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World Oil

Originally appeared in

aPRIL 2013 issue, pgs 163-168. Posted with permission.

special section: GEOLOgical & Geophysical technology

Application of cuttings gas/oil analysis, rapid XRF and


high-resolution photography to reservoir evaluation
TECHNIQUES

Rock and fluid analyses


are essential for prediction
and characterization of
produced hydrocarbons and
for understanding reservoir
architecture. A new approach
for archived drill cuttings,
or cores of any age, allows
evaluation of small rock
samples and associated
trapped fluid with a single,
semi-automated workflow.

DON HALL, MIKE STERNER and ROHIT


SHUKLA, Fluid Inclusion Technologies, Inc.

Exploration and exploitation of increasingly complex reservoirs, along


with technical challenges associated with
optimizing horizontal wells into tight or
unconventional pay sections, benefits
from new approaches involving additional data collected in a cost- and timeAn ultra-high-resolution photographic
profile of the borehole lithology recorded
from drill chip cuttings.

effective manner. This article describes


one such methodology applicable to
samples that are historically viewed as
containing limited value, namely, unpreserved cuttings. During this procedure,
the rock is first photographed under
visible and UV light, then crushed and
analyzed for included hydrocarbon and
non-hydrocarbon species with a sensitive mass spectrometry system, and
finally probed for its elemental composition with a customized X-ray fluorescence (XRF) analyzer.
A key aspect of the process is that all
analyses are conducted on the same 1-gm
rock sample with an automated system,
thus preserving interrelationships among
rock type, fluid type and rock chemistry.
Automation and rapid analytical cycles
allow collection of large data sets, and encourage analysis of entire wellbores from
first returns to TD. Individually, the techniques are useful. Together they provide
unique insights into controls on hydrocarbon, reservoir and pay distribution, represent an additional tool for well placement,
and allow organized archival of rock type,
fluid and rock chemistry information that
is easily retrieved and studied in the context of future wells, even in the absence of
the original rock material.

Photography. Washed and dried


samples are photographed in white light
and under broadband UV excitation with
a special, high-resolution imaging system
to produce a stratigraphic catalog of every
sample submitted for analysis. Ideally, this
would represent all samples collected such
that a complete record of the penetrated
section is available for subsequent study.
Grain-scale details of porosity, rock type
and texture can be identified. UV images
indicate specific mineral fluorescence that
can be correlated with cement or rock types
that are hard to distinguish under white
light. Also, kerogen fluorescence is observable and can be related to thermal maturity
when appropriate macerals are identified.
Rock fluorescence is unlikely to represent
residual oil (unlike similar procedures conducted with fresh samples at the well site),
because the samples have been washed and
dried and may have been stored.
Images are stored and can be reviewed
with a special viewer (see section below).
These archived photographs are easier to
manage than the samples themselves, are
preserved for future use even when original samples have been lost, disposed of or
depleted, and allow geologists to study
rocks at their desks without relying on
sample descriptions or lower quality images from wellsites. These images also
can be made available to well site personnel on subsequent wells to aid in sample
description and recognition of key stratigraphic markers.
Trapped fluid analysis. Petroleum
migration, reservoir charging, and local
generation of hydrocarbons from mature
source rocks leave trace evidence as fluid
inclusions: micron to sub-micron sized
sealed fluid-filled cavities in diagenetic
cements and healed microfractures.1
Fluid inclusions are not identified during conventional show analysis and are
commonly present even in the absence
of these classical shows. In addition to
migrated fluids, Adsorbed or free-phase
volatiles within converted kerogen nanoWorld Oil/April 2013163

geological & geophysical technology

pores can comprise an appreciable component of trapped fluid in mature, organic-rich rocks.2 Destructive bulk analysis
of trapped organic and inorganic fluids
is accomplished via the Fluid Inclusion
Stratigraphy (FIS) technique.3 Samples
are crushed in a vacuum system, and
liberated fluids are analyzed via direct
quadrapole mass spectrometry for C1C13 petroleum species, and inorganic
volatiles (e.g., CO2, H2S, He). Mass spectra and depth profiles of critical species

provide a full wellbore profile of trapped


fluids that document trapped petroleum
distribution within the stratigraphic section, the chemistry of migrated or locally
generated petroleum, the location and
effectiveness of seals and evidence of
proximal charged reservoirs that may not
have been penetrated by the borehole.
The latter application relies on entrapment of water-soluble organic species
such as acetic acid and benzene. These
compounds are concentrated in water-

Fig. 1. Static image from an interactive software program that allows mud gas
compositions, rock and fluid chemical data, electric logs and rock images to be viewed
and manipulated.

Fig. 2. Selected XRF and FIS data from a horizontal well within Cardium sandstone. Data
document a sweet spot which was found to have highest initial production.

164april 2013/WorldOil.com

bearing intervals within kilometers of


petroleum reservoirs, and produce diffusion halos centered on these deposits.4
Within unconventional reservoirs, FIS
can infer sweet spots, calculate likely produced-fluid characteristics and help distinguish poor completions from poorly
placed laterals. FIS provides a convenient
geochemical screening tool for follow-up
petrographic and microthermometric
work. These techniques help identify specific hydrocarbon charge events, quantitative API gravities, saturation state of
hydrocarbon fluid, and salinities for log
calculations of water saturation.5
Elemental analysis. XRF of rock material has been shown to have a number of
invaluable applications to petroleum exploration, with more recent focus toward
unconventional systems.6,7 XRF analyzers
determine the chemistry of a sample by
measuring the spectrum of the characteristic fluorescence X-rays emitted by the
different elements in the sample when it
is illuminated by X-rays of sufficient energy. The data provide information that
can be related to rock and cement type
via computer programs,8 although quantitative analysis also benefits from spot
analyses via additional techniques (e.g.,
XRD, QEMSCAN).9 Historically, chemical stratigraphy via XRF and ICP-MS has
been used to correlate monotonous stratigraphic intervals with unclear or variable
lateral extent and thickness, particularly in
the absence of sufficient biostratigraphic or
lithostratigraphic markers. Trends in element abundance and ratios have also been
used to infer depositional environment,
anoxic events conducive to preservation of
organic matter, transgressive vs. regressive
cycles and sediment provenance. Empirical
correlations can provide semi-quantitative
indications of TOC, and elemental summations have been proposed as a means
of quickly determining relative brittleness.
The latter is relevant to completions. Once
delineated from vertical penetrations, key
chemostratigraphic markers can be used to
steer the wellbore in real time,10 or, in the
case of the present method, retrospectively
determine or confirm the wellbore path.
Viewer. The results of these three steps
are loaded into a viewer that allows the
user to rapidly assess relationships among
the various image and chemical data sets,
Fig. 1. Although not a data analysis tool in
the strict sense, the software has virtually
no learning curve and is uniquely suited
to this specific dataset. LAS files and stan-

geological & geophysical technology

dard image files are created as well, which


are compatible with virtually all other industry programs.

Fig. 3. FIS, XRF and image data from a vertical well illustrating three zones.

EXAMPLES

Si

Al

FIS

Fe

Ca

Sr

CO2

C1

C4

C7

Zone 1

2,000
3,000
4,000
5,000
6,000
7,000
8,000

0
60,000
120,000
180,000
240,000
0
8,000
16,000
24,000
32,000
0
8,000
16,000
24,000
32,000
0
25,000
50,000
75,000
100,000
0
2,000
4,000
6,000
8,000
0
90,000
180,000
270,000
360,000
0
150
300
450
600
0
262,5000
525,0000
7875,000
10,500,000
0
500,000
1,000,000
1,500,000
2,000,000
0
30,000
60,000
90,000
120,000
0
1,250
2,500
3,750
5,000

9,000

Si

b)

Al

Fe

Ca

Sr

XRF
Si

Al

Fe

Ca

Sr

CO2

CO2

CH4

Parafins 57 AlkNaphtha

FIS

C1

C4

C7

2,000
3,000
4,000
5,000
6,000

Zone 2

7,000
8,000

0
60,000
120,000
180,000
240,000
0
8,000
16,000
24,000
32,000
0
8,000
16,000
24,000
32,000
0
25,000
50,000
75,000
100,000
0
2,000
4,000
6,000
8,000
0
90,000
180,000
270,000
360,000
0
150
300
450
600
0
262,5000
525,0000
7875,000
10,500,000
0
500,000
1,000,000
1,500,000
2,000,000
0
30,000
60,000
90,000
120,000
0
1,250
2,500
3,750
5,000

9,000

Si

c)

Al

Fe

Ca

Sr

XRF
Si

Al

Fe

Ca

Sr

CO2

CH4

CO2

C1

Parafins 57 AlkNaphtha

FIS
C4

C7

2,000
3,000
4,000
5,000
6,000
7,000
8,000

Zone 3

9,000

0
60,000
120,000
180,000
240,000
0
8,000
16,000
24,000
32,000
0
8,000
16,000
24,000
32,000
0
25,000
50,000
75,000
100,000
0
2,000
4,000
6,000
8,000
0
90,000
180,000
270,000
360,000
0
150
300
450
600
0
262,5000
525,0000
7875,000
10,500,000
0
500,000
1,000,000
1,500,000
2,000,000
0
30,000
60,000
90,000
120,000
0
1,250
2,500
3,750
5,000

Figure 2 shows selected XRF and FIS


data from a horizontal well within Cardium sandstone. The wellbore encountered an unexpected fault, and drilled
out of section into the overlying shale in
the lower part of the well. The transition
from sandstone to shale and back again
is clearly identified in the XRF data as an
increase in Al and K (dominantly related
to clay minerals in this case), and a concomitant decrease in Si (reflecting lower
bulk quartz percentage). A simple cross
plot of Al vs. Si defines the basic rock
types here. However, of greater interest
is the relationship between Fe, Ca, Si and
FIS petroleum indications (represented
by C1 and C7). The highlighted interval
is characterized by increased Fe and Ca,
decreased Si and increased light oil indications in FIS data. Petrographic work
indicates that the zone contains increased
visible porosity related to the presence of
siderite cement. High visible petroleum
inclusion abundance is consistent with
high petroleum saturation, in this case
42 gravity undersaturated light oil (derived from fluid inclusion petrography
and microthermometry). This zone was
tested independently and found to be the
best producing interval in the wellbore.
If laterally continuous, it may represent a
target for future wells in the area. FIS acetic acid anomalies are present throughout
the well, consistent with the presence of
penetrated liquid petroleum charge with
probable elevated water saturation.
Figure 3 illustrates FIS, XRF and compressed image data from a vertical well,
along with three zones that will be discussed in more detail. The upper zone is
siliciclastic dominated with thin carbonate-enriched intervals, some of which have
distinctive UV fluorescence. Two Fe-S
anomalies correlate with what appear to
be thin red beds or exposure surfaces, as
images indicate the presence of hematitestained rock. Covariance of Ca and Sr is
noted in carbonate bearing beds, and, in
this well, distinguishes limestone from dolomite. Thin, dry to wet gas FIS anomalies
correspond to these carbonate-enriched
intervals, and indicate petroleum migration through these zones. Overall, however, the upper section appears to have limited petroleum prospectivity, contains no

XRF

a)

Si

Al

Fe

Ca

Sr

CO2

CH4

Parafins 57 AlkNaphtha

World Oil/april 2013165

geological & geophysical technology

Fig. 4. Correlation of elemental sulfur response with gamma ray response suggests
variation in source potential, and correlates with visual organic matter in images and
thin section.

5,750

100

200

Gamma
400 500

300

Source rock

6,250

600

700

5,750

Sulfur
2,000 4,000 6,000 8,000 10,000 12,000 14,000 16,000

Fig. 5. Cross plot of Zr and Si illustrating


the difference between biogenic silica
(chert in this case) and terrestrial derived
silica (quartz associated with sandstone
and siltstone). Sample point colors are
grouped according for formation.

500

Bio

400

6,250

ge

nic

300
6,750

7,250

7,750

-Z
l Si

ria

100

t
res
Ter

0
7,750

8,250

8,250

8,750

8,750

9,250

9,250

-100

PetroFecta from Fluid Inclusion Technologies


is a unique approach combining XRF (PDQ-XRF ), Trapped Fluid Analysis (FIS ), and
High Resolution Photography (RockEye ) of the entire wellbore from well cuttings or core samples
of any age. All analyses are conducted on the same 1 gram sample (up to 575 samples per well)
with an analytical cycle of four days. Data provided on a DVD with previewer software.
Information about PetroFecta and the umbrella of FIT services,
call 918.461.8984 or visit www.fittulsa.com

Visit Us at: NAPE East Booth #122; GeoConvention Booth #1004;


AAPG Booth #2033; SPWLA Booth #500

100

200
Zr

300

400

500

proximity to pay indications and reported


no significant drilling shows. Shallow CO2
is interpreted to be bacterial in origin and
is interpreted to have been formed by bacterial sulfate reduction in the presence of
vertically seeping light thermogenic hydrocarbons. These FIS microseeps are statistically correlated to deeper liquids potential
in many instances, and here are consistent
with FIS and mud gas indications of penetrated liquid petroleum deeper in the well.
The middle of the well is carbonatedominated with little or no covariance of
Ca and Sr. The zone is dolomitic, and records UV fluorescence. FIS hydrocarbon
indications increase, with the bulk trapped
phase varying in character from dry gas to
oil. Thin, dry gas zones and decoupled C1
and C7 behavior imply at least two distinct charges, consistent with petrographic
work described below. FIS CO2 response
is elevated through this zone, but does not
covary with hydrocarbons; thus, a separate
source (probably diagenetic) is suggested.
FIS data suggest the upper and lower thirds
of this section have better prospectivity,
and petrographic analysis documents the
presence of liquid petroleum inclusions
in high abundance within these high FIS
response zones. High petroleum inclusion abundance implies high oil saturation
or paleo-saturation. Moderate to uppermoderate gravity (~30 to low 40 gravity),
undersaturated oils are inferred from fluid
inclusion relationships, consistent with
produced fluids in the area. A dual porosity
system is indicated, with intergranular and
fracture porosity being significant.
The lower section contains mixed siliciclastics and carbonates with some covari-

166april 2013/WorldOil.com
FIT_UmbrellaThird.indd 1

end
r tr

200

7,250
Mature oil-prone
organic matter

ca

SI, 10A 3

6,750

sili

3/11/13 10:45 PM

geological & geophysical technology

ance of Ca and Sr consistent with a mixed


limestone and dolomite interval. Elemental sulfur response correlates with the gamma ray curve in this zone and throughout
this well, Fig. 4, and likely reflects source
potential.11 Mature oil-prone kerogen is
identified in thin section. A flat to negative
Si/Zr profile through the upper portion of
this section is consistent with biogenic silica, Fig. 5, in contrast to the generally positive relationship obtained in siliciclastics,12
and phosphorus anomalies are consistent
with the presence of apatite in thin section,
a near-shore depositional environment
with relatively low sedimentation rates and
elevated surface productivity.
The most promising zone, based on
FIS response, is at about 9,000 ft, corresponding to a fractured cherty carbonate,
which also displayed significant mud gas
anomalies while drilling. CO2 covaries
with hydrocarbons, and was also recorded
in the mud gas, suggesting that some CO2
will be present in the produced petroleum. The source of CO2 and intermittent
sulfur species is thought to be related to
thermochemical sulfate reduction at high
temperature. As it is unlikely that maximum burial temperature at this depth exceeded the threshold for local TSR (about
130oC), influx of mature gas from deeper
in the basin is suggested. This is consistent with the presence of discrete dry gas
phase in the FIS data. High visible liquid
petroleum inclusion abundance is documented here, and suggests high saturation
of light oil and gas-condensate in fractured cherty carbonate.
There is evidence from fluid inclusion
data that the reservoir contains both gas
and condensate or light oil. Lower inclusion
abundance and presence of tar-like dead oil
deeper in the section represents residual
oil. Some of this dead hydrocarbon may
have been sourced via gas-deasphaltening
during emplacement of the previously

mentioned dry, mature gas from depth.


Compositional calculations of the bulk
FIS volatiles in this lower interval suggest a
slightly lighter bulk petroleum phase in the
deeper zone as compared to the lower section of the middle interval described above.
CONCLUSIONS

The combination of photography,


trapped fluid chemistry and bulk rock
elemental analysis has been shown to
provide valuable and otherwise unobtainable information with broad application,
including present and past petroleum
distribution, source and chemistry, rock
and cement type, chemical stratigraphy
and mineralogical trends necessary for log
calculations, depositional environment
and likely source rock potential, and rock
properties relevant to completion. Data
are all collected on a single approximately
1-gm aliquot of washed and dried rock
material, with an analytical cycle of four
days. Approximately 600 samples per well
can be analyzed. Data can be used to help
understand petroleum systems in conventional and unconventional reservoirs, and
optimize wellbores and completions.
REFERENCES
1. Hall, D. L., Fluid Inclusions in Petroleum Systems: A
Compendium of Influential Papers, AAPG Getting
Started Series, vol. 15, 2008.
2. Kausik, R., C. C. Minh, L. Zielinski, B. Vissapragada,
R. Akkurt, Y. Song, C. Liu, S. Jones and E. Blair, Characterization of Gas Dynamics in Kerogen Nanopores
by NMR, SPE, Denver, 2011.
3. Hall, D. L., W. Shentwu, S. M. Sterner and P. D. Wagner, Using fluid inclusions to explore for oil and gas,
Harts Petroleum Engineer International, pp. 2934,
1997.
4. Burtell, S. G., and V. T. Jones, Benzene content of
subsurface brines can indicate proximity of oil, gas,
Oil and Gas Journal, June 3, pp. 5963, 1996.
5. Munz, I. A., Petroleum inclusions in sedimentary basins: systematic analytical methods and applications,
Lithos, vol. 55, pp. 195212, 2001.
6. Hildred, G. V., and C. R. Rice, Using high resolution
chemostratigraphy to determine well-bore pathways in
multilateral drilling campaigns: an example from the
Horn River Formation, British Columbia, Canada,
Geoconvention 2012: Vision, pp. 14, 2012.
7. Ratcliffe, K. T., A. M. Wright and K. Schmidt, Appli-

Article copyright 2013 by Gulf Publishing Company. All rights reserved.

cation of inorganic whole-rock geochemistry to shale


resource plays: an example from the Eagle Ford Shale
Formation, Texas, The Sedimentary Record, vol. 10, no.
2, pp. 49, 2012.
8. Cohen, D., and C. R. Ward, SEDNORM a program
to calculate a normative mineralogy for sedimentary
rocks based on chemical analyses, Computers &
Geosciences, vol. 17, no. 9, pp. 12351253, 1991.
9. Butcher, A. R., Getting the most out of ditch cuttings:
Find out how a new technology is revolutionizing the
way we can automatically quantify mineralogy, texture
and lithotype on a cutting-by-cutting basis, Petroleum
Exploration Society of Australia, PESA NSW, Sydney,
Australia, Sept. 12, 2008.
10. Marsala, A. F., A. M. Loermans, S. Shen, C. Scheibe
and R. Zereik, Real-time mineralogy, lithology and
chemostratigraphy while drilling, using portable
energy-dispersive X-ray fluorescence, Saudi Aramco
Journal of Technology, Summer issue, p. 1824, 2011.
11. Berner, R. A., Sedimentary pyrite formation: an
update, Geochimica et Cosmochmica Acta, vol. 48, pp.
605615, 1984.
12. Wright, A. M., D. R. Spain and K. T. Ratcliffe, Application of inorganic whole rock geochemistry to shale
resource plays, CSUG/SPE Paper 137946, Calgary,
2010.
Don Hall received BS (1982)
and MS (1985) degrees in
geology from the University of
California at Riverside, and a
PhD (1989) in geology from
Virginia Tech. He joined Amoco
Production Research in 1990 as
a research scientist, where he worked on
development and implementation of novel fluid
inclusion instrumentation and techniques. He
left Amoco in 1997 and co-founded Fluid
Inclusion Technologies, Inc.
Mike Sterner has a BS in
chemistry from the University
of Michigan and a PhD in
geology from Virginia Tech.
After post-doctoral research
positions in Germany and at
U.C. Berkley, he joined Pacific
Northwest Laboratory where he was involved in
thermodynamic modeling of electrolyte
solutions. Mike co-founded Fluid Inclusion
Technologies, Inc.
Rohit Shukla received his
Bachelors in Mechanical
Engineering from the University
of Mumbai in May 2005, and his
Masters in Mechanical
Engineering from the Oklahoma
State University in December
2007. He started working at FIT in March 2008.

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