Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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Procedures
for
kerogen isolation
il.
ISOLATION
METHODS
FOR
PHYSICO.CHEMICAL ANALYSIS
Among
the methods used,
we
will
distinguish physical methods
from
chemical
methods.
A. Physical
methods.
Almost all ore dressing
processes
were
used,
i.e. flotation,
ultrasonic
methods,
electroma-
gnetic
and electrostatic
methods,
processes
based on the
wetting
properties
of
OM and
mine-
rais, etc.
[32,
33,
34].
These
processes
are applied
after
fine
grinding
of the
sediment.
Organic fractions
are thus
obtained which should
not, in theory, be chemically altered.
However the rate
of recovery
for
OM
containing small amounts
of minerals
is low,
and
the chemical
composition of
the reco-
vered
fraction
is
rarely
representative of the whole. In order
to improve
recovery it is neces-
sary
to carry out successive
grindings
and
to
repeat
the operations several times, which
is
long
and
costly.
We will however note that, according
to Robinson
[32]
,
use of
a
method
derived
from
that
of
Quass
129,
371has
made it
possibie
to considerably
reduce
(24-99V0)
the
proportion
of the
mineral fraction from oil shales of
various origins. This method
is
based on
wettability diffe-
rences
between
kerogen and the
mineral matrix.
It
consists
in incorporating
water and an oil
phase
(mineral
oil or
n-hexadecane in the cases mentioned) during
attrition
grinding.
The
kerogen
tends
to form
progressively
a
separate
phase
with the oil.
Good
results were
also
obtained
with
Green River Shales by centrifuging
in
a CaCl,
solu-
tion
[32,
36]
with
a
method
based
on
that of Luts
[25].
It
is
easy
to
understand the
lack
of
effectiveness and
general
applicability
of
these methods
in
view
of
the diversity
of
the situations
which
occur. Success cannot therefore
be expected
except in
particular
cases, and
the methods must
be
modified in terms
of the
characteristics
of
the
samples.
B.
Chemical
methods.
Theoretically the objective of these methods is to isolate the kerogen
by
making
the mineral
phase
solubie
while
keeping modifications
in
the chemical composition
of the
OM as
small
as
possible.
They do
in
fact make
possible good
recovery of the
OM
which
is
little
altered
except for
recent
OM
(recent
sediments, soil,
peat,
etc.).
Foliowing the work
of Down
[7]
,
Giedroyc
[4]
and Dancy
[4]
the
methods
now
used are
all
based
upon
the
dissolution of carbonates, sulfides,
sulfates, oxides
and
hydroxides
by HCI
and the dissolution
of
silicates
by HF, after fine
grinding
of
the
rock
(-
100
p)
in order
to
lacilitate
the reactions.
It
is
usually
recommended that
operations
be
carried out
at a
tempe-
rature which is
sufficient to dissolve all carbonates but not too high
to
prevent
possible
oxida-
tion
of
the organic
matter
15,14,361
i.e. about
70'
C.
illilli
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Sample,
IFP
No.
H/C*
o/c*
x
100)
Organic
S,/C*
(x
100)
N,/CX
(x
100)
Fe
(weight
9o)
C
(weight
vo)
C
recovery
(.qo)
Green
River
Shales,
USA,
Eocene
t5760
1
2
|.64
7.8
0.6
1.&
0.i
78.0
95.9
l
.55
8.1 0.4
I
.65
0.1
'76.0
Green
River
Shales,
USA,
Eocene
15190
1
2
1.16
3.3
1.7 2_5
1.9
75.1
101.4
1.12
3.6
0.9 2.1
t.l
77.8
Torbanite,
Australia,
Permian
15844
I
2
I .54
3.5
0.6 1.2
0
83. r
97.1
I
.53
3.7
0.6 1.1
0
80.8
Messel
Shales,
Germany,
Eocene
I
15132
2
I .39
21.'7
t.7
2.1
I.0
65.3
94.6
I .33
19.6
0.9 2.3
0.6
67.1
Lower
Toarcian
Shales,
France
1
10696
2
1.21
14.9
2.5 2.3
6.2
58.8
98.6
1.24
14.2
2.9
2.2
I
_2.
68. I
Siluro-Devonian
Shales,
Algeria
1 4085
I
2
0. Bl 5.0
0.7
3.8
8.2
66.9
101.8
0.74 8.6
2.3
3.8
0.8
10.3
Jurassic,
Mexico
25838
1
2
1.2'7 13"8
14.5 2.9
15.6
24.8
101.9
1.08
6.5
1.2
2.3
t0.7
53.1
Springhill
Shales,
Chile,
Jurassic
1 1463
1
2
0.60
t1.1
0
0.8
3l
.9 20_9
95
0.'/0
9.9 3"9
1.8
/1
50.7
Peat,
F{olland,
recent
1
5557
i
2
r.00
54.5 0.8 1.4
0 53.1
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7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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In
the
end
the
attitude
towards
the
problem
of
mineral
impurities
in
the
kerogen
isolated
by
hemical
means
should
be
pragmatic:ii;;;.."
observed
at
IFp
thatstatisticaily
it
is
possi-
le
to
tolerate
a
pvrite
content
as
high
as
40vo
by
weight
"r;/;;;.;;tent
of
orher
minerals
as
igh
as 15vo
by
weight
(chapter
+i*lirr"ut
.xcessive
difficulties
io.
rur..
analyses.
Procedures
for
kerogen
isolation
a
Aromolic
C=C
mostly,bonded
qurnones,poionzed
woier
I
{-=O
I
CH2
+[H3
llJ'i'
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C-H
(bendrnq-
-ou1-of-plone
)
1,,,
>4
I
I
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roied
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1800
1600
1400
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rooo
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of f/uosrlico/es
b
--.------
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3200
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1200
1000
800
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zuuu
jB00
1600
l4O0
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cm_r]
liiim,
til
lllln
,ilntf
lllir.lt
ltr iilii
lrl
illL
llr
,
, ri
rn
L
Fig.
2.1.a.
-
IR
spectra
of
a kerogen
sample
from
Mexico
(IFp
No
25g3g):
1.
Before.
2.
After
boiling
HCI
treatment,
showing
the
disappgarance
of
bsorption
bands
of
neofoimed
nuo.ijer.
Fig. 2.1.b.
-
IR
Spectrum
of
a
ralstonite
sample.
-
7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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Procedures
for
kerogen
isolation
3. Effects
of reagents
on
organic
matter.
Surveys
of this
question
have
been
made
by
Saxby
[33,
34,
351.
a.
HCI
and
HF.
HCI
and
to
a
lesser
extent
HF
have a
hydrolyzing effect
on the
oM
of
sediments. The
lesser
evolved
the
OM,
the
stronger
is
the
effect.
Reactions
other
than
hyclrolysis
are
possible
[33,
341
'
(According
to
the
erperience
acquired
at IFP,
the
addition
of
chlorine
and fluorine
is
probable)'
Oxidation
of
the
OM
can
be feared
if
the
temperature
is
too high (
>
70.
C),
espe-
cially
if
the
preparations
run
dry
[5,
14,36].
Therefore performing
the
attacks
under
an inert
atmosphere
is
advisable.
The
extent
of hydrolysis
can
be
evaluated
by
an
organic
carbon
balance.
Durand
et ot.
l10l
have
shown
that
for
a
series
of
coals
ihe
carbon
loss
was
about
l0
to
15%
at the
peat
stage
and
was negligible
beyond
the lignite
stage.
For
an
equal
degree
of
evolution,
this
carbon
loss
is
greater
for
so-called
"marine"
or
"lacustrine"
OM
(as
ofposed
to
so-called
,,continental,,
which
like
coal
is largely
derived
from
the
constituents
of higher
vegetation
and
especially
lignin)'
It
is
probable
that
this
figure
can in
certain
cases
exceed
50go
at
the
recent
sediment
stage
[1,
6, 18].
Measurements
made
at
IFP
indicate
however
that
for
ancient
sediments
the
carbon ioss
due
to hydrolysis during
the
preparation
of
the kerogen
is
generally
Iow.
Statistics
for
45
samples
of
very
varied
origin
show
an
average
carbon
loss
of
5.8g0.
Most
of
this
car-
bon loss
moreover
is
very
probably
due to
handling.
The
effect
of HCI
and
HF on
the
chemical
composition
can
be
studied
with
rock
which
is
very
rich in
oM.
Table
2.2.
shows
the results
of
elemental
analysis
made
before
and
after the
treatment
of
such
rock.
The
corresponding
OM represents
a
quite
broad
range
of
the
chemi-
cal
slructures
to
be found
in
kerogen.
with
theexception
of slightlyevolvedrocks,
elemental
analysis
are not
modified
to
a
great
extent.
This result
was
also
obiained
for
a
series
of
coals
[10]
'
However,
fixation
of Cl
and
F has
been
experienced
in
some
cases.
It
increases
with
evo-
lution
of
oM
due
to burial,
owing
probably
to
the
increase
of
microporosity
and
aromaticity,
and may
reach
several
percents
weight;
this
fixation
could
occur
by
absorption
of
HCI
and
HF
in the
microporosity
or by
addition
and
substitution
reactions.
other
methods
of
investigation
such
as
IR
spectroscopy,
dark-field
electron
microscopy
(EM),
electron
spin resonance
(ESR),
spectroscopy
and
thermogravimetry
do not
show
important
rnodifications
either
(tl0l
,
Fig.
2.2.).
once
again immature
oM is
the
rnosr
affect-
ed'
For
example
we
can
indicate
the
very
marked
increase
in the
lunction
C
:
O at I
700
cm
r
in the
IR
spectra
of
pear
and
lignite ([10],
Fig.
2.3.)
Since
all these
observations
were
macie
with
overall
study
methods,
it
is
obviously
not
pos-
sible
to
state
that
there
were
no
modifications
in
detail.
In
addition,
in
the
case
of
sediments
with
less
oM,
the
chemical
bonds
between
the
organic phase
and
the
mineral phase
wouid
necessarily
be destroyed"
The
effect
of hydrolysis
on
oM which
is
not
greatly
evolved
and
especially
on recent
sedi-
rnents
is
such
that
in this
case
the
term
kerogen
should
not
be
used
for
the
residue
of
acid
attack.
The
analytical
object
(the
residue
of the
attacks)
is very
different
here
from
the
initial
concept.
In
the
case
of
so-called
"marine"
or
"lacustrine"
OM
where
the
effect
is
greater,
a
large
part
of
the
organic
residue
of the
acid
attack
probably
consists
of
the
organic
fraction
which
is
not
contemporary
with
sedimentation
(reworked
products)
which
are
more
resistant
-
7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
9/19
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7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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44
procedures
for
kerogen
isolation
2
ItiJil',lfli;.?:'n'
other
hand
for
ancient
sedimenrs
rhis
organic
residue
seems
to
be
very
It has
been
proposed
[17,
39]
to
use
acelic
acid
or
carbonic
acid
fbr
reducing
the possible
ffects
of
hydrochloric
acid.
The
first
has
the
disadvantage
of
being
an
organic
acid.
There
is
he
risk
that
it
will
not
be
possible
to
eliminatert
comptJtety
ur,.r',t.
attack.
The
second
isffective
only
at
high pressures.
In
anv
case
the
fact
that
it;;r;;;r;".y
ro
use
HF
for
the
des_
ruction
or
silicates
does
away
with
the improvement which
was
intended.
b.
Agents
for
destroying
pyrite.
Reducing
agents.
LiAlHo:
this
is
the
only.
reducing
agent
whose
..^fI".-,1
on
kerogen
have
been
systematica'y
tudied'
It
is
used
in
solution
in
tetralivdro
fuiran
[22,33],
or
di";;;;
mixed
with
diethyl
ether
EFFECT
oF
No3H
rREArMENldi. tli;'.NrAL
ANALysrs
oF
KER.GEN
(NO3H
40V0,70"
C)
l.
Before
NO,H
treatment
2.
After
NO,H
treatment
*
Atomic
rarios
I
'
L,
I
Sample,
IFp
No.
H/C*
o/c*
(x
100)
Organic
S,/C*
(x
100)
N,/C*
(x
100)
Fe
(weighr
vo)
C
(weight
vo)
C
(recoverl
vo)
Lignite,
Germany,
Eccene
I
15238
2
Green
River
Shales,
USA,
Eocene
I
15760
2
Green
River
Shales,
USA,
Eocene
I
15409
2
Lower
Toarcian,
Shales,
France
I
I
i
ro6e6
2l
0.'77
35.7
1.0
59.1
0.55
57.8
1.8
0.4
6.9
1.8
0.4
0.5
49.5
t.64
4.6
80.0
68.8
1.65
r
3.5
0.6
1.3
4.1
0.7
0.0
2.0
72.3
r .56
10.
I
72.4
61.9
1.48
21.9
0.5
7.5
0.2
6.2
65.2
L26
13. 1
3.1 2.'7
61.5
45.0
t.t9
35.5
2.0
8.2
0.2
57.0
uouala
Basrn,
cameroon,
Cretaceous
2
13356
2
Green
River
Shales,
USA,
Eocene
I
15789
(Heavy
fraction)
2
0.54
6.5
0.0
2.4
4.8
17.4
6l
.3
0.45
27.4
0.5
7.6
0.t
64.1
r.48
20.7
t+.J
0.0
36.0
7.8
1.01
))4
R-
Noz
3400 3000
2600
1800
1600
1400
1200
1000
800
4
I
Aromotrc
C=C
mosl1y,
bonded
qutnones,po
or zed
woler
c=o
I
cHr*cHr
I
I
l'i'
Soturoled
n-u
Aromolic
C-H
I
+
+WAVINUMBERcm-r
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7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
14/19
O
COALS
^
UINTA
BASIN
r
TOARCIAN
FI
()l
=15
ilE
t
rl=
zlu
lrJl
Y
(rl(-)
olc)
rlE
9l-
=lH
l=
=l
,i
.:
Fig.
2.6.
-
Weight
ratio
of kerogen
extract
reflectance
for:
to
rock
extract
as
a function
of
vitrinite
o
Coals.
A
Uinta
Basin
series.
I
Lower
Toarcian
series (paris
Basin
and
Posidonien
Schiefer
from
Germany).
Kerogen
is
prepared
from
the
CHCI,
extracted
sediment,
then
extracted.
Fig,
2.7.
-
Gas
chromatograms
of
saturates
from:
l'
cHCl3
extract
of
the
sediment.
2.
cHcrr
ertracr
of
the
kerogen
prepared
from
the
cHC'ri
extracted
sediment.
Lower
Toarcian
sample
frJm
c".'.u,ry
(Posidonien
Schiefer,
IFp.
No
20508).
L
t
a
^-
--"---.,-.-1,...1-.'",,,,-..,,_r
l-,.,-,1"
r.1
.-
1,,
*l
AROI\4ATICS
"G"'
3a_)
2A
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1
'
,
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b
l
ll
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.
I
]I
rll
i-i
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,
17
"
1i1
A
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7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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50
Procedures
for
kerogen isolation
2
vered will
be
richer
in minerals,
either
original
(physical
and chemical methods)
or
neoforma-
tions
(chemical
methods).
Petrographers
generally
prefer
physical
methods
to
chemical
methods.
Physical methods have
a tendency
to favor the recovery
of large-size
elements,
especially
microfossils,
organic debris
and
large
areas of macerals
which
are the
special
objects of study. Separation methods
by
centrifuging,
heavy
liquids
or flotation
(Chapters
3
and
12)
are
the most
frequently
used.
In
addition,
chemical methods
are
thought to modify
the optical
properties
which
are
used
for
analysis
and especially
for
fluorescence
(Chapter
12).
Among
petrographers,
palynologists
are
perhaps
the most
exigent
as
to the
preservation
of
the
morphology
since the ornementation
of
pollen
are
often
indispensable
for
the
determina-
tions. The
problem
of
grinding
is therefore
even
more important
for them.
They
prefer
che-
mical methods
to
physical
methods
since
they work
principally
with transmitted light
methods.
In this case
chemical
methods
make it
possible
to obtain
cleaner
preparations.
For
them,
pyrite,
because
of
its
opaqueness, is an obstacle
to
observation,
and they often elimi-
nate
it
by
nitric
acid
treatment
which obviously has
the
result
of making
the
recovered
frac-
tion of OM still
less
representative
of
the
whole
(cf.
paragr.II.B.3b).
This treatment
does not
change
the morphology
and has some
effect
on the
colors
(the preparation
becomes
brighter
or darker). Pyrite
and other residual minerals may
also be eliminated
by centrifuging.
It
is
probable
that the
contradictory
requirements
of
chemists,
petrographers
and
palyno-
logists
could
be
reconciled
by
means
of
a systematic
study which
would
define, more
closely
than
has
been done
up
to now, the
consequences
of
grinding
on morphology,
the
quality
of
extractions and chemical attacks
as
well
as
the
consequences
of
chemical
attacks on optical
properties.
A unification
of
operating
procedures
if
possible
would
greatly
facilitate
the
synthesis
of
petrographic, palynologic
and
geochemical
analysis
for
the
same samples.
IV.
OPERATING
PROCEDURE
USED
AT
IFP
Operating
procedures
are very
varied
in
spite of the fact that
there
are many
restrictive
con-
ditions. As
an example we
will
describe the
procedure
used aI
IFP.
This
procedure was
designed
for
physico-chemical
rather than
petrographic
analysis.
However many
petrographic
analysis with reflected
light
have
been made
with
kerogen
pre-
pared
in this way.
On the other hand
it
seems to
be
difficult
at the
present
time
to
use these
preparations
in
palynology,
mainly
because drying
and
grinding.
The
sediment
is first
ground
in
an Aurec ring
mill
for
30
s. In most
cases
the
grain-size
mode
produced
in
this way
is 80 to 100 p.
There is
then chloroform
extraction in
a
beaker
placed
on
a
magnetic
heating
agitator
cove-
red
with
a
cap
filled
with
water. The
operation lasts
for
an
hour
and
the temperature
of the
chloroform
is
around
50"
C.
The
extracted rock
is
then
collected
by
filtration
with
fiberglass
paper.
The rock
is then
placed
in
an apparatus
in which
acid attacks
and washings
are carried
out
followed
by filtration
with
an 0.6
p
filter
[9],
(Fig.
2.S).
All operations
take
place
between
60
and
70o
C
in
a
nitrogen
atmosphere
so as to avoid
possible
oxidation
of
the
kerogen
during
preparation.
-
7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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52
Procedures
for
kerogen
isolation
REFERENCES
are removed
from
the
reactor
by
means
of
a
peristaltic
pump.
The
proper
temperature
is
maintained
by
means
of
hot
water
circulation
inheating;uct.tt.
The
reactors
have
a
capacity
of
0'750
litre
and
are
made
of
a transparent
fluorinateJ
polyme..
The
maximum
amounts
of
rock
subjected
to
attack
are
about
50
g
for
highly
silicate
rock
and
100
to
200
g
ro.
u..f.u.-
bonate
rock.
The residue
of
the
acid
attacks
is
recovered
by
means
of
the
0.6
p
filter.
At
this
stage
an ali-
quot part
may
also
be
recovered
for
microscopic
study
and is preserved
in
acidulated
water.
Indeed
kerogens
are
more
difficult
to
study
under
the
microscope
if
they
have
been
dried.
There
is
no
extraction
from
the
residue
with
organic
solvents.
It
is
dried
in
a vacuum
at
100"
C
(80'
C for
slightly
evolved
oM).
Aliquot parts
for various
types
of
analysis
are
pla-
ced in
sealed
small
containers (l-10
ml).
It
has
been verified
that
they
can
be
preserved
in
these
containers
without
significant
alteration
by
means
of
elementary
analyses
carried
out
at
regular
intervals
on kerogen
which
has
been
frequently
handled
and
iherefore
exposed
to
the
light
and
air.
At
the
present
time
residual
minerals
are
not
eliminated.
Is has
been
observed
empirically
that
physico-chemical
analysis
were
generally
possible
if
the iron
content
was
under
1890
(corresponding
to
a
pyrite
content
of
around
40Voj
and/or
if
the
contents
for
minerals
other
than
pyrite
were
under
l5go.
Most
of the
physico-chemical
analysis
mentioned
in
this
study
were
carried
out
with
kero-
gen
prepared
in
this
way.
It
is
planned
to
make
the
method
for
eliminating pyrite
with
iron
sulfate
in
an
acid
medium
a
routine
operation.
For
this
purpose
the
acid
attack
residues
will
be
given
a treatment
for
twc
hours
with
a ferric
sulfate
solution
(150
g/1)
in
HCI 4i/.
only
the
kerogen
which,
accor-
ding
to
element
analysis
contains
iron
contents
of
more
than
1090
by
weight
will
be treated
in
this
way.
Under
this
value,
the
risk
of
oxidizing
the
kerogen
cancels
out the
advantage
of
working
on
cleaner
kerogen.
The
operation
is
followed
bytreatment
with
HCI
4.Vfor
t hr
and
then
by washings
in
order
to
eliminate
the
residual
iron
sulfate.
It
is
also
planned
to
retreat
the
kerogen
with
low
pyrite
contents
(Fe
< 10Vo
by weight)
but
which
is
rich
in
other residual
minerals (>
7-8Vo)
by hot
HCI
6l/ior
2
hrs
in
order
to
eiimi-
nate
possible
neoformed
fluorides.
All
this
can
been
made
in
the
apparatus
shown
on
Fig.
2.gby
replacing
water
by
polyethy_
leneglycol
in
the
heating
jackets,
which
makes
it
possible
to
increase
the
treatmentiempera-
ture up
to 95'
C.
It
is worthwhile
to note
that
this
apparatus
can
be
used
for
other
kinds
of
preparation:
It
is
for
example
well
suited
to
palynological
preparation
by modification
oi
tir.
procedure
(coarse
grinding,
no
stirring,
shorter
attack
times).
l.
Bordowskiy,
O.K.,
(1965),
Marine
Geotogy,
3,3.
2.
Burlingame,
A.L.,
Haug,
p.A.,
Schnoes,
H.K.
and
Simoneit,
B.R.,
(1969),
in:
Advonces
in
Organic
Geochemistry
1968,
p.A.
Schenck
and I.
Havenaar
ed.,
Pergamon
Press,
Oxford,
85.
3.
Combaz,
A.,
(1970),
C.R.A.S.
270D,2240.
4.
Dancy,
T.8.,
(1948),
ph.
D.
Thesis,
London
Uni_
versity.
5. Dancy,
T.E.
and
Giedroyc
V.,
(1950),
J.
Inst.
Petroleum,
36,
593.
6.
Debyser,
Y.,
Dastillung,
M.
and
Gadel,
F.,
(1977),
Proceedings
of
the
9th
International Meeting
of
Organic
Geochemistry,
Moscow,
1977.
-
7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation
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