Paul C. Hackley1, Alana M. Bove1, Frank T.

Dulong1,
Michael D. Lewan2, Brett J. Valentine1

1U.S.

Geological Survey, MS 956 National Center, Reston VA 20192

2U.S. Geological Survey, DFC Bldg. 20, MS 977, Lakewood CO 80225

Outline of this presentation

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Problem vitrinite reflectance suppression

Hydrous Pyrolysis Approach
Sample Materials
Petrographic Results Reflectance Results
Conclusions

Statement of Problem
Petroleum formation is defined within a range of reflectance
values
Oil Window: Ro 0.6-1.2%
Gas Window: Ro >1.2%
Gas Shales: Ro >1.2%
Thermogenic CBM: Ro >0.9%

If vitrinite reflectance is suppressed then it becomes more

difficult to predict thermal history and petroleum formation.

Important to characterize conditions which can cause vitrinite

reflectance suppression and retardation.
- overpressure, bitumen impregnation, a priori differences in
composition and maturation kinetics, others ...(?)

vitrinite reflectance
suppression, na reduction in

vitrinite reflectance values

below thermal maturity levels
determined by geochemical or
other petrographic parameters
arising as a result of atypical
hydrogen-rich vitrinite
chemistry inherited from the
precursor plant material or
introduced into the vitrinite by
the chemical microenviroments
of deposition, diagenesis, and
catagenesis ASTM, 2011

0.2

0.6

1.0

1.4

Original

HP Temperature (C) for 72h

Vitrinite Reflectance
Suppression

%Ro

1.8
Blackhawk coal
Frontier coal
Wilcox lignite
Phosphoria Shale
Woodford Shale
Alum Shale
Skull Ck. Shale
Mowry Shale

300
310
320
330
340
350
360
0.2

0.6

1.0

1.4

1.8

(Lewan, 1993)

Preparation

20C
Room Temp.

Heat-up

Pyrolysis

360C

72 h

Cool-down &
Collection
20C
Room Temp.

Generated
Gases
Water
12-15 g
Source
Rock
2.5-5.0 g

Expelled
Oil
Spent
Rock

Can be performed over a range of different temperatures and

heating times to assess different levels of thermal maturation

Hydrous Pyrolysis Experimental Approach

SwageLok mini-reactors

Sealing reactor

Filtering product

Pellet mount for reflectance

GC ovens for hydrous pyrolysis

Reflectance microscope

72 hr experiments at 300C, 320C, 340C, 350C, and 360C completed on seven source rocks (2 Wilcox
coals, Green River, Woodford, Boquillas, Alum, and Huron shales)

Samples Used in Experiments

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Green River Shale (Eocene Mahogany Ledge)

Wilcox Coal (Paleocene-Eocene, Texas)
Wilcox Coal (Paleocene-Eocene, Louisiana)
Boquillas Shale (Cretaceous, Eagle Ford equiv.)
Woodford Shale (Devonian)
Huron Shale (Devonian)
Alum Shale (Cambrian-Ordovician)
Samples are immature: Ro 0.30 to 0.50%

XRD Mineralogy
Green River, LOI 23.6 wt.%

Huron, LOI 21.6 wt.%

Alum, LOI 10.0 wt.%

QTZ

Boquillas, LOI 5.7 wt.%

QTZ

FLD

FLD

CARB

CARB

ILLITE

ILLITE

KAOL

KAOL

CHLR

CHLR

PY

PY

OTHER

OTHER

QTZ
FLD

Woodford, LOI 12.0 wt.%

QTZ
FLD

CARB

CARB

ILLITE

ILLITE

KAOL

KAOL

CHLR

CHLR

PY

PY

OTHER

OTHER

QTZ
FLD

Wilcox LA, LOI 79.3 wt.%

QTZ
FLD

CARB

CARB

ILLITE

ILLITE

KAOL

KAOL

CHLR

CHLR

PY

PY

OTHER

OTHER

Organic Geochemistry
1000

l
Green River
l

900

300

TYPE I

TYPE I
oil-prone
usually lacustrine

250

800

oil-prone
usually marine

700

Green River

200

Boquillas
II
II

600

Mixed TYPE II-III

oil-gas-prone

Woodford

Coals

150

400

Huron

100

Woodford
Alum

50

Coals

300

TYPE III
gas-prone

200

Boquillas

III
TYPEIII
III

100

TYPE IV

TYPE IV

inert

0
0

10

20

TYPE II

Huron
Alum

500
HI

S2, mg HC/g rock)

TYPE II

30

40

50

TOTAL ORGANIC CARBON (TOC, wt.%)

60

70

80

IV
IV

0
0

20

40

60

80 100 120 140 160 180 200

OI

Petrographic Results

Wilcox Coal TX & LA

Ro 0.46%

Original sample; subbituminous coal

with vitrinite, inertinite, fluorescent
liptinite
300C; no organic fluorescence
remaining, development of
fluorescent radial carbonate(?)

Ro 0.89%

Ro 1.05%

Ro 1.35%

320C; pitting and cracking of vitrinite

common; radial carbonate(?)

340C; pitting and cracking of vitrinite

common; ragged vacuoles; radial
carbonate(?)

Wilcox Coal - TX & LA

350C; Pitted and cracked; ragged
vacuoles; vitrinite same reflectance
as relict funginite

Ro 1.44%
360C; very similar to 350C sample;
vitrinite is pitted and cracked,
ragged vacuoles common

Ro 1.57%

Huron & Woodford Shales

Ro 0.48%

Ro 0.56%

Original sample; abundant AOM,

Tasmanites; original solid bitumen
texturally obvious
300C; Tasmanites still brightly
fluorescent but developing silky
luster in white light and showing
devolatilization features: shrinkage
cracks; bitumen abundant
320C; Tasmanites fluorescence
diminished, silky luster more
prominent

Ro 0.68%

Ro 1.02%

340C; Tasmanites largely volatilized,

replaced by carbonate and sulfide;
bitumen abundant

Huron & Woodford Shales

350C; Tasmanites completely
replaced by carbonate/sulfide,
bitumen forms network
groundmass, embayed against
euhedral neo-carbonate

Ro 1.21%

Ro 1.28%

360C; Tasmanites completely

replaced by carbonate/sulfide,
bitumen forms network groundmass

Green River Mahogany Ledge

Original sample; abundant AOM,
some original solid bitumen present
Ro 0.30%
300C; neo-bitumen forms from
AOM, original solid bitumen less
common
Ro 0.09%

Ro 0.15%

R 0.49%

320C; neo-bitumen forms a

gummy tar which remobilizes
during heat setting of pellets,
original solid bitumen very
scarce
340C; neo-bitumen very
abundant, migrates to grain
margins, entrains mineral
matter, original solid bitumen no
longer present

Green River Mahogany Ledge

350C; neo-bitumen shows coked
texture with mesophase, organic
fluorescence no longer present,
original bitumen has disappeared

Ro 1.00%
360C; neo-bitumen mesophase
domains have coalesced; formation
of neo-sulfides and oxides;
qualitatively less neo-bitumen is
present than lower temperature
experiments
Green River Gas

Ro 1.31%

0.00
280
300
T (C) 320
340
360
380

0.20

Gas (g)
0.40

0.60

0.80

Reflectance Results

Reflectance Results

Reflectance Results

Reflectance Results

Reflectance Results

Conclusions
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Hydrous pyrolysis of coals and shale source rocks

produces a host of physical changes, including:

Tasmanites devolatilizes and is replaced by minerals

Qualitatively greater quantities of bitumen forms at higher
temperatures in the shales
AOM in Green River becomes a neo-bitumen
Vitrinite devolatilizes in coals leaving pits, cracks and ragged
vacuoles

Kinetic barriers to bitumen maturation in response

to thermal stress are higher than for vitrinite; the
effect is more pronounced at lower heating levels
If petrographers mistake bitumen for vitrinite due to
absence of void-filling textures ... this work explains
reports of vitrinite reflectance suppression at low
thermal maturity, particularly in the Paleozoic