27 Modes of Coprecipitation of Ba and Sr with Calcite 2+
2+
Nicholas E. Pingitore, Jr. Department of Geological Sciences, University of Texas at El Paso, El Paso, TX 79968-0555 Non-lattice incorporation can play a significant role in the aqueous coprecipitation of large cations with calcite. Coprecipitation experimental results yield a partition coefficient of Ba into calcite of 0.04; the partition coefficient is affected by rate of precipitation, presence of other ions, and type of seed used to nucleate growth. Such sensitivity to experimental conditions characterizes non-lattice incorporation, a conclusion suggested by earlier EPR studies of calcites doped simultaneously with Ba and Mn . Previous coprecipitation experiments have shown that the incorporation of Sr into calcite involves both lattice and non-lattice substitution, a finding also consistent with published EPR data. A model of increasing importance of non-lattice incorporation with increasing deviation of the ionic radii of host and trace cations emerges. 2+
2+
2+
2+
The
incorporation
of
trace
areas
of
environmental
range
of
chemical,
the
mineral
marine the
human
compositions mation element of
These
and t e r r e s t r i a l
caliche, cision,
biological,
calcite.
continental of
and
calculi, these
speleology,
of
impacts
deep
encode,
limestone, crusts. with
the solutions
The a n a l y s i s limestone
paleo-oceanography,
composed
of
element of
pre-
for their of such
understanding
of
many
deposits,
degrees
of
and d i a g e n e s i s , and
of
The trace
varying
of
wide
sediments
and i n t e r p r e t a t i o n
genesis
the
cave
responsible
has l e d to a better
to
and tests
the calcareous
ocean,
a number
due
materials
the shells
and hard-water
the compositions compositions
calcite
and g e o l o g i c a l include
materials
or alteration.
into
and geochemistry
invertebrates,
shelf
biomineralization,
tion,
elements
chemistry
fortrace
processes lithifica-
environmental
chemistry
(1-10)* Experimental certain (e.g.,
doubly Mn2 + ,
incorporated
and
charged Zn2+,
into
empirical cations
Fe +, 2
calcite
of
Cd2+,
studies ionic
have radius
and
C o 2+)
precipitated
from
0097-6156/ 86/ 0323-0574506.00/0 © 1986 American Chemical Society
demonstrated less can
be
aqueous
than
that
calcium
extensively solution
at
27.
PINGITORE
earth
Coprecipitation
surface
conditions
diffraction, these in
and
trace
cations
calcite
carbonate
salt
true,
2
,
+
and The
2
may
enter
which may
are
participate (21).
to
crystal
a
tice
S r
calcite
even
tice. ity
2
Note of
the
that
The little most
calcite and
appropriate
that
or bonding
both
of
of
this
even
a
the
Sr
2
+
2
cation
modes
the
adsorption/trapping calcite.
tation
at
surface
and a p p l i c a t i o n
cipitation
of
experiments.
terminology,
and
be
i n Driessens
The
Incorporation
At
least
value
of
a dozen
papers The
to
+
+
,
or
Pb
2
+
,
and
Therefore in
i t
conditions) these
calcite,
an
but
substitu
ion
"adapts" the
lat
structure.
Very
For
lattice
of lat
groups
limited
with
2 +
calcite
and
in
miscibil
a
the
into
limited
integrates
then,
of
these
of
investi-
This large
processes
paper
solid
and
cations
which
to the
can
interpre-
and any o t h e r on
to
their
formation
of
crucial
is
discuss
and p r a c t i c a l
of
is
which
incorporation
copre-
characteristics,
solution
formation
volume). Calcite;
the past
coefficient different
and
information
aspects
the
experiments the
solution
range
(the
not the
geochemistry.
a mineral
Ç3,7_,
is
Our p u r p o s e ,
solid
decades
presented
paper
coprecipitation
with
(31)
in into
2 +
two
that
present
dominates
and
Sr
incorporation
incorporation,
the
of
appeared
locus
partitioning
2 +
attracted
elements
characterize
The
calcite.
(this
have
Eastman
at
lattice)
of
has
these
the past
non-lattice
cation
Ba
of
the p a r t i t i o n i n g
the results
over
,
2 +
the carbonate
for experimental
of
Sr(II)
the p a r t i t i o n
16,18,19,23-29).
and
thermodynamic
of
2
also
Additional
can
found
2
6-fold
an orthorhombic
over
interplay
Familiarity
the growth
S r
chemistry
affects
Ba
surface
that
partitioning
cation
environmental how
in
investigated
into
of
,
2+
when
forms
substitution
and i m p l i c a t i o n s
occur
Zn
carbonate,
i n the rhombohedral
2 +
and R a
a new s e t o f
larger
ion
calcite.
recognition
with
,
substitution.
calcite
into
+
occurs
Pingitore
gations
illustrates
2 +
isomorphous"
different.
foreign
non-lattice
these in
(Mn
i t s own b y o c c u p y i n g
In contrast
Ba
of
with
that
document
these
calcite,
calcite.
"forced
of
+
isodimorphy
in
2 +
findings
indicates
of
2
Sr
t h e low c o n c e n t r a t i o n s
Recently
trapping
Ca
such
of P b
intensively
evidence for
on
calcite,
may e n t e r
substitution
major
quite
(22).
studies
16,18,19,23-30).
those
is
due t o
has been
substitution
Thus
orthorhombic
earth
with
from
for Ca
i t
e.g.,
strontianite,
3
characterizes
several
site
SrC0 ,
waters
that
(at
substitution
different
coprecipitation
natural
expected
with
miscibility
the
,
+
or
the coordination
attention
2
isomorphous
structures
normally
of
site
rhombohedral
calcite.
carbonate,
form Ca
isodimorphous
though
these
to
than
may s u b s t i t u t e
+
a l l
lattice
a
solutions
size
isomorphous
of
structure
of
example,
each
course,
in
a
carbonates
Isodimorphous
site
such
larger
incapable
tion
of
the rhombohedral
orthorhombic
are not, of
cations
x-ray
or
is
forms
with
solid
or limited
coordination
Cations form
is
produce
9-fold
only
2 +
ion
to
aragonite. Ra
)
2 +
behavior
cations
isostructural (Cd
many
).
+
calcium
coordination
these
experiments,
that
i n the calcium
2 +
isomorphous,
by complete
Co
Ca
substitution
of
is
or
indicated
for
575
Calcite
Partitioning
have
Such
each
which
form
characterized Fe
(20).
3
with
2+
(11-19).
studies
grounds;
and Sr
2+
substitute
(CaC0 )
structural cations
Ε PR
of Ba
of
A
Review
two d e c a d e s S r
2
+
into
experimental
have
discussed
calcite, systems
the
r
03>Z>
and
their
k
c
S
G E O C H E M I C A L P R O C E S S E S AT M I N E R A L S U R F A C E S
576
conditions cently
have
cipitation those
previous runs
a a
that
tribution
to
the
amounts
in k
of
Ba
S
or
2 +
encountered
high
in
interpreted S r
at 2
of
cient
rapid
due In
to
lattice
and
of
each
of
k
c
S
run.
Experimental
Methods
the
to 7
Ba
2
10~
selected cite
runs.
seed
evolve
4 χ
red
(magnetic
temperature
three
days to
one
40
approximately
85%
lated
partition
yield
in
hastened
hours per
this
cc).
of
Chemicals
and
g
c
S
(0.05
to
sites
This these
greater
to
an
the
low range
which
increase to
the
0.07).
in
have
An
the small
with
to
r
effect
attributed
in
tendency k
c
S
with
r
increase
in
partition
2
a
NaCl the
rate
and
the
bubbling of
6
the
the
coeffi
g
not
solutions
Baker
in χ
Analyzed
from
g
of
were
suspended
were SrC03,
from
ranging
(precipitation The
calcu time
or
decarboxylation
nitrogen g
to
stir
lasted
cc).
which 5
in cal
allowed
precipitation
10"
ml
ranging
precipitate per
200
added
seed
runs
procedures
Reagents
in
0.005
the
the
introduced
dissolved
with 4
of
to
calcu of
were
3
solutions
hour
runs
experimental
(30,31).
BaC0
were
keep
related
approximately
dissolved
Normal
per
the
CaC03,
to
of the
Calcite
solution
The
recoveries
Speed
these
the
originally
was
with
of
also
18°C.
calcite
overall
conditions
dissolution
and
model
calcite,
compositions
sufficient at
the
were
opening.
runs.
rate
Eastman
Puratronic
of
to
amounts
SrC03
flask
calcite
of
and
a
into
+
Ba(II)
calcite
yielded
10~
of
solution
.
+
presented Sr*
specific
Varying
2
in
3 x
(31) of
the
of
C0 ·
coefficient
Details
runs
sites.
of
experiments k
non-
for
Addition
of
cation
on
maintained
(precipitation
Pingitore
in
+
value
At sites
of
account
of con
lattice number
may
coprecipitation
constricted
at
series by
Na
Eastman
completion
week
rate
was
a
was
from
of the
be
and
0.11
placed
bar)
to
substantial
studies.
Coprecipitation
Ba
5
through
and
earlier
(defect)
starting
10" M Upon
were
CO2
concentrations a
limited
concentrations,
of
with
typical
to
8
for
bubbling
produce χ
in
depending
experiments
+
by
the effect
incorporation
mode
r
experimental
water
of
to
number
crystallization.
lated
of
limited
of
may
Pingitore
contribution
For
artifact. results
coefficient.
non-lattice
non-lattice
value
low
3
transforma
of a
10"
almost
occupancy
non-lattice
summary,
Into
for
the
partition
concentration
likewise
in
experimental
makes
fall
0.2
increasing
amounts
+
to
and
reported
sets
from
explain
found 0.1
(25)
At
sites
and
may
ratio
both
defects.
competitive
the
an
copre
calculated
respective
rate
contribution
2
al.
favorably
decreased
a
was
r
Re
of
aragonite-calcite
were
occupancy
+
S r
occupy
precipitation
2
as
their
to
+
Sr
S
molar
et
concentration
large
of
cations,
the
encountered
concentrations
the
c
which
between
interpreted
overall
r
k
a
Katz
non-lattice
This c
(below
data
probably
saturated
of
results. range
technique
model
values
partitions
+
the
sites.
variation
than
2
sites,
the
lattice
was
(31)
Sr
of
value
using the
wide
experimental
to
ratio
+
98°C
concentrations
dominates
2
a
partitioning
calcite).
at
some
occupancy
higher
/Ca
+
Eastman
non-lattice ,
2
conflicting
explored
single
rose
concluded
and
apparently (31)
The
but
resultant
they
indicate +
Sr
findings
but
Pingitore
2
0.07,
low
the
identical
S r
with
constructed and
a
in
tion,
some
Eastman
inconsistencies. 0.05
with
range
and
conditions
results
between
of
yielded
Pingitore
gas
lasted
calcite are
per
available
Johnson Fisher
12 hour in
Matthey Certified
27.
PINGITORE
ACS
NaCl
pure of
Coprecipitation
and
BaC0 , The
3
the
solid VI
Precision for
the
for
in
the
only
Details
of
the
an
the
evolving
In
light of
broader
of
B a
of
(30).
varying
initial
and a
the
Ba a
the
the
An
Beckman
10%
Spectra-
the
as
Ba
high
as
which
Calcite calcite
under
one
produced
available
in
except
5%.
runs
of
(DCP).
2%
2 +
speed
hour
vaterite.
Pingitore
and
radii
are
and
Attempts of
limited
c
B
varies
a
the
A value this
refine therefore
and
(31);
suggest
A;
Sr
2
results in
the
0.04
a
partition set
of
extreme
lower
value
ratios.
,
1.21
A;
that
l i t t l e
0.01
thus char-
the
Figure reflect
k
c
c
S r
of and
B a
appropri,
1.44
A
none
of
the
2
+
the
defects, grows.
Ba
and
2 +
is
Hahn
differentiated
1,
with
the
more
as
(34)
between
along
preferred
trace
experimental
element
experimental
from any
would
be
is, the
procedure
warranted;
value
random
of
to
to
in
the
B
a
of the
one
of
(21,34).
achieve more
applicable
c
more
of
fact,
latter
resultant
k
behavior
Sensitivity
conditions
former
the
compared
substitution.
coefficient
Ba or
(the
k
crystal).
in
the
for
Instead,
calcite
of
misfit
The
and
various
further
the
conditions.
0.05
and
value
the
is
+
on
may
not
•+/-
absolute
calcite.
as
and
lattice
are
and
results
adsorption/trapping
the
0.03
covered
trapping
distinguishing
of
precipita-
solutions
concentrated
by
of
These
and
0.05,
widely
addition
which
+
surface,
points
a
and
system,
2
in
of
concentration
throughout
a
concentration ratio.
would 1.08
with
the
between
in
formation
to
the
B a
,
Pingitore
rates
element
coefficient to
differing
(31),
covering
solutions
without
crystal
of
consistency
in
and
trace
to
appropriate
seed. k
the
sites
behavior
for
of
process
of
of
crystal
Eastman
in
mixed
coprecipitation
tests
with
with
and
(the
0.03
used
model a
undertaken,
anomalous
scatter
the
was
of
proved
considered
concentrations
+
these
physical this
has
was
conducted
of
low
2 +
interior
Pingitore
those
that
at
calcite
by
by
partitioning
lattice
the
reproducible
than
in
of
during
(32)
Doerner-Hoskins the
solution
(y-axis).
+
Ca
explanation
from
partition
2
changed
equation
Discussion
were
lattice
distributed
The ranging
2
of
concentration effect
Sr
occlusion
randomly
Ba
the
solution
experiments
types
dependence
described
surfaces)
and
solution,
of
calcite
on
internal
more
for
The
the
ratios,
+
calcites
with
incorporated
value
the
2
magnitude
occupies
adsorbs
the
a
diffractometer;
the
presented
runs
/Ca
+
characterize
ionic
has
Ultra-
5 and
x-ray
study)
in
of
partitioning of
odds
in
+
2
range
orders
(33). Ba~2
Alfa
coprecipitation.
demonstrates
pronounced
ate
rose
equilibration
different
1
wide
at
2 +
to
resultant
which
it in
on
Doerner-Hoskins
conditions Ba
with
acterizes seem
and
coefficients.
model
These
NaCl
Figure
the
partitioning
+
Eastman
three
was
between
spectrophotometer
3%
are
ratio
+
Results
the
2
range
or
2
aqueous
Experiments:
set
/Ca
composition
Ba(II) the
2 +
without
low-temperature
in
which
procedures
partition
to
under
was
this
seed
analyzed
emission
except in
the
comprised
run.
a Philips
recorded
Ba
to
tion,
a
were
in
on
experiment,
calculate
3
samples
noted,
of
analyses
included
coprecipitation
SrCO
end
plasma
2 +
analytic
Because
new
as
577
Calcite
(30,31).
course to
the
determined
(not
of
Eastman
Ca
phase
duration
at
with
2+
typically
precipitates
dilute
was
seed
current
the
most
mineralogy was
and
direct
and Sr
2+
except
calcite
recovered
Solutions Span
and,
3
CaC0 .
of Ba
greater precise
only
to
a
G E O C H E M I C A L P R O C E S S E S AT M I N E R A L S U R F A C E S
578
10.0
1.0
0.1
0.01
-L
0.001 0.01
0.02
0.03
0.04
JL
±
0.05
0.06
0.07
0.08
calcite Figure Ba
2 +
0.03
/Ca to
calcite
1. 2 +
The solid
0.05 and
partitioning solution
independently also,
by
of
Ba
ratios. of
the
implication,
2
+
into
Note
calcite
that
k
concentration in
the
parent
c
B
a
of
at
various
varies Ba
2
+
solution.
from in
the
27.
PINGITORE To
explore
lattice were k
c
B
sites
added .
a
0.1
wise,
surface
adsorption of
Ba
non-lattice
0.1
at
low
with the
habit
fewer
being
2
and
S r
3).
foreign
of
favorable by
Ba
large
2
but
not
for a
,
+
a
direct
inappropriate.
is
B
c
not
can
NaCl
per
fell
to
the
surprising
that
such
an
;
displace
Ba
displaced
lower
the
lattice
coefficient
internal
to
from
2 +
S r
2
value
of
k
experimental
adsorption
and
the
c
of
a
vacancy crys
conditions of
the
solution to
on
signi range
quantity
surface
(31).
in
res
0.03
sites,
sites.
but
did
not
Sensitivity
conditions mixed
of
probability
overwhelming
S r
anomalous
calcite surfaces
growing
0.02
defect
for
occupancy
low
yielding
adsorption
from
+
2.)
liter
is
calcite
the
growth
a
by
values
a
in
comparison
of
k
;
+
In
it
into
2 +
experimental
of
mois
2
radius,
other
rendering
0.48
Ba
with
larger
(approximately
change
Sr
but
its
coefficient
yielding
for
ionic
or
equiva
effective
versa,
calcite
encroachment
seed
vice
the
Like
an
The more
partition
,
+
.
+
with
1.) 2
2
dehydration.
into
Ba
displace
partial
that
of
ranged
consistent +
+
Sr
2 +
on
on
of
coefficients
NaCl
partition
2
to
Sr
effect
calcites by
the
of
efficiently
(31).
the
Sr
partial
the
2
include:
sites its
in
Sr
exceeds
sites
to
is ease
that of
presence
studies
+
ions
contrast,
istic
2
It
significantly a
note
after
depressed
(Figure In
due
addition
ficantly of
the
site
partition
The
to
shown
occupy
apparent
dislodged
sites
2 +
not
amounts
resultant
not
displaces
+
no
adsorbs
been Sr
explanations
differences
pective
to
does
+
with
2 +
is
greater
incorporation
trapped
+
2
non-lattice
unfavorable Ba
Ba
2
varying
the
Ba
and
have
2 +
relative
to
in
2 +
non-lattice
non-lattice
or the
Ba
that
due
of
3.)
of
2),
that
concentrations)
favorable
tal;
Ba
defects
from
+
Possible
growth
on
therefore,
the
to
+
appears
Ba
calcites,
(Figure
consequent
fact
surprising,
2
that
579
Calcite
2
these
runs
Sr
2 +
and
the
(0.04).
2
and Sr + with
2+
in
+
It
Sr
of
radius
view
of
and
of
2
of
amounts
amount
ionic
set
100.
minor
lent
a
of Ba
Interpretation
Ca
ratio
to
calcite
the
for
to
The
from
Coprecipitation
is
a
of
character
crystal
formation
(21,34,35). Speed
runs,
in
in
rapid
coprecipitation.
in
the
Figure
number
and/or
more
The be
noted.
Since
witherite
equilibrium ratios χ
10~
3
these
1:3. from to
to
3.6
2.3
χ in
χ
with
200 ml
the
C0
solution
boxylation
to
to
4
To the
2
would in 3
2
at
"
3.9
can
the
to
exceed
calcite
appear
presence start
atmospheric
of
times
ratio speed
final
calcite
levels
a
run of
C0
is 2
9.1 and
increase
to
enhanced
as a
of
soluble
Ba
2
to
+
had
Ba
2
+
seed. χ
10~ M. 7
g
+
the Such
decarboxyla
Viewed 0.11
2
2.6
from
required.
of
+
during
ranging
by
at 2
/Ca
from
witherite
been
as
Ca
supersaturates
achieve
the must
solution
of runs
in
also
compositions
have to
concentration
of
due
supersaturations
would
an
crystallization,
from
solubility
difficult
hours,
precipitated
decarboxylation
minimum
12
characterize
diffraction)
molar
and
3
in
a
growth.
three
the
B
c
ions
2 +
phase
3
x-ray
for
the
rapid
saturation the
BaC0
the
10"
k
include
precipitate
i f χ
calcite,
respect
Ba
rapid
by
compositions
ΙΟ" . to
with
approximately
only
which
especially
fashion,
10"
relative
130
is
of
disorderly
adsorbed
separate
latter
calcite
supersaturations tion,
the
Starting
runs,
solution 14
with
of
to
undetectable
calcite
(BaC03),
a
completed
values
interpretations due
entrapment
that
levels
was
higher
sites
capture
physical
(at
that
Possible
defect
possibility
runs
exceeds
of
of
precipitation
document
efficient
probability speed
4
which
shown
in
another
calcite After
precipitation
of
per
decar calcite
580
G E O C H E M I C A L P R O C E S S E S AT M I N E R A L S U R F A C E S
100
10
I
0.1
0.01
JL
L 0.02
0.03
_L
X
0.04
0.05
0.06
0.07
0.08
, Ba calcite Figure
2.
calcite. Ba
2 +
into
vertical
The The the axis.
effect
of
S r
incorporation calcite
does
2
on
+
of
up
not
the to
partitioning 100
alter
times k
c
B
a
«
as
of
Ba
much
Note
into
2 +
Sr
2 +
as
change
in
PINGITORE
Coprecipitation
of Ba
and
2+
5r
2+
with
Calcite
581
10.
0.48
M
NaCl
1.0
0.1
—
0.01
x
o.ooi I 0.01
1
I
0.02
0.03
I
I
0.04
I
0.05
0.06
I
I
0.07
0.08
calcite Figure
3.
calcite. trations
The e f f e c t The
presence
significantly
of of
NaCl
on
NaCl
lowers
at
the
partitioning
approximately
the value
of
k
c
B
a
·
of
Ba
marine
2 +
into
concen-
582
G E O C H E M I C A L P R O C E S S E S AT M I N E R A L S U R F A C E S
10.
1.0
0.1
0.01
0.001 0.14
0.09
0.15
calcite Figure of
4.
The
partitioning
precipitation.
days Figure
to
hours 1.
Note
Reduction
yields change
larger of
of
Ba
of
precipitation
2
+
values
horizontal
into of
calcite k
c
scale.
B
a
,
at
times as
high from
rates several
compared
with
27.
PINGITORE
the
C0
duct
2
3
~
Coprecipitation
concentration
of witherite
maximum
Ba
minimum
C03 ~
χ
A
of
set
seed
used
to i n i t i a t e
k
reported
of
value
encountered
cern.
The
studies B
a
and
batch
Alfa
of
laboratory
reproduce surface
the
area
or
more
are
since
layers
many
coefficient Increases
run
did
2
also
not
to affect
+
imately
nonetheless template sites
not
k
B
c
a
.
.
a
between
in
seed
used
in
experimental
runs
by
the with in
Figure
Eastman
(30).
the
seed
the
during
a
EPR
Studies
2
The
growth
and
experimental
is
demonstrate
unaffected
k
suggest sites
and i s
Ba
over
B
c
l i t t l e
but
by growth
tion
of
S r
gest
that
and
the
(37,38).
by
spectra
for
different indicated ions
the
which
2 +
is
with
the
most
the Mn
a change Angus
2 +
i n the l o c a l
et
a l .
with
broad
of
Sr
2
.
+
the B a
2
+
is
adsorbs
the c r y s t a l .
a
amount with
of both
calcites
Sr
to
2 +
2
+
.
lattice
of
additional
et
a l .
(20)
are
previously sites
in
amounts
and M n
2 +
2 +
been
calcite of
were
previously.
the paramagnetic
strain
not
ppm M n
The r e s u l t a n t
produced
environment
related
had
sug
substi
an
hundred
varying
Mn
study
interest
few
that
coprecipita
non-lattice
lattice
with
indicate
the
Angus
It
into
calcites
doped
of
(31)
of
EPR s p e c t r a .
-doped
the
precipitation
(EPR) o f f e r s
cations
calcites
small
partition
2 +
the present
lattice.
incorporated
the c a l c i t e s
from
that
produced
of
chiefly
resonance
the c a l c i t e
resultant
next
along
2
involves
precipitating
the Mn They
Ba +,
in
limitation
measuring
and the r e s u l t s
paramagnetic
conditions
established or
calcite
coprecipitation
+
Electron
paramagnetic
a
which
i n Calcite
characterize
overcame
is
favorable
instead
of
and Eastman
into
It
provides
amounts
o r none
i n Pingitore
with
2+
and r a p i d
a
in calcite,
trapped
and Ba(II)
that
substitution
tution.
approx
masses
Ba
by moderate
decrease
results
of
results
probe
seed
provide
and n o n - l a t t i c e 2
in a
sufficient
one ppm.
polycrystalline
a
preci
contained
crystallized
B
c
par
used
contained seed
k
the
seed
lattice
+
r u n and
was b e l o w
the
of
calcite
concentration
lattice
+
of Sr(II)
2
in
value
of
crystal
which Greater
of
seed
fresh
5,
t h e amount seed
gas,
A
produced
larger
the commercial
o f NaCl
and defects
Ba
nitrogen study.
i n t h e amount
of
con
showed
Neither
consists
for
two
in
the rapidly
the
i t
These
in C a
surfaces
B
experiments
on
quantities
incorporated on
these
and that
Substantial
c
0 . 0 6 , and
cause
difference
results
of
10 f o l d )
(30),
the
substantial
and
formed
of
between
the
i n
explain
are
subsequent
depend
tested
increases
or
5
incorporation.
+
summary,
does
range
defects 2
the
independent
that
χ
The d i s p a r i t y
solutions
and the l a b o r a t o r y
+
during
for B a In
ing
2
possible
for
propagate
calcite
k
5.5
i n the present
defects to
the experiment;
3 ppm B a
the
Pingitore
surface
affect
the
difference
the
yielded
(up to
10~ M,
0.04, i s
produced
bubbling
of
was
pitated.
2.9
pro
and the
precipitation,
and Eastman
procedures
was
insufficient of
(36)
the importance
growth. work,
explain
on
seed
was
demonstrates
CaC03 was u s e d
findings
laboratory tition
by
runs
temperature
(30)
Ultrapure
the s o l u b i l i t y
strengths
witherite
i n Pingitore
check
decarboxylation
whereas
for
calcite
to
Eastman
speed
the present
(7°C)
complete
Pingitore
Ba
in
insufficient
A
rapid
B
slight
is
.
a
c
Since
low i o n i c
the
experiments
value
.
5
583
Calcite
exceeded.
final
of
10"
at
needed
was n o t
the
c
in
9
with
2+
1.25 χ 1 0 "
concentration
the
k
is
1.6 χ
apparently
5
and Sr
2+
concentration
+
2
10~ M,
type
2
is
of Ba
associated
Sr
2
+
EPR quite This Mn
2 +
with
584
G E O C H E M I C A L P R O C E S S E S AT M I N E R A L S U R F A C E S
0.1
0.01
APPROXIMATE LIMITS OF k [ ?
a
FROM
l c i t e
PINGITORE & EASTMAN (1984)
J
L
0.02
0.03
0.001 0.01
J 0.04
ing
5.
of
The
Ba
nuclei
the S r
2
produced
reagent)
reported
effects
240
to
effect was
1270 on
not
cation with the
ppm
the
the
the Ba
Mn
would
Sr
2
EPR
+
.
2
less
spectrum
pretation
In Ca
into
tion
due
with
the
than
in
to
These
EPR
of
from
+
Ca
20,000 was,
provide of
S r
2
lattice
+
to
Cd
2 +
Cd
calcite
(rather
Ca
than
with
a
the
lattice
2 +
the
of
incorporation
of
produced
2
+
,
no of
than
that an
the
et
independent calcite
the
al.
a
Ba
a
2
+
large
associated
ionic
radius
distortion
calcite.
minimal
that
such
with
in
radii,
significant
concluded
significant that
ppm
sites.
range
no
with
Davis
partition-
with
19,400
al.
strain
atomic
in
the
substitution
course,
of
Into
et
of
occurs in
on
consistent
a
90
showed
of
sites
B
c
calcites
ppm
0.08
(30).
Angus
sites;
,
+
k
contrast,
lattice 2
evidence
studies
clusion
2
of
seed
ion
investigation
similarity
incorporation Ba
more
0.07
experiment
the
In
lattice
case
experimental
of
2 +
2 +
that
partial
Sr
Mn - d o p e d
lattice
the
large
even
an
Eastman
spectrum.
in
below
this 2 +
and
0.06
precipitation
values
throughout
EPR
similar
calcite
rapid
calcites.
+
2 +
yield A
C d
+
of
in
by
Pingitore
incorporated
slightly
2
in
of
Seeding
yields
persisted
produced
+
type
previously
incorporation
These
of
calcite.
+
commercial 0.06
effect
into
2
0.05
Ba calcite
k
Figure
L
The
incorporation strain
or
finding
of
interof
distor-
consistent
(39).
evidence lattice
for sites
at
least
and
the
the ex-
sites.
Implications The
range
of
experimental into
calcite.
tion
emerges
coprecipitation and
practical
Distinguishing as
a
primary
behavior
studies
of
lattice
concern.
discussed
herein
partitioning from
of
non-lattice
Experiments
which
impacts
trace
both
elements
coprecipita-
explore
a
wide
27.
PINGITORE
range
of
Coprecipitation
parameters:
precipitation
rate,
coprecipitation. vide esis
Ca
are
2
which
+
these the
are present
calcites
sible
by
contamination of
i t s relative
waters, bility the
S r
2
limited
of
of calcites
gests
that
i n many
of
S r
Ba
2
conditions.
growth
may p r o v e
+
carbonate
occurs,
inappropriate
impos-
the p o s s i -
component
i n general, of
large
of
under
the Ba
2 +
variation
composition,
rate).
as a diagenetic
to
Because
and n a t u r a l
despite
(solution
precipitation
(or
the rock.
The i n t e r p r e t a t i o n
of precipitation
of
waters and
materials tool
some
and subject
by the p o t e n t i a l l y
surface,
2
The n o n - l a t t i c e
calcite
i s hampered
of
of
radius
e . g . , Cd +
difficult
microprobe)
diagenetic
into
2+
i n ionic
i n natural
fraction
exclu-
the compositions
Unfortunately
analysis
incorporation.
the conditions
carbonate
making
diagen-
substitution
substitution,
tracers.
electron
an important
and p r e d i c t a b l e
kçBawith
type
as
abundance
coprecipitation
of
a l . (20), can pro-
but s i m i l a r
lattice
the non-carbonate
remains
+
therefrom,
of non-lattice
contents of
from
smaller
low concentrations
techniques
composition,
to the nature
of carbonate
lattice
for reconstructing
diagenetic
i n very
et
for the study
exclusively
derived
such
as Angus
exhibiting
Cations
the best
clues
regard.
reliable
exhibit
solution
e t c . provide such
585
Calcite
concentration,
cations
solutions.
i n theory
2
standpoint,
that
a r e t h e most
diagenetic to
aid i n this
i t i s clear
sively
cation
temperature,
a practical
and Sr + with
2+
EPR s t u d i e s ,
an obvious From
of Ba
This
sug-
tracer.
Acknowledgments Discussions gy,
Goodell ously and
with
my c o l l e a g u e s
especially
M.P. Eastman,
flavored
provided
t h e outcome equipment
0.1. Cilatan
Aguirre
typed
reviewers improved
provided
a t UT E l P a s o C A . of
Chang,
this
and supplies assistance
the camera-ready
and t h e suggestions
copy.
i n chemistry
and g e o l o -
J . D . Hoover,
and P . C .
project. and C . i n
M . P . Eastman Podpora,
the laboratory.
T h e comments
of editors
B.
J.A.
of
Davis
gener-
Deshler, Julieta
two a n o n y m o u s and K . F . Hayes
the manuscript.
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