arab Medium crude oil, the blue fluoresc-
The fluorescence characteristics of the Jabiru oil ing liquid that forms in the presence of ethane and propane
(42 °API) changed significantly in the presence of methane shows unusual behaviour with increasing temperature.
Fig. 6. Histograms of the homogenisation temperatures of the oil inclusions belonging to the uniform and variable OIAs from the gas zone
(PD3X) and the oil zone (PD4X).
From 20 to 70 °C its fluorescence is red shifted. At about phase of the FSCCs A3, A4, J3 and J4 (See Table 3 for
70–80 °C, two new liquids that fluoresce white and yellow FSCCs descriptions). The pressures estimated using the
appear, coincident with critical state homogenisation of Raman methane peak position technique for the system
the blue fluorescing liquid and vapour. The fluorescence CH4–H2O, by Lu et al. (2007), are between 95 and 180 bars
of the critical fluid is further blue shifted compared to the (indicated in Fig. 15). CH3 and CH2 vibration bands of
blue fluorescing liquid oil the formed initially at room tem- molecules fractionating from the oil to the vapour phase
perature. During formation of the new blue fluorescing are detected with methane in the vapour phase in J3 and
liquid, the fluorescence of the residual Arab Medium oil J4 and are less pronounced in J4 than J3. This is probably
is gradually red-shifted with increasing temperature due to a combination of lower pressure and the presence of
(Fig. 12B). water in J4, affecting the molecular fractionation from the
FT-IR and Raman spectra, at room temperature, con- oil to the vapour phase. Ethane is clearly detected in the
firmed the presence of methane in the oil and in the vapour vapour phase of A5, A6, J5 and J6, and in the oil phase
Fig. 7. Synchrotron FT-IR Spectra of petroleum inclusions from the current gas zone and oil leg in the 3800–2200 cm 1 area. Detail views of
the 3200–2800 cm 1 area show the CH4 and CH stretching bands. The spectra were normalised at the CH2 peak located at about 2925 cm 1 to
emphasise the variation of absorption intensity of the other bands.
in J5 and J6. Ethane is the only detected compound in the 34.3 °API oil. The White OIA in cuttings from the oil zone
non-fluorescent liquid phase in A5. The blue-fluorescent have an average 35 °API that is consistent with the pro-
liquid phase in A6 is certainly mostly ethane but no duced oil. The Blue to white OIA in cuttings from the gas
FT-IR spectrum could be recorded in this phase. Propane zone with an average estimated 52 °API is consistent with
is detected in the vapour phase in A7, A8, J7 and J8 by the condensate produced from the PD-3X well. Inclusions
FT-IR. CH3 and CH2 vibration bands of molecules frac- that homogenise into the gas phase, typically represented
tionating from the oil to the vapour phase, are detected by the Blue and Blue to white OIAs, are consistent with
with propane in the vapour phase in J7 and J8. The pro- the current reservoir gas phase while heavier oils, typically
pane band is strong in the oil phase in J7 and J8 and in represented by the Yellow OIAs, were liquid at the time of
the new blue fluorescing liquid phases in A7 and A8. CH3 trapping. The Yellow-1 and Yellow-2 OIAs have the lowest
and CH2 vibration bands of molecules fractionating from °API and methane contents and oils that fluoresce in this
the oil to the new blue fluorescing liquid phase are also part of the visible spectrum are typically associated with
detected in A7 and A8. lower thermal maturity (George et al., 2001). The estimated
Solid phases show CH vibration bands in association °API of the Yellow-1 OIA are more variable than the
with water, even in FSCCs without added water. Images Yellow-2 OIA, which has a tighter cluster of data points.
of the FSCCs with enclosed mixtures of oil, gas and water The White OIA represents an intermediate oil, liquid at res-
are shown in Figs. 9–11. Fluorescence colour, measured by ervoir conditions, with consistent °API and CH4 content
CIE x–y chromaticity, is shown in Fig. 12 for the reference but variable CH2/CH3 ratios.
oil and on oil mixed with gas and water at different temper- Homogenisation temperatures (Th), when plotted
atures. Changes in the shape of the fluorescence spectra of against the estimated °API or the FT-IR derived CH4, show
the oil, due to the presence of gas and water at different that Th > 130 °C are associated with high °API and high
temperatures, are illustrated in Figs. 13 and 14. CH4 content, a characteristic generally of blue fluorescing
inclusions from uniform or variable OIAs. These inclusions
5. DISCUSSION typically homogenise into the gas phase and the high Th are
unlikely to indicate minimum temperatures of trapping but
5.1. Properties of inclusion oils at Phuong Dong rather suggest that inclusions formed by two-phase trap-
ping when gas and oil were trapped together at reservoir
The PD-3X well in the gas zone produces 51.4 °API con- conditions. Most other inclusions that homogenise into
densate and the PD-4X well in the oil zone produces the liquid phase have °API ranging between 20 and 40
Fig. 8. Photomicrographs with corresponding synchrotron FT-IR maps of the CH2 + CH3 peaks area summation in the range 3200–
2800 cm 1, CH2/CH3 peaks area ratio in the range 3200–2800 cm 1 and methane peak intensity at 3012 cm 1 of two yellow fluorescing (a–b)
and one white fluorescing (c) oil inclusions from uniform OIAs present in the gas zone and in the oil zone. Length of bars on
photomicrographs and maps correspond to 10 lm. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)
and CH4 contents between 20 and 40 mol% and their Th inclusions from the different OIAs (Fig. 16). Oils with
range from 110 to 130 °C. Some blue fluorescing inclusions higher methane content have higher °API and vice versa.
from the Blue OIA, that homogenise in gas, critical or This trend is reversed in plots of CH2/CH3 ratios versus
liquid, have Th that are also between 110 and 130 °C and methane content for the same oil inclusions. Oils with
could be associated with minimum trapping temperatures higher methane content have lower CH2/CH3 ratios, which
of the gas condensate. This might suggest that the temper- is consistent with a higher proportion of shorter chain mol-
ature of the reservoir did not exceed 130 °C and was rela- ecules. These trends are consistent with trapping of oils of
tively stable during the fill history. different thermal maturity. It is unlikely that OIA’s with
The physical and chemical properties of the inclusion different physical and chemical properties were trapped at
oils including methane content, estimated °API, and CH2/ the same time. Our evidence of chemically distinct types
CH3 ratio, are less variable in the current oil leg of the Phu- of petroleum in the OIAs implies multiples stages of hydro-
ong Dong Field compared to the gas-condensate zone. carbon charge during the filling history of the reservoir.
Taken as a whole, there is a positive correlation between However, the variability of fluorescence of oil in inclusions
estimated °API and FT-IR derived methane content of oil belonging to a same OIA suggests some interaction between
Fig. 9. Paired bright field and UV-fluorescence photomicrographs of the FSCCs filled with Arab Medium oil (30 °API), gas and water. The
numbers refer to the CIE x–y parameters measured and plotted on Fig. 13.
Fig. 10. Paired bright field and UV-fluorescence photomicrographs of the FSCCs filled with Jabiru oil (42 °API), gas and water. The numbers
refer to the CIE x–y parameters measured and plotted on Fig. 13.
the initial oil in the pore space and a later hydrocarbon expected to have similar geochemical properties to the pro-
phase that causes molecular fractionation. Mixing of duced oil and the adsorbed oil is characterised by relatively
charges is very common in reservoirs (Wilhelms and low aliphatic and higher NSO content compared to the free
Larter, 2004). A simplistic model called onion skin oil. Leythaeuser et al. (2007) developed the pore-size charge
(Wilhelms et al., 1996) described phenomena happening model based on the differences of maturity of extracts mea-
at the pore scale. They stated that the polar fraction along sured between large and small pores in the uppermost por-
with other hydrocarbons (Behar and Vandenbroucke, 1988) tion of a reservoir that contrasts with uniform maturity for
of an initial charge in a sandstone reservoir are adsorbed different pore sizes, lower in the oil column. They argue that
onto the mineral surfaces/water layers and subsequent where several charges occur in a reservoir making the oil
petroleum charge interacts with this initial petroleum. The column thicker, the oil of the initial charge is displaced into
concept of an immobile portion of oil, also named adsorbed the finer pores by the increase of the buoyancy forces as the
oil or residual oil, and a mobile or free oil at the pore scale oil column is growing while the latest oil charge occupies
has been developed by Schwark et al. (1997). The free oil is the larger pores.
Fig. 11. Bright field and UV-fluorescence detail photomicrographs of the FSCCs filled with oil, gas and water. The evolution of fluorescence
of L2 and L3 are reported on Fig. 12.
When fluid inclusions are trapped in pore filling cement, in an OIA would contain the same relative proportion of
it is not clear to what extent mixing phenomena may influ- the bitumen phase. Waxes observed in the Yellow and
ence the chemical contrast between trapped oil and the bulk White-2 OIA do occur in the same relative proportion to
oil in the pore space. Depending on the oil composition, the the liquid phase and are likely to have precipitated in situ.
amount of adsorbed oil should be different, with strongly The origin of the bitumen associated with blue, yellow or
coated pores in case of heavy oil and mostly “clean” min- white visual fluorescence inclusions could result from sev-
eral surfaces in case of very light oil. In reservoirs with mul- eral processes. Pyrobitumens can form via thermal cracking
tiple charges of oils of different thermal maturities it is of hydrocarbons or by oxidative processes such as thermo-
difficult to predict the extent to which the mixture between chemical sulfate reduction (TSR). Viscous tars are reported
the new charge and the pre-existing free oil modifies the to form by biodegradation of oil (Connan, 1984), and
adsorbed oil already present around grains. asphaltenes can precipitate from oil by addition of low
Brown solids within petroleum inclusions that do not molecular weight alkanes (gas deasphalting).
mix at homogenisation temperature and causes a high Biodegradation as the origin of the bitumen can be ruled
CH2/CH3 ratio in FT-IR spectra is consistent with agglom- out because of the elevated reservoir temperature at the time
eration of high molecular weight hydrocarbon molecules. of the fluid inclusion entrapment. Biodegradation is a phe-
These solids may be solid bitumen sensu Rogers et al. nomenon taking place at temperatures below 65 °C
(1974) who define solid bitumens as viscous or solid petro- (Milner et al., 1977) while the minimum trapping tempera-
leum residues that fill reservoir pore space. The presence of ture of the oil inclusions containing bitumen are above 90 °C.
variable amounts of bitumen in the Phuong Dong petro- Formation of pyrobitumen by thermal cracking of
leum inclusions indicates that it did not precipitate in situ oil appears to require reservoir temperatures of at least
from the oil, post fluid entrapment. Otherwise all inclusions 150–160 °C (Horsfield et al., 1992; Schenk et al., 1997),
Fig. 12. CIE-chromaticity diagrams plotting the fluorescence colour of the liquid hydrocarbon phases or solid residues contained in the
FSCCs at different temperatures. The numbers correspond to temperatures.
Fig. 13. Graphs plotting the difference between the reference fluorescence spectrum of Jabiru oil at 25 °C and the fluorescence spectrum of
Jabiru oil in presence of gas and water in FSCCs at different temperatures.
while TSR begins oil destruction at about 120–130 °C content or from trapping of oil with a limited amount of
(Dahl et al., 1999). Homogenisation temperatures of the low molecular weight hydrocarbons (Sutton and Roberts,
oil inclusions that trap bitumen in the Phuong Dong reser- 1974) because the light ends contribute to the solubility of
voir are mainly between 90 and 130 °C and higher Th are waxes (Misra et al., 1994). Gas deasphalting provides an
associated with Blue to white OIAs. The higher Th are likely appropriate mechanism for the presence of bitumen in
to result from two-phase trapping of oil and gas, consistent inclusions, the lack of light end in oil responsible of the in
with variable liquid–vapour phase ratios in those assem- situ wax precipitation and suits the Phuong Dong fluid
blages. Furthermore, thermal cracking fails to explain the inclusion record of oil inclusion in current gas zone. The
presence of bitumen associated with waxes which should variability in the fluorescence colour of oil between petro-
be highly sensitive to thermal breakdown. Wax in the leum inclusions belonging to the same assemblage might
Yellow and White-2 OIAs could originate during cooling originate from the interaction of oil with gas, responsible
of inclusions that trapped an oil with unusually high wax of a molecular fractionation.
Fig. 14. Graphs plotting the difference between the reference fluorescence spectrum of Arab Medium at 25 °C and the fluorescence spectrum
of Arab Medium oil in presence of gas and water in FSCCs at different temperatures.
5.2. Effect of introduction of gas on residual oil colour due to an increase in the relative abundance of high
molecular weight fluorophores in the oil emitting in the
Our experiments on gas-washing of oil in FSCCs shows 480–700 nm range). The fluorescence colour change
that the introduction of gases strongly alters the residual observed during heating in the FSCC with methane-oil
oil, but the gases interact with the two crude oils in different and ethane-oil mixtures indicates that temperature rise,
manners. With the light oil (Jabiru), gases dissolved into the and probably pressure rise, favours molecular transfer from
oil and components of the oil partitioned into the gas the oil to the vapour phase. The more pronounced fluores-
phase. Partitioning of oil components into the vapour is cence change observed with ethane at elevated temperature,
consistent with the presence of CH vibrations in the FT- compared to methane, suggests that the fractionation effect
IR spectra of the vapour and may be responsible for the is more pronounced with higher molecular weight gases.
change in fluorescence colour of the oil. This can be With the heavier oil (Arab Medium), the gases did not
explained by the vaporisation of light aliphatic, small aro- dissolve into the oil as readily compared to the lighter oil.
matic and resin molecules causing a red-shift in fluorescence Gases concentrated in the vapour phase and formed a
Fig. 15. FT-IR spectra measured in FSCCs. A3–A8: Arab Medium oil, J3–J8: Jabiru oil.
new immiscible liquid with ethane and propane. The newly residual oil in the 400–480 nm range observed in those cap-
formed liquid contains light aliphatic compounds and rela- illaries (Figs. 13–15).
tively low molecular weight, fluorescent aromatic and resin We interpret factors contributing to changes in the resid-
molecules stripped from the oil inducing fluorescence emis- ual oil as: (1) relative decrease of fluorescence at short
sion in the 400–480 nm range (a blue-shift in fluorescence wavelengths (red-shift) due to partitioning of low molecular
colour). The higher molecular weight fluorophores weight aromatic molecules into the vapour phase and/or
remained in the residual oil and the fluorescence was red- into the new immiscible liquid phase; (2) relative decrease
shifted. of fluorescence response at long wavelengths (blue shift)
Significant amounts of semi-solid residues, with dark- due to a loss of high molecular weight aromatics by precip-
orange low-intensity fluorescence, precipitated form the itation of solid residues; and (3) relative increase of fluores-
Arab Medium on the addition of propane and addition of cence response at short wavelengths (blue-shift) is due to
ethane and propane in the presence of water. The Arab desorption of aromatics and resins from asphaltenes. In
Medium oil has a high asphaltene content compared to the lower API gravity and higher asphaltene content oil,
the Jabiru crude oil. The orange fluorescence of the residue water has a strong effect on precipitation of semi-solid res-
and the correlation between high asphaltene content and idue and stability of the oil phase. The change in fluores-
large amounts of solid precipitation, we believe the precipi- cence colour of the residual oil in the presence of excess
tates concentrated the heaviest and most polar fractions of gas appears to be due to a combination of all these phe-
crude oil. In crude oils, asphaltenes exist in the form of col- nomena. The intensity of the colour changes depends on
loidal dispersions and are stabilised in solution by resins and the initial composition of the oil. Pressure and type of gas
aromatics that act as peptising agents (Hammami et al., present in the vapour phase probably has an impact on
1995). According to Hammami and Ratulowski (2007), the solubility of aromatic-bearing molecules in the vapour.
when gas or n-alkanes are added to the crude oil, the change However this interpretation requires further experiments.
in composition leads to precipitation of the asphaltenes.
Resin and aromatic molecules desorb from the surface of 5.3. Fill history of the Phuong Dong Field
the asphaltenes in an attempt to re-establish the thermody-
namic equilibrium that existed in the oil. This desorption of The Phuong Dong fluid inclusion record is remarkably
peptising resins forces the asphaltenes to agglomerate in similar to the effects we observed with the addition of gases
order to reduce their overall surface free energy. The precip- and water to oils in FSSCs. This strongly suggests that the
itation of solid residues in those FSCCs reduces the amount characteristics of the OIAs in the present day gas zone of
of asphaltenes in the oil, which reduces the fluorescence the Phuong Dong Field are due to the displacement of a
spectra at wavelengths longer than 480 nm. The release of palaeo-oil column by gas that was added to the reservoir.
resin and aromatic peptising agents, however, counterbal- Overall, we interpret the origin of the current oil leg to be
ances this change in fluorescence and is likely to be respon- the result of gas washing of the palaeo-oil that increased
sible for an overall increase in fluorescence response of the its API gravity, changed its fluorescence by a general
Fig. 16. 2D graphs plotting the measured methane content, the derived API, the CH2/CH3 ratio and the Th of petroleum inclusions
populating uniform and variable OIAs present in the gas zone and in the oil zone. BTW: Blue to white assemblages; BTY: Blue to yellow
assemblages; WTY: White to yellow assemblages. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)
blue-shift, and precipitated the asphaltenes as bitumen. size and Th. They appear to represent an initial palaeo-
Based on the properties of the OIAs we propose a scenario oil. Similarly the Yellow OIAs in both the current gas zone
for the history of petroleum charge to the reservoir. and the oil leg contain 20–25 °API gravity oil with an aver-
age methane content of about 25 mol% (Fig. 17). The con-
5.3.1. Time 1: Palaeo-oil zone sistency of the characteristics of the Yellow and Yellow-2
The Yellow-2 OIAs in the gas zone with an average OIAs in both current reservoir zones suggests that they
22 °API gravity oil are unlike any fluids currently produced trapped oil in a single palaeo-oil column (Fig. 17). How-
in the Phuong Dong field. They contain about 26 mol% ever, these inclusions often enclose bitumen and wax along
methane and show little variability in fluorescence, bubble with the oil and minor amount of water. The measured
Fig. 17. Step filling history of the Phuong Dong reservoir showing the CIE chromaticity diagram of the fluorescence colours of the oil trapped
in fluid inclusions at Time 1, when the palaeo-oil was present in the reservoir and at Time 2 when the gas accumulated in the top of the
reservoir. Cartoons are an illustration of the pores scale phases at reservoir conditions (in fluorescence colour). (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
fluorescence colour of the oil shows a significant spread in interpret the uniform White OIA in the current oil leg to
the CIE chromaticity diagram. Those characteristics indi- be samples of oil trapped contemporaneously with the addi-
cate that the oil has been gas washed. tion of gas that created the current gas zone (Fig. 17).
5.3.2. Time 2: Current oil leg 5.3.3. Time 2: Current gas zone
The uniform White OIA, characterised by white fluo- The uniform Blue fluorescing OIA, characterised by
rescing oil with a medium-size vapour phase at 20 °C, is large vapour bubbles and a rim of oil that at room temper-
present in the current gas zone but is more abundant in ature, are present only in the current gas zone at the Phu-
the oil leg. In the oil leg, these inclusions contain oil of ong Dong Field. They contain the highest methane
about 35 °API gravity and an averaged methane content content (Fig. 16) and homogenise mostly into the vapour
of about 33 mol% (Fig. 16). This is consistent with the phase, which is consistent with entrapment of gas-conden-
34.3 °API crude oil produced from the PD4X well, suggest- sate at reservoir conditions.
ing that this OIA trapped oil similar to that currently in the These vapour-dominated blue fluorescing inclusions are
reservoir. The White assemblage has higher °API, higher not only found in uniform OIAs but also in association
methane and lower CH2/CH3 ratio than the uniform Yellow with liquid-dominated white (Blue to white OIA) or yellow
OIA from the same zone. We interpret the White OIA to be (Blue to yellow OIA) fluorescing inclusions. These OIA have
samples of an evolved oil that resulted from mixing of gas high and variable Th consistent with heterogeneous
into the palaeo-oil column. This increased the API gravity trapping described by Goldstein and Reynolds (1994) for
of the oil as asphaltenes precipitated and smaller-chain gas–aqueous fluids. The homogenisation of inclusions in
hydrocarbons dissolved into the oil from the gas. We these OIAs into either the liquid or vapour phase clearly
indicates that, at the pore scale, both oil and gas were pres- residual oil in reservoirs. Variable attributes are interpreted
ent at the same time. as resulting from trapping of unmixed fluids such as oil and
It is well known in petroleum reservoir engineering that gas or unmixed oils at the pores scale. At Phuong Dong, the
the displacement of oil from pore space by gas results in a fluid inclusion study shows that a palaeo-oil column was
small amount of residual oil in the smaller pores and pore present in the reservoir before gas-condensate. The palae-
throats due to capillary forces. The variable Blue to yellow o-oil was characterised by low °API oil and low methane
and White to yellow OIAs appear to be trapped from resid- content. Gas charge subsequently displaced the palaeo-oil
ual oils in the Phuong Dong field. As demonstrated by the column and the interaction between residual oil and gas,
FSCC experiments on a lower °API gravity Arab Medium at the pore scale, is preserved in the fluid inclusion record.
crude oil, this residual oil was then able to interact with the The charge scenario could be further investigated by phase
gas to form new immiscible hydrocarbon liquids (white envelop reconstruction using Petroleum Inclusion Thermo-
fluorescence) in the same process that modified the initial dynamic (PIT) procedure (Pironon, 2004) or composition
oil charge. We interpret the assemblages with variable and biomarker signature of the palaeo-oil and the oil leg
fluorescence from Blue to white, White to yellow and Blue using Molecular Composition of Inclusion oil (MCI) proce-
to yellow to be a result of this interaction between the dure (George et al., 2007).
residual palaeo-oil and gas. Mixing of hydrocarbon charges in the Phuong Dong res-
The variable Blue to white and Blue to yellow OIAs have ervoirs results in a complex pattern at the pore scale but fol-
characteristics of two-phase trapping of both gas and oil at lows the general concept describe by Wilhelms et al. (1996)
reservoir conditions. The variable White to yellow OIA, with asphaltenic fractions adsorbed onto the mineral sur-
which homogenise into the liquid phase and contain bitu- faces/water layers. Calibration of fluorescence spectrometer
men could be poorly mixed liquids that were present locally by a set of crude oils is revealed useful to derive physical
at the scale of individual fractures. The estimated API grav- and chemical properties of oil trapped in oil inclusions such
ities are highly variable, between 10 and 34 °API. Trapping as their density expressed as degree API. The methane con-
of gradational compositions between the residual palaeo-oil centrations in petroleum inclusions calculated by synchro-
(yellow) and new immiscible oil (white) could form the tron FT-IR present reasonable correlation trend with the
inclusions with variable fluorescence colour associated with derived API and with the CH2/CH3 ratio of the oil. Overall,
this OIA. It appears that some of the yellow fluorescing oil the observed trends were consistent with a decreasing den-
inclusions from this OIA are even poorer in methane, have sity and increasing light-end content of the oil during the
lower °API and higher relative CH2/CH3 ratios than the stepwise history of the field despite the trapping of gas
residual palaeo-oil from the oil leg. The enrichment in aro- washed residual oil. However, the fluorescence of oils and
matic hydrocarbons, resins, and asphaltenes is consistent their CH2/CH3 ratio are the more sensitive measurable
with alteration of the palaeo-oil by gas and fractionation attributes of individual inclusions to detect in-reservoir
of lower molecular weight compounds into a new immisci- processes.
ble liquid phase. Overall, the evolution in the gravity of oil
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Evidence for a palaeo-oil column and alteration of residual oil

1. INTRODUCTION assemblages (OIAs, Eadington and Kempton, 2008) can

Fluorescence and infrared spectroscopy are widely Table 1

medium and low gas/liquid ratio, respectively. A

On the CIE chromaticity diagram the ﬂuorescence col-

4.1.2. Estimated API gravity of inclusion oils

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