Reduction of CO2 during serpentinization of olivine at 300 °C

and 500 bar

Michael E. Berndt
Douglas E. Allen Department of Geology and Geophysics, University of Minnesota, Minneapolis, Minnesota 55455
William E. Seyfried, Jr.

ABSTRACT tions. Initial reaction involved 20 g of olivine

CO2 reduction processes occurring during experimental serpentinization of olivine at and 45 g of fluid.
300 &C and 500 bar confirm that ultramafic rocks can play an important role in the gen- Fluid samples were taken directly into
eration of abiogenic hydrocarbon gas. Data reveal that conversion of Fe(II) in olivine to glass/Teflon gas-tight syringes by using
Fe(III) in magnetite during serpentinization leads to production of H2 and conversion of low-dead-volume sampling apparatus. Each
dissolved CO2 to reduced-C species including methane, ethane, propane, and an amor- sample was analyzed by gas chromatography
phous carbonaceous phase. Hydrocarbon gases generated in the process fit a Schulz-Flory (H2, CO2, CH4, C2H6, C3H8), inductively
distribution consistent with catalysis by mineral reactants or products. Magnetite is in- coupled plasma mass spectrometry (cat-
ferred to be the catalyst for methanization during serpentinization, because it has been ions), and ion chromatography (anions). Al-
previously shown to accelerate Fischer-Tropsch synthesis of methane in industrial appli- kalinity was determined by acid titration.
cations involving mixtures of H2 and CO2. The carbonaceous phase was predominantly Olivine was prepared from polished re-
aliphatic, but had a significant aromatic component. Although this phase should ultimately search-grade olivine (Fo88; Ward Scientific,
be converted to hydrocarbon gases and graphite, if full thermodynamic equilibrium were Pennsylvania) by grinding in an agate ball
established, its formation in these experiments indicates that the pathway for reduction of mill and passing the entire sample through a
CO2 during serpentinization processes is complex and involves a series of metastable 325 mesh sieve (#75 mm). Solid reaction
intermediates. products were analyzed by optical micros-
copy, X-ray diffraction, scanning electron
INTRODUCTION conversion of CO2 to CH4 in the absence of microscopy (SEM), and Fourier transform
Methane of probable abiogenic origin has a catalyst is prohibitively slow at these con- infrared spectroscopy (FTIR).
been observed in seeps from ultramafic ditions (Sackett and Chung, 1979). Thus, Activities of aqueous components were
rocks on land (Coveney et al., 1987; Abra- it is unclear exactly how and when metha- determined by using the EQ3 aqueous spe-
jano et al., 1988, 1990; Sherwood-Lollar et nization occurs and which, if any, of the ciation program (Wolery, 1992) and ther-
al., 1993), in plumes above ultramafic rocks known catalysts (e.g., metallic Fe, magnet- modynamic data from the SUPCRT92 code
on the sea floor (Rona et al., 1992; Charlou ite) might accelerate methanization during (Johnson et al., 1992). In addition, data for
and Donval, 1993), and in fluid inclusions in serpentinization. MgCl1, CaOH1, FeCl1, and FeCl20 used in
olivine-rich drill core from oceanic crust Janecky and Seyfried (1986) performed the calculations were from Saccocia and
(Vanko and Stakes, 1991; Kelley, 1996). an experimental study of serpentinization at Seyfried (1989), Seewald and Seyfried
Methane gas hydrates (clathrates) and 300 8C and 500 bar. Methane, however, was (1991), and Ding and Seyfried (1992), re-
methane-rich fluids have also been found in analyzed in only one sample at the end of a spectively. Speciation calculations were
sea-floor serpentinites (Haggerty, 1991; two-year experiment. Although that sample performed by using measured H2 concen-
Mottl, 1992). These occurrences indicate did, indeed, contain significant methane (66 trations to constrain redox, alkalinity mea-
that abiogenic methanogenesis may be more mmol/kg), the lack of analysis of methane in surements to constrain pH, and concentra-
widespread than previously thought, possi- other fluid samples taken during the study tions of aqueous species to constrain ion
bly occurring in any environment where ul- precluded unambiguous interpretation of activities. Redox equilibria involving re-
tramafic rocks undergo serpentinization methane-controlling reactions. Thus, to bet- duced-C species were suppressed for specia-
during reaction with CO2-bearing hydro- ter understand the behavior of gas species tion calculations, because CO2 is metastable
thermal fluids. Because large parts of the during serpentinization of olivine at ele- at the reducing conditions of the experiments.
oceanic crust are composed of ultramafic vated temperature and pressure, we per-
lithologies (Bonatti and Hamlyn, 1981; formed a similar experiment, but took ex- RESULTS
Snow, 1995) and because seawater, carbon- plicit account of gas-generating reactions. Fluid Chemistry
ate rocks, and degassing magmas are poten- Gas concentrations changed rapidly dur-
tially large and ubiquitous sources of CO2, ing the experiment (Fig. 1, Table 1). H2
methanogenesis during serpentinization may METHODS gradually increased from essentially nothing
be an important process affecting the redox Olivine (Fo88) was reacted with a CO2- to 158 mmol/kg by the end of the experiment
state of C in many parts of the Earth’s crust. bearing NaCl fluid (0.5 mol/kg dissolved (69 d). Total CO2 increased to 11.5 mmol/kg
Despite a growing number of field obser- NaCl; 8.9 mmol/kg dissolved NaHCO3) at after 48 h, but decreased subsequently to 2.3
vations indicating an association between ser- 300 8C and 500 bar. The experimental ap- mmol/kg at the termination of the experi-
pentinites and methane, relatively little is proach was essentially the same as that de- ment. Systematic increases in the concen-
known about rates and mechanisms of abio- scribed by Seyfried et al. (1987) in that re- trations of CH4, C2H6, and C3H8 were ob-
genic methane formation during serpentini- actants were loaded into a flexible Au/Ti served throughout the experiment to final
zation. Although methane is thermodynam- reaction cell that was sealed into a steel alloy values of 84, 26, and 12 mmol/kg, re-
ically the most stable form of C in highly autoclave. A thin capillary tube extending spectively.
reducing environments at low to moderate from the reaction cell permitted periodic Although a significant fraction of the CO2
temperatures (#350 8C) (Holloway, 1984), sampling of fluids at experimental condi- was converted to hydrocarbon gases (;1%),

Geology; April 1996; v. 24; no. 4; p. 351–354; 4 figures; 1 table. 351


Figure 1. Gas concentrations as a function of time during serpentinization of olivine at 300 °C
and 500 bar.
a much larger fraction (.75%) was reduced
and converted to carbonaceous material
(see below). The slight increase in CO2 early
in the experiment is attributed to dissolution
of trace magnesite in the olivine.
Cl was the only significant noncarbonate
anion, and Na was the only significant cation
(Table 1); the concentrations of both species
increased slightly throughout the experi-
ment owing to olivine hydrolysis. Fluid spe-
ciation calculations revealed the solutions to
be at undersaturation, saturation, and su-
persaturation, with respect to carbonate
minerals, brucite and forsterite, and mag-
netite and graphite, respectively.
Solids
Run products consisted of abundant fi-
brous serpentine (chrysotile) and euhedral
grains of brucite and magnetite. Microprobe
analysis revealed that brucite and serpentine
contained small amounts of Fe, but much
less than that in primary olivine. This result
indicates that the Fe released from the
352
fayalite component in olivine was seques-
tered predominantly by magnetite during
serpentinization, whereas the Mg from the
forsterite component of olivine effectively
cycled into brucite and serpentine. It has
been shown that the change in the oxidation
state of Fe during serpentinization can lead
to H2 production in coexisting aqueous so-
lutions (Moody, 1976a, 1976b), which is con-
sistent with our observation.
The only C-bearing material observed in
abundance was a series of unusual pale yel-
low particles ranging in size from ;30 to 80
mm (Fig. 2). Although the size of the parti-
cles varied, each had the same characteristic
shape: two symmetrical lobes attached to a
basal plate. SEM analysis of non–C-coated
particles revealed that the material is com-
posed predominantly of C with no detect-
able O, but small amounts (,1%) of other
elements including Fe, Cl, and K. FTIR
analysis of the phase indicated that the C is
predominantly aliphatic (saturated), but
there is also a distinct aromatic component.
Figure 2. One of many metastable carbona-
ceous particles (SEM image) formed during
serpentinization of olivine at 300 °C and 500
bar. All of these particles had the same unu-
sual bilobed morphology.
In this regard it is similar to carbonaceous
deposits observed on run products from in-
dustrial Fischer-Tropsch applications (Ga-
luszka et al., 1992). In addition to this phase,
we located one small black C grain (graph-
ite?) in the run products. Owing to the rel-
atively insignificant abundance of the phase,
however, we could not unambiguously de-
termine its mode of origin.
DISCUSSION
Fischer-Tropsch synthesis is a well-known
industrial process whereby CO2 is converted
to hydrocarbon gas by reaction with H2:
CO2 1 4H2 5 CH4 1 2H2O. (1)
Because Fischer-Tropsch synthesis is typi-
cally performed by using H2O-free CO2-H2
gas mixtures, to maximize CH4 production
rates (Huff and Satterfield, 1984), little is
known about how methanogenesis takes
place in a hydrothermal fluid where water is
the dominant medium and H2 is typically
scarce.
H2 may not be scarce, however, during
serpentinization of ultramafic rocks (Barnes
et al., 1972; Moody, 1976a, 1976b; Frost,
1985). As noted, high H2 concentrations
during serpentinization are linked to redox
GEOLOGY, April 1996
reactions attending olivine dissolution and
alteration mineralization. Specifically, the
relative tendency for serpentine and brucite
to exclude Fe leads to a lack of a suitable
host for Fe(II) released from the fayalite
component of olivine during serpentiniza-
tion. Although FeO (wüstite) and FeCO3
(siderite) are potential sinks for Fe(II),
these phases are metastable with respect to
magnetite over large ranges of fO2 and fCO2
conditions (Frost, 1985; Fig. 3). Thus, ser-
pentinization leads to oxidation of approxi-
mately two-thirds of the Fe(II) released
from olivine to Fe(III) in magnetite. H2 gas
is generated during this process, because the
O2 required for conversion of Fe(II) to
Fe(III) is derived from the hydrothermal
fluid (Moody, 1976a; Frost, 1985; O’Hanley,
1996). The tendency to generate H2 by this
mechanism was clearly demonstrated in our
experiment by the observed increase in H2
concentration from 0 to 158 mmol/kg and
the existence of abundant magnetite in the
run products.
Although formation of magnetite is ex-
tremely important as a H2 source during ser-
pentinization, it may also play a key role as
a catalyst for Fischer-Tropsch synthesis of
methane (Szatmari, 1989; Sherwood-Lollar
et al., 1993). Magnetite has been recognized
as a potent catalyzing agent for producing
CH4 from CO2-H2 gas mixtures (Yoshida et
al., 1993). Reduced C in the form of iron
carbides (Satterfield et al., 1986a, 1986b;
Lee et al., 1990) and chemically bound C
atoms (Tamaura and Tabata, 1990), which
form on the catalyst surface in high-H2 en-
vironments, can act as reaction intermedi-
ates for methanogenesis. Their presence ef-
fectively lowers the activation energy of
Fischer-Tropsch reactions and greatly accel-
erates conversion of CO2 to CH4.
Although the identity of the catalyst re-
sponsible for methanogenesis during our ex-
periment cannot be determined unambigu-
ously, several possibilities exist, including
magnetite, olivine, serpentine, and brucite
(results from a ‘‘blank experiment’’ ruled
out catalysis by materials in the reaction cell
itself). Of the reaction products, only mag-
netite has a demonstrated ability to catalyze
methanogenesis. Although it is also possible
that the C phase observed in the run prod-
ucts is the reaction intermediary, rather than
magnetite-surface C, accumulated carbona-
ceous material in Fischer-Tropsch applica-
tions usually results in decreased conversion
of CO2 to methane rather than an increase
(Galuszka et al., 1992, and references there-
in). Thus, carbonaceous material generally
does not react quickly with H2 to form meth-
ane. If, on the other hand, magnetite is the
catalyzing agent, it would suggest that mag-
GEOLOGY, April 1996
Figure 3. Phase relations and gas chemistry in
the system FeO-H 2O-O2-CO2 at 300 °C and
500 bar. Fluid chemistry from experiment is
shown for comparison. Numbers 1 to 5 refer
to sample number. CO2/CH4 line shows where
CO2 and CH4 fugacities would be equal if full
equilibrium were established. All of samples
from experiment were well within methane
stability region and well within graphite field,
indicating strong thermodynamic drive for
methanization and graphitization of CO2.
netite’s catalyzing effect on Fischer-Tropsch
synthesis is not lost during reaction under
high water pressures. The implication is that
the conversion of CO2 to methane may be
far more widespread in Earth’s crust than
previously thought. because all of the com-
ponents of the process are commonly
available.
Methane is not the only hydrocarbon
gas typically synthesized during surface-
catalyzed Fischer-Tropsch processes; signif-
icant concentrations of ethane, propane,
and other hydrocarbons can also be gener-
ated. Indeed, the distribution of hydrocar-
bon gases in a reaction product is commonly
controlled by the relative probabilities of
C-C and C-H bonding taking place on the
mineral surface (Shulz, 1935; Flory, 1936).
Experimental studies have shown that in the
absence of another process, such as thermal
cracking, the ratios of hydrocarbons with
successive C numbers in a run product will
be nearly constant such that
C2/C1 5 C3/C2
5 C4/C3 . . . Cn/Cn21 5 a, (2)
where Cn is the concentration of hydrocar-
bon molecules containing n C atoms and a
is the probability of surface species combin-
ing with C rather than H. The resulting dis-
tribution of gases can be represented by a
Schulz-Flory distribution, whereby the log
of gas concentration is linearly related to C
number (n). An equilibrium distribution of
hydrocarbon species, by comparison, would
result in nearly pure methane at the condi-
tions of the experiment.
Hydrocarbon gas production rates do, in
Figure 4. Schulz-Flory distribution of hydro-
carbons produced during final stage of exper-
iment (674 to 1678 h). Linearity in this type of
plot suggests hydrocarbon formation at sur-
face of a catalyst. In this case, Cn11/Cn is 0.33,
indicating that C on surface of catalyst (mag-
netite?) is 0.33 times as likely to combine with
a C atom rather than H.
fact, suggest a Schulz-Flory relationship
(Fig. 4). The slope of the observed distribu-
tion is consistent with a 5 0.33 and indicates
a high probability for C-C bonding at min-
eral surfaces during the experiment. A value
of 0.33 is within typical ranges reported for
Fischer-Tropsch synthesis catalyzed by Fe
metal or magnetite (Lee et al., 1990; Yo-
shida et al., 1993), although the value can
vary widely with temperature and concen-
trations of gases. These data suggest that in
addition to methane, other hydrocarbon
gases found in association with altered ul-
tramafic rocks (Abrajano et al., 1990; Sher-
wood-Lollar et al., 1993) may have an abio-
genic origin.
Although hydrocarbon gases were ob-
served, it is important to note that it re-
quired approximately two months to achieve
only 1% conversion of CO2 to CH4. Thus,
full conversion would likely require decadal
time scales at 300 8C and much longer re-
action times at lower temperatures. For ex-
ample, if we assume an activation energy of
85 kJ/mol (a typical value for Fe-catalyzed
Fischer-Tropsch synthesis; Huff and Satter-
field, 1984; Zimmerman and Bukur, 1990),
we can estimate that conversion of CO2 to
CH4 may take thousands of years at 200 8C
and hundreds of thousands of years at
100 8C. The relatively long reaction times at
low temperatures are geologically signifi-
cant and imply that very long residence
times are probably needed for hydrocarbon
generation during serpentinization at low
temperatures.
Although our data demonstrate that
Fischer-Tropsch–type synthesis of CH4 can
take place during serpentinization, another
important process that occurred was precip-
itation of a carbonaceous compound. The
fact that the most abundant C phase that
precipitated during our experiment was not
graphite, which is the most stable form of C
at the conditions of the experiment, suggests
353
that graphite precipitation rates are sluggish
compared to those of other metastable
forms of C. Thus, the overall C reduction
process during serpentinization may involve
a series of complex metastable intermedi-
ates. More work is needed, however, to de-
termine the long-term stability of such
phases and the role they play in the overall
methanization process.
CONCLUSIONS
Experimental results indicate that CO2 in
hydrothermal fluids is reduced to a variety
of hydrocarbon gases and carbonaceous
compounds during serpentinization of oli-
vine at 300 8C and 500 bar. We believe these
data have important implications for the
abundance and redox state of C in oceanic
crust because C in magmatic fluids and sea-
water is overwhelmingly in the form of CO2
and ultramafic rocks are a ubiquitous com-
ponent of oceanic crust. These data help to
account for the often-reported association
between serpentinites and methane and
other hydrocarbon gases.
ACKNOWLEDGMENTS
Supported by National Science Foundation
grant OCE-9402507. We thank D. Kerrick, J. Hol-
loway, and B. R. Frost for reviews, and J. Seewald
and D. O’Hanley for discussions. B. Ditmar at 3M
performed the FTIR analysis.
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Manuscript received September 27, 1995
Revised manuscript received January 9, 1996
Manuscript accepted January 23, 1996
GEOLOGY, April 1996