Chemical Geology, 109 ( 1993 ) 227-237 227

Elsevier Science Publishers B.V., Amsterdam

[ALl

Adsorption of organic c o m p o u n d s on carbonate minerals

3. Influence on dissolution rates

Michele Moisio Thomas*, Jamie A. Clouse and John M. Longo

Exxon Production Research Company, P.O. Box 2189, Houston, TX 77252-2189, USA
(Received February 26, 1993; revised and accepted February 26, 1993 )

ABSTRACT

This is the third in a series of papers to investigate the role of organic compounds on wettability, porosity and permea-
bility of carbonate rocks. These are important reservoir characteristics that influence the performance of petroleum reser-
voirs. This paper reports dissolution studies to address diagenetic effects on carbonate porosity and permeability.
Comparative dissolution measurements were performed to assess the influence of adsorbed organic material on the
reactivity of calcite and dolomite in the geologic environment. Organic compounds that adsorb strongly on carbonate
minerals (fatty acids and carboxylated polymers) were found to dramatically inhibit dissolution, while weak adsorbates
and nonadsorbates showed little or no effect on the dissolution rates. Experiments were performed at 20 °, 50 ° and 80°C
to examine the role of organic adsorbates at reservoir temperatures, and the strong adsorbates inhibited dissolution at all
temperatures. Experiments from various initial pH's confirmed that strong adsorption is an ionic interaction and demon-
strated that the inhibition of dissolution is limited to pH's above 4.5-5.

1. Introduction swer several fundamental questions concern-

The value of an oil reservoir depends upon
important rock characteristics such as poros-
ity, permeability and wettability. Porosity and
permeability depend not only upon the type of
facies but also on the diagenesis (physical and
chemical changes) of the rock as it is buried.
Porosity relates to the amount of oil in place,
and permeability relates to the rate at which
the oil can be produced. Wettability governs the
way that oil and water flow through the rock as
the reservoir is produced and can have a sig-
nificant effect on the fraction of oil that is ul-
timately recoverable. Organic material, if it is
present, can influence all three of these
properties.
The purpose of this series of papers is to an-
*Correspondence to: M.M. Thomas at present affiliation:
Exxon Company, U.S.A., P.O. Box 1600, Midland, T X
79702, USA.
ing the influence of organic material on car-
bonate reservoir properties. The first paper
(Thomas et al., 1993 in this issue) reports on
investigations with model compounds to de-
termine the type of compound that adsorbs, the
strength of the adsorption and its influence on
mineral wettability. The second paper (Frye
and Thomas, 1993 in this issue) reports the
abundance of fatty acids (strong adsorbates)
in natural sediments and rocks. In this paper,
we seek resolution to the question:
How do organic adsorbates influence car-
bonate diagenesis and ultimate porosity and
permeability?
Researchers have long suspected that or-
ganic coatings on carbonate particles may ex-
plain the enigma of supersaturation of seawa-
ter with respect to calcium carbonate and
dolomite. Supersaturation persists despite
abundant suspended particles that should serve
as nucleation sites. This has prompted several
228
studies of the influence of organic material on
carbonate dissolution and precipitation rates.
Pesret ( 1972 ) showed that stearic acid and
albumin decrease the calcite dissolution rate by
a factor of 5-10. Morse (1974) studied the in-
fluence of a variety of organic compounds (in-
cluding palmitate, oleate and stearate) on the
rate of calcite dissolution in seawater. He found
that the dissolution rate decreased 5% when
each of 22 compounds was present at a con-
centration of 200/lg 1-~, and the dissolution
rate decreased 25% when each was present at a
concentration of 1000/~g 1-~. Sj/~berg (1978 )
employed free drift runs (such as used here)
to study the effect of individual organic com-
pounds on calcite dissolution rate. He found
no effect by glycine, alanine, glutamic acid, so-
dium citrate, sodium succinate (each at 10-6
mol l- ~) and egg albumin (at 10 mg l- ~).
Simkiss (1964) found that organic phos-
phates inhibit carbonate precipitation from
seawater. Kitano and Hood ( 1965 ) found that
amino acids, carboxylic acids and sugars de-
creased precipitation rates. Chave and Suess
(1967) found that the organic material pres-
ent in the seawater was sufficient to totally in-
hibit precipitation for small quantities of cal-
cite seed crystals (presumably by coating the
surfaces), whereas, when larger quantities of
calcite were introduced, precipitation pro-
ceeded toward equilibrium. They later found
that increasing organic concentrations gave
decreasing calcium carbonate precipitation
rates from supersaturated solutions of artifi-
cial and natural seawater (Chave and Suess,
1970). Pytkowicz (1973) found that the rate
of spontaneous precipitation of calcium car-
bonate from supersaturated artificial seawater
was decreased by magnesium ion, phosphate
and citric acid. He found stearic acid (concen-
tration not reported) to have no effect.
Berner et al. (1978) studied the rates of
seeded aragonite precipitation from artificial
seawater in the presence of a variety of pure
and naturally occurring materials. They found
rates decreased by as much as a factor of 50,
M.M. THOMAS ET AL.
although some compounds demonstrated little
or no inhibition. The strongest inhibitors were
multifunctional aromatic molecules: gallic
acid, mellitic acid, tannic acid, and fulvic and
humic acids. Their limited examination of
amino acids and fatty acids resulted in weak
inhibition or none at all. Other work has also
demonstrated that calcite precipitation is in-
hibited by polyphenols (Reynolds, 1978 ), and
by sugars and alcohols (Krishnan et al., 1981 ).
Mitterer and his colleagues have suggested
that amino acids may assist in nonbiogenic
carbonate precipitation from seawater (Mit-
terer, 1971; Mitterer and Carter, 1977; Carter,
1978; Carter and Mitterer, 1978; Mitterer and
Cunningham, 1978 ). They found that organic
material rich in aspartic acid is preferentially
found with carbonate grains rather than sili-
cates. They attribute this to the free carboxyl
group on aspartic acid and its similarity to the
carbonate anion.
Bathurst (1975, p.254) refers to the critical
role that organic matter is likely to play in car-
bonate diagenesis, but little work has been done
in this field. Jackson and Bischoff (1971)
found that the acidic amino acids inhibited the
aragonite-calcite transformation rate, al-
though the basic and neutral amino acids cat-
alyzed it. They suggest that the free carboxyl
group on the acidic species chemisorbs to the
carbonate and decreases its reactivity and that
the neutral and basic molecules enhance reac-
tivity by a general catalytic mechanism. Cail-
leau et al. (1979), in a study aimed at calcite
cementing, found that several organic acids,
amino acids and sugars inhibited calcite growth
and influenced its morphology. Ferguson et al.
(1984) took an approach closer to the natural
environment. They experimentally simulated
the diagenesis of carbonate ooids at tempera-
tures ranging from 120 ° to 210 °C. Under
identical experimental conditions, the or-
ganic-rich ooids formed only rim cements, but
the organic-poor ooids showed replacement
calcites. Ferguson et al. attribute this result to
the organic matter acting in a protective man-
ADSORPTION OF ORGANIC COMPOUNDS ON CARBONATE MINERALS, 3
ner, physically preventing or slowing the dis-
solution/precipitation process.
Some of these investigations indicate that
organic material inhibits carbonate reactivity,
while others conclude that organic material
enhances carbonate reactivity. From the re-
ported work, there is no clear resolution to this
apparent contradiction. The key lies in the fact
that organic material cannot be treated as a
single species. Different organics behave dif-
ferently with respect to their adsorption on
carbonate surfaces and their ultimate effect on
carbonate reactivity. In this work, we have
coupled our investigations of organic adsorp-
tion on carbonates (Thomas et al., 1993 in this
issue; Frye and Thomas, 1993 in this issue)
with an investigation of the influence of those
same organics on carbonate dissolution rates.
This has enabled us to learn about the mecha-
nisms by which carbonate reactivity is influ-
enced and thus to characterize various organic
c o m p o u n d types according to their influence.
2. Materials and methods
Dissolution measurements were performed
on single crystals of calcite or dolomite ob-
tained from Wards Natural Science Establish-
ment, Inc. The calcite crystals were Iceland spar
from Creel and Chihuahua, Mexico; only clear,
colorless samples were used. The dolomite
crystals were clear and colorless or very pale
gray from Eugui and Pamplona, Spain. X-ray
diffraction analyses showed no impurities in
either mineral.
The water was building-deionized water,
further purified by passage through an acti-
vated carbon cartridge, two mixed-bed ion-ex-
change cartridges, a 0.2 p m filter, and finally
distilled. Wherever possible, the chemicals
were analytical reagent quality or better; they
were used as received.
Dissolution measurements were performed
by placing a single crystal ~1 c m × ~ l
cm × ~ 2 m m in 100 ml of deionized distilled
water, 0.100 M NaCI, or a mixed solvent of
229
40% isopropanol and 60% water. Dissolution
was followed by pH drift, measured with a cal-
omel combination electrode. Either a Corn-
ing ® model 130 pH meter or a Fisher ® model
825 MP pH meter was used, and the output was
recorded with a Linear ® model 1800 strip chart
recorder. Instrument drift was checked with
fresh buffers after overnight runs, and it was
~< +_0.02 pH-unit. Solutions were stirred with
a 0.5-in ( 1.27 cm) stir bar at a rate that kept
the solution well mixed but did not disturb the
crystal ( ~ 1000 rpm). Before the addition of
the crystal, solutions were adjusted with hy-
drochloric acid from the original pH of ~ 5.5
to the initial pH chosen for the experiment.
When adsorbates were soluble in this solution,
they were added directly and dissolved before
the crystal was inserted. When adsorbates were
not soluble, crystals were pretreated 15 min in
an appropriate solution of adsorbate and al-
lowed to dry. In these cases, the dissolution so-
lution was presaturated with adsorbate by add-
ing to it a few grains or a drop of adsorbate.
Then the crystal was placed in the solution, and
pH drift was monitored. Each crystal was
cleaved to yield two clean surfaces. Before test-
ing the adsorbate, each crystal was dissolved
alone to ensure that it matched a typical clean-
crystal pH-drift curve. This did not dramati-
cally alter the size or surface area of the crystal,
as was demonstrated by the fact that such a run
could be reproduced. Crystals were rinsed once
in deionized distilled water and four times in
toluene and air dried before treatment with
adsorbate and subsequent dissolution.
High-temperature studies of dissolution were
carried out on a Whatman ® Dataplate 440,
which is a hot plate-stir plate with a feedback
temperature probe. The actual temperature was
maintained within +_2 °C of the set
temperature.
3. Results
To assess the influence of the various ad-
sorbed organics on carbonate reactivity, we
230 M.M. T H O M A S ET AL.

performed comparative dissolution measure- lower than the surface pH-values for those
ments. Single crystals of calcite or dolomite wells.
were dissolved in aqueous solutions. The prog- Fig. 1 shows dissolution curves for calcite
ress of dissolution was followed by pH drift. with and without adsorbed fatty acids. The
As carbonate minerals dissolve, they yield car- clean crystal dissolves rapidly and reaches its
bonate ions that consume protons to become equilibrium pH of 8 in ~ 4 hr. The role of ad-
bicarbonate ions or carbonic acid molecules, so sorbed oleate was probed in two ways. One
the pH drifts toward more basic values. Com- crystal was pretreated with a solution of oleic
parison of the pH-drift curves in the presence acid in heptane; then it was immersed in the
of adsorbed organics gave us a good indication experimental solution, which had been presa-
of the difference in carbonate reactivity. turated with a small amount of oleic acid. An-
Our experiments generally started at an ini- other fresh crystal was immersed without pre-
tial pH of 4, a realistic m i n i m u m for diagene- treatment into a solution of 1.5 m M sodium
sis. Kharaka et al. (1986) report that pH-val- oleate. (The sodium oleate is not very soluble
ues of petroleum reservoir brines typically in water, and this solution was turbid, an indi-
range from 5.5 to 7.5 at the surface and that cation of incomplete solubility.) The two
subsurface pH-values would be more acidic curves are essentially identical, so we con-
because of the CO2 and H2S dissolved in the cluded that:
brine. They report subsurface pH-values of ( 1 ) Pretreatment and immersion in a satu-
4.0-5.5 for geothermal wells, 2.5 pH-units rated aqueous solution is adequate to test the

t~ _ ~3_ E] - E]~ "~ - ~ - E3- - ~ - "~7- -[3-- "~Q- -E}- - ~ - -~3- -E3

S . ~ ,., -.4~..---~- ~
Zr- f
I
t .G/~ . . . . . E] CLEAN CRYSTALS

6 -- --- ~ OCTANOIC ACID

/
/ ,,A" -- - - ~ OLEICACID

~a, .~ - - • SODIUM OLEATE

,/
W • U

3 i i i i ~ _ i i i i

2 4 6 8 10 12 14 16 18 20
TTME, HOURS

Fig. l. Calcite dissolution in 0.100 M NaC1 in the presence of fatty acids. Oleic acid was a d s o r b e d by p r e t r e a t m e n t in a
h e p t a n e Solution. Octanoic acid (3.2 m M ) a n d s o d i u m oleate (1.5 r m ~ ) were present in the aqueous phase during
dissolution,
A D S O R P T I O N OF O R G A N I C C O M P O U N D S ON CARBONATE MINERALS, 3 2 31

..ak' ' ' ' ' ' ' ~ ~ ' - ' 4 ( - ' - - "~-'- ~ " k ~ ' - ' - ' ~ " - ~+ ~ ~ ~ "~"'-'"J¢"'-- "R'-'------~
J

U ---- . HE×AOEOANEO,O.CAO
C,
::i: 6 U ........ CLE CRYSTALS

iV ::::::::::::::::::::::::::
3 i i i i i i i , i i

0 2 4 6 8 10 12 14 16 18 20
TIME, HOURS

Fig. 2. Calcite dissolution in 0.100 M NaC1 in the presence of various organics. Sodium dodecylsulfate was in the aqueous
solution (3.5 raM). Other organics were applied by pretreatment in organic solvents.

role of adsorbates with low water solubilities. The curve with octanoic acid shows some in-
(2) Oleate adsorbs on calcite quickly; it does hibition of dissolution, but not as much as oleic
not require pretreatment to inhibit dissolution. acid. While the octanoic acid adsorbs strongly,
The remaining adsorbates were applied in it is fairly soluble in water (4.7 m M ) . Some of
either of these ways, depending on their water it may be desorbing and leaving the calcite vul-
solubilities, and we assume that the results are nerable to dissolution. The C8 chain does not
independent of the method of adsorption. Both present as much of a hydrophobic barrier as
of the oleate curves show dramatic inhibition does the C~8 chain of oleic acid.
of dissolution. They drift up to pH ~ 4.6 and Fig. 2 shows dissolution curves with several
level off there. One experiment for this system
more adsorbates. None of these show signifi-
was carried out for an extended time, and it
cant inhibition of dissolution. The dicarboxy-
remained below pH 5 for a month. The PKa of
late may even enhance dissolution by com-
oleic acid is ~ 4.8; at this pH there are equal
plexing calcium in solution. These results fit
amounts of oleic acid and oleate ion in solu-
tion. At more basic pH's, the anion dominates. with our adsorption and wettability studies
The dissolution curves for oleate level off be- (Thomas et al., 1993 in this issue) that indi-
tween pH 4.5 and 5, probably because this is cate that the dicarboxylates, sulfates, sulfo-
where the a m o u n t of oleate anion, the actual nares and amines do not adsorb strongly or al-
adsorbing species, becomes appreciable in so- ter wettability.
lution. At these pH's, if an adsorbed oleate is Three carboxylated polymers and a natural
disrupted from the surface, there are sufficient geopolymer were tested for their influence of
oleates in solution to replace it. calcite dissolution, and the results are shown
232 M . M . T H O M A S E T AL.

8 ., 4]---'~-- -,D-- ~- --~- - .,El,-- - 'E3,-- - , D , - - - ~- -..El-- - B- - ~ - - ~,-- - ~---t~3

t
J ...... [] CLEAN CRYSTALS
7 it
z~ MILTEMP

/ • POLY QUIKTHIN

s/ O HUMIC ACID

t -- ~ REAX
/
/

5 t~ ~ _ ..~.__ .& _ _ . _ ~ _ ._G..- - --d~- - - ~ - ' - - ' A

/ . ~ ~ - ..4b.----~ -'''tin _

I . . . . , ~ - ~ " ~ _ __ _.o--.o---~--o---o G --~

4 ~ ~ 'X ~ " - - - ~ ~ ~'--'~ ~ "~

3
2 4 6 8 10 12 14 16 18 20
TIME, HOURS

Fig. 3. Calcite dissolution in the presence of polymers. REAX® and Miltemp® were 1.4% in 0.050 M NaC1; Poly Quik
Thin ®was 0.7% in 0.100 M NaC1; and humic acid was 1.4%in 0.100 M NaC1.

in Fig. 3. The most effective inhibitor is it does not adsorb on dolomite as extensively
REAX ®, a carboxylated Kraft lignin. H u m i c as it does on calcite ( T h o m a s et al., 1993 in
acid, a natural geopolymer f o r m e d in the early this issue). Overall, the influence of these or-
diagenesis o f organic matter, inhibited nearly ganics on dolomite dissolution is essentially the
as m u c h as R E A X ®. Poly Quik Thin ®, a syn- same as it is for calcite.
thetic polyacrylate, and Miltemp ®, a synthetic To better assess the role o f these adsorbates
copolymer o f benzenesulfonate and maleic an- at reservoir temperature, we ran dissolution
hydride, also inhibit dissolution significantly. curves at 50 ° and 80°C. The results are shown
As was discussed regarding their strong ad- in Figs. 5 and 6, respectively. These curves were
sorption ( T h o m a s et al., 1993 in this issue), run for just 7 hr because safety considerations
polymers possess the powerful combination of precluded us from leaving the hot plate on
the carboxylate group and multiple points of overnight. We found oleic acid to be an ex-
attachment. tremely effective inhibitor as long as the
Dolomite dissolution curves with a few of the aqueous solution was saturated with it. (In
adsorbates are presented in Fig. 4. REAX ®, the some runs in which the excess oleic acid dis-
carboxylated lignin, is the most inhibiting, as solved completely as the temperature rose, in-
it was for calcite. Oleic acid inhibits strongly, hibition was not as great. ) REAX ® did not in-
leveling off again at pH ~ 5. Sodium hexade- hibit as strongly as it did at 20°C, but it still
canesulfonate shows no effect on the dissolu- exerted a significant influence on the dissolu-
tion rate. This is what we would expect be- tion rate. We attempted the high-temperature
cause it did not inhibit calcite dissolution, and runs with octanoic acid too, but it is suffi-
ADSORPTION OF ORGANIC COMPOUNDS ON CARBONATE MINERALS, 3 233

_ . . . . . [] C,_EA. CRYSTALS . . . . . . . . . . .

~6 [ ~ M HEXADECANESULFONATE
t~'~ - - - - -,X- OLEIC ACID
I ,¢ .... A REAX
5

4
!
i
!
[ , ,
0 2 4 6 8 10 12 14 16 18 20

TIME, HOURS

Fig. 4. Dolomite dissolution in 0.100 M NaCI in the presence of various organics. Oleic acid and the sulfonate wer~
adsorbed by pretreatment in an organic solvent. The REAX ® polymer was 1.4% in the aqueous solution.
I
°t

--Ek'- . . . . . "El . . . . . 'El . . . . .

z k~

i
tt
7 s
] . . . . . [] CLEAN CRYSTALS
I . . . . A REAX
OLEtC ACI D
I

/
/ 4 _ _ I - -
.------" ~ - -

4 ~ -"~--'-'~------'~"1~------"-"#------'-"1~'-------

3
0 1 2 3 4 5 6 7 8
TIME, HOURS
Fig. 5. Calcite dissolution at 50°C in O. 100 M NaC1. Oleic acid was adsorbed by pretreatment in heptane. REAX ® was
1.4% in the aqueous solution.
234 M.M. THOMASET AL.

s " ,,[3- . . . . . . ~ ....... --2 . . . . . . . ~] . . . . . . . "~'}-- . . . . . . -F3

/
/

;" ...... E] CLEAN CRYSTALS

// . . . . ~ REAX

~ ~ _)(_ OLEIC ACID

!
i
t
i
/
t
i
I
/
i

d
/
i

1 2 3 4 S 6 7 8
TIME, HOURS

Fig, 6. Calcite dissolution at 80°C in 0.100 M NaC1. Oleic acid was adsorbed by pretreatment in heptane. REAX ® was
1.4% in the ac ueous solution.

8 .,~8._ .4~- - - [ 3 - - E l - - 4 ~ - - - 3 - - - [ 9 - --~--El--E}--- ~-- -E3- - -El-- --E}- _ ~ _ _ _Fj

y-
t t . . . . [:3 CLEAN CRYSTALS
7 t

," • OLEIC ACID

6

d
i
it
/
°1
z~
_)(_

5
/" ^ ...A.... _N-.---.-*5- d~ dx -& H
~ 4
/, . . ~ , ~.- - e, . - -@
- ~ - ~~ . z -~~ =.- ~ .- ~ -~- ~ --- - ~- - - -- ~ ".t['"~ " " ~ ~_
--~---~-- ~t x

3 .~

..,,w
1 . . ~ j "~'/

2 4 6 8 10 12 14 16 18 20
TIME, HOURS

Fig. 7. Calcite dissolution in 0.100 M NaCI from various initial pH's. Oleic acid was adsorbed by pretreatment in heptane.
ADSORPTION OF ORGANIC COMPOUNDS ON CARBONATE MINERALS, 3
ciently soluble at 50 ° and 80°C that the pH
drift of calcite dissolution was obscured by the
buffering of the solution by excess octanoic
acid. The oleic acid and REAX ® solutions were
checked for this buffering effect by titration
with base, but it was not observed there. We
see here that fatty acids can inhibit carbonate
dissolution at high temperatures if they are
present in sufficient quantities. Polymers are
still effective, though less so than at 20 ° C.
Oleic acid was tested for its inhibiting influ-
ence at several more acidic initial pH's. This
work addressed conditions present during aci-
dization of a production well. The results are
shown in Fig. 7. All curves level off at pH's
~4.5-5. As was discussed above (p.231), this
is near the PKa of oleic acid, and the presence
of oleate in solution appears necessary for ef-
fective inhibition. In the more acidic regime,
only the acid form of the adsorbate is present,
and some desorption probably occurs. Conse-
quently, oleic acid is not an effective inhibitor
of dissolution below pH ~ 4.
4. Discussion
In these investigations of dissolution, just as
in the adsorption studies (Thomas et al., 1993
in this issue), we have found fatty acids and
carboxylated polymers to be the most influen-
tial species. It is likely that the dissolution in-
hibition occurs as a direct result of the organic
adsorbate's preventing access to the surface by
water molecules. The correlation of our find-
ings in these two areas supports that notion.
The wettability results (Thomas et al., 1993 in
this issue) also corroborate the adsorption and
dissolution experiments, when one allows for
the fact that not all adsorbates are oil-wet. The
three approaches of this experimental program
(adsorption, wettability and dissolution ) have
served to complement one another. Together,
they provide us with the complete picture of
not only what is happening but also how and
why it is happening. This permits us to predict
better the adsorption and influence of new or-
235
ganic molecules that cannot be experimentally
tested.
We found fatty acids to dramatically de-
crease carbonate dissolution rates, which con-
tradicts previous investigations that showed
little or no influence of fatty acids on dissolu-
tion (Morse, 1974) and precipitation (Pyt-
kowicz, 1973; Berner, 1978). How can we ex-
plain this apparent discrepancy? Sj/fberg
(1978, p.9) points us to the answer when he
states,
"only the effect of the rate-limiting step or steps, the
slowest steps, in the reaction are studied".
In all three of these literature examples, the
fatty acids were added to the aqueous solution
in which the carbonate was to react. Consid-
ering the low aqueous solubilities of fatty acids,
the rate-limiting steps in those studies were
very likely transport to and adsorption on the
carbonate surface; hence the dissolution and
precipitation measurements tested a clean or
partially clean carbonate surface. Zullig and
Morse ( 1988 ) note that:
"due to the solubility barrier, monolayer coverage by
adsorption cannot be achieved from aqueous solution
for palmitate and stearate at concentrations below their
limiting solubilities",
which they report to be 1- 10 -7 and 6.10 -8 M,
respectively. We found it necessary to pretreat
the carbonates in a heptane solution of stearic
acid to obtain monolayer coverage within a
reasonable laboratory time frame; only then
did we observe dramatic dissolution inhibition.
The majority of previous work suggests that
organic matter inhibits carbonate reactivity.
When adsorption studies have been coupled
with investigations of carbonate reactivity, as
in our work and the work of Chave and Suess
(1967, 1970), the inhibition mechanism
strongly suggested is adsorption of the organ-
ics on the carbonate surface. The only reported
case of enhanced reactivity is with the neutral
and basic amino acids of Jackson and Bischoff
(1971). Our work indicates that this type of
organic is not adsorbed, so changes in the so-
236
lution chemistry probably caused the en-
hanced reactivity. Therefore, we conclude that
when organics adsorb on carbonates, they in-
hibit carbonate reactivity.
This holds several implications for carbon-
ate diagenesis. Organic-rich carbonate sedi-
ments will resist dissolution and precipitation
processes. Aragonite may be preserved to un-
usual depths in the presence of an organic ma-
trix (Bathurst, 1975, p.275 ). What controls the
preservation of organic matter in carbonate
sediments? More directly in terms of carbon-
ate diagenesis, this question becomes, "How
can we predict when adsorbed organic matter
will inhibit carbonate reactivity?".
It is important to recognize that nearly all
carbonates are formed in an environment that
is rich in organic matter. Many grains are bio-
genic, and others, such as ooids, are intimately
associated with organic matter (Mitterer,
1968 ). It is well known that the early diagene-
sis of organic matter includes the removal of
most of the carboxyl groups (Tissot and Welte,
1984, p.71). However, our work (Frye and
Thomas, 1993 in this issue) indicates that this
decarboxylation may not apply to acid groups
that are strongly bound to the carbonates or to
the kerogen. Hence, the most important acids
from the standpoint of carbonate diagenesis
may be preserved. The products of early sedi-
ment diagenesis are often geopolymers that are
also quite likely to adsorb. Thus, in the ab-
sence of specific removal mechanisms, car-
bonates are likely to be coated with either bio-
logical organics, such as the fatty acids, or
geopolymers formed during burial.
We can speculate on possible mechanisms for
the removal of organic coatings. We know that
carbonates typically exhibit dissolution fea-
tures when they have been exposed to an influx
of fresh water. Such a recharge not only lowers
the concentrations of calcium and carbonate
but also probably lowers the organic concen-
tration so that some desorption occurs over
long periods of time. The freshwater recharge
may also carry bacteria into the system. Bac-
M.M. THOMAS ET AL.
teria are known to preferentially consume
straight-chain hydrocarbons; they would at-
tack fatty-acid tails with ease.
With deep burial, temperatures may remove
adsorbed organics. This was demonstrated in
our high-temperature dissolution studies. If we
maintained the system with excess fatty acid,
dissolution was inhibited effectively at 50 ° and
80 ° C. If, however, the solution became under-
saturated as the temperature rose, we observed
desorption and much less inhibition of disso-
lution. The depth or temperature at which de-
sorption takes place will be determined largely
by the type and quantity of organic matter in
the sediment and by its fluid/rock ratio.
5. Summary
We draw several conclusions from this work:
( 1 ) Carbonate mineral dissolution is inhib-
ited by compounds that adsorb strongly, i.e.
fatty acids and carboxylated polymers. These
compounds inhibit dissolution by effectively
coating the entire carbonate surface, thereby
isolating it from the solution.
(2) The carboxylic acids adsorb as anions.
Therefore, they are effective adsorbates and
inhibitors only at pH's above 4.5-5, where they
exist as anions in aqueous solution.
(3) Adsorption and dissolution inhibition
decrease somewhat as temperature increases
because most adsorbates exhibit enhanced
aqueous solubility at elevated temperatures.
However, if sufficient adsorbate is present in
the system, dissolution is effectively inhibited
at temperatures up to 80°C (the maximum
temperature investigated here).
Acknowledgments
We thank Exxon Production Research Com-
pany for permission to publish this paper. We
appreciate the experimental contributions of
A.M. Bishop, R.W. Brown and G.A. Otten.
ADSORPTION OF ORGANIC COMPOUNDS ON CARBONATE MINERALS, 3
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