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Geology

Biogenic origin for Earth's oldest putative microfossils


Bradley T. De Gregorio, Thomas G. Sharp, George J. Flynn, Sue Wirick and Richard L. Hervig

Geology 2009;37;631-634
doi: 10.1130/G25683A.1

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Notes

© 2009 Geological Society of America


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Biogenic origin for Earth’s oldest putative microfossils


Bradley T. De Gregorio1*, Thomas G. Sharp1, George J. Flynn2, Sue Wirick3, and Richard L. Hervig1
1
School of Earth and Space Exploration, Arizona State University, Tempe, Arizona 85287-1404, USA
2
Department of Physics, State University of New York Plattsburgh, Plattsburgh, New York 12901, USA
3
National Synchrotron Light Source, Brookhaven National Laboratory, Upton, New York 11973, USA

ABSTRACT similar to those of amorphous carbon than those


Carbonaceous microbe-like features preserved within a local chert unit of the 3.5 Ga old of graphite, implying the presence of randomly
Apex Basalt in Western Australia may represent some of the oldest evidence of life on Earth. oriented polyaromatic domains. STXM-based
However, the biogenicity of these putative microfossils has been called into question, primarily X-ray absorption near-edge structure spec-
because the sample collection locality is a black, carbon-rich, brecciated chert dike represent- troscopy (XANES) studies of humic acids
ing an Archean submarine hydrothermal spring, suggesting a formation via an abiotic organic and kerogens indicate the presence of various
synthesis mechanism. Here we describe the macromolecular hydrocarbon structure, carbon oxygenic functional groups in addition to aro-
bonding, functional group chemistry, and biotic element abundance of carbonaceous matter matic carbon with the absence of characteristic
associated with these filamentous features. These characteristics are similar to those of bio- absorptions due to graphitic ordering (Boyce
genic kerogen from the ca. 1.9 Ga old Gunflint Formation. Although an abiotic origin cannot et al., 2002; Jokic et al., 2003). In ELNES and
be entirely ruled out, it is unlikely that known abiotic synthesis mechanisms could recreate XANES spectra, peak positions are determined
both the structural and compositional complexity of this ancient carbonaceous matter. Thus, by chemical bonding and functionality, while
we find that a biogenic origin for this material is more likely, implying that the Apex microbe- relative abundance influences peak intensity.
like features represent authentic biogenic organic matter. SIMS is used to measure in situ biotic elements
commonly present in kerogen, including nitro-
gen, sulfur, and phosphorus at parts per billion
INTRODUCTION than simple amorphous carbon, graphite, or sensitivity. Overall, if Apex carbonaceous mat-
The 3.456 Ga old Apex chert dike is part of a other complex organic matter created via abiotic ter is indeed biogenic, it should display features
swarm of black hydrothermal chert veins feed- chemical reactions, such as FTT synthesis. The similar to those observed in bona fide kerogen
ing conformable lenses of bedded sedimentary general tertiary structure of kerogen consists of using the above techniques.
chert and silicified volcaniclastic tuff within randomly oriented, nanometer-scale sheets of
the regional Apex Basalt, Western Australia polycyclic aromatic carbon connected by bridg- RESULTS
(Brasier et al., 2005; Van Kranendonk, 2006). ing aliphatic hydrocarbon chains (Tissot and Commonly, chert-hosted carbonaceous mat-
Oxygen isotope and native metal concentrations Welte, 1978; Behar and Vandenbroucke, 1987). ter resides along grain boundaries and triple
within the chert dike indicate fluid temperatures Laser Raman spectroscopy of the putative Apex junctions between microquartz grains (Moreau
of 250–350 °C during silica deposition (Brasier microfossils (Brasier et al., 2002; Schopf et al., and Sharp, 2004; De Gregorio and Sharp,
et al., 2002, 2005), higher than the upper tem- 2002, 2007) is similar to that of several poorly 2006). In TEM images of ultramicrotomed
perature limit for extant hyperthermophiles and ordered and amorphous carbonaceous materi- Apex and Gunflint chert sections, the ancient
presumably much higher than that survivable by als, including kerogen (Pasteris and Wopenka, carbonaceous matter often exhibits a strip-
the earliest microorganisms. Abiotic Fischer- 2003), indicating the presence of abundant sp2- like or string-like morphology (Fig. 1A). This
Tropsch–type (FTT) synthesis has been pro- bonded carbon organized in 30–40 nm polyaro- strip morphology is generated during ultrami-
posed as an alternative mechanism for carbon matic domains (Allwood et al., 2006). crotomy as mechanical stick-slip vibrations,
reduction in such a paleoenvironment (Brasier In this study we use a combination of trans- or chattering, separate the carbonaceous mat-
et al., 2002, 2005). mission electron microscopy (TEM), syn- ter from the microquartz, creating a carbona-
While the putative microfossils exhibit fila- chrotron-based scanning-transmission X-ray ceous strip with a width roughly equivalent to
mentous or coccoidal cellular morphology microscopy (STXM), and secondary ion mass the sectioning thickness and a strip thickness
(Schopf and Packer, 1987; Schopf, 1993; Schopf spectrometry (SIMS) to characterize the struc- equal to the width of the grain boundary film.
et al., 2002) similar to other Archean microfos- ture, carbon bonding, functional group chem- In high-resolution TEM imaging, Apex carbo-
sils (Schopf et a1., 2007), their degraded appear- istry, and light element composition of ancient naceous matter appears structurally amorphous
ance has led to additional doubts regarding their organic matter preserved within Apex chert (see (Fig. 1C), lacking the characteristic 3.4 Å lat-
biogenicity (Brasier et al., 2002, 2005). In such the GSA Data Repository1). Previous TEM- tice fringes visible in disordered graphitized
cases, morphology alone is insufficient to dem- based electron energy loss near-edge structure carbon (Buseck et al., 1988) (Fig. 1D). Carbon
onstrate a microbial origin, and detailed char- spectroscopy (ELNES) of kerogen comprising K-shell ELNES spectra of Apex carbonaceous
acterization of the structure and composition well-accepted, ca. 1.9 Ga old Gunflint micro- matter (Figs. 2B, 2C, and 2D) contain a sharp
of the carbonaceous matter composing these fossils (Moreau and Sharp, 2004) and Apex peak at 285 eV, corresponding to a 1s → π*
features is necessary. The goal of such studies carbonaceous matter (De Gregorio and Sharp, (anti-bonding) electronic transition in carbon-
is to identify suspected biogenic carbonaceous 2006) indicate the presence of abundant aro- carbon double bonds, and indicate abundant
matter reliably as kerogen, the insoluble carbo- matic carbon. These ELNES spectra are more aromatic carbon (De Gregorio and Sharp,
naceous residue remaining from the degradation 2006). However, the characteristic graphitic
and maturation of deceased organisms, rather σ*1 peak at 292 eV present in graphite and
1
GSA Data Repository item 2009147, sample de- highly disordered graphitic carbon (Fig. 2A)
scription and detailed methods, is available online at
*Current address: Naval Research Laboratory, www.geosociety.org/pubs/ft2009.htm, or on request
is not observed in Apex carbonaceous matter.
Code 6366, Washington, D.C. 20375, USA: E-mail: from editing@geosociety.org or Documents Secre- The abundance of aromatic carbon without
brad.degregorio@gmail.com. tary, GSA, P.O. Box 9140, Boulder, CO 80301, USA. long-range graphitic ordering indicates the

© 2009 Geological Society of America. For permission to copy, contact Copyright Permissions, GSA, or editing@geosociety.org.
GEOLOGY,
Geology, JulyJuly 2009
2009; v. 37; no. 7; p. 631–634; doi: 10.1130/G25683A.1; 3 figures; Data Repository item 2009147. 631
Downloaded from geology.gsapubs.org on May 16, 2010

DISCUSSION
A 1 μm
B Apex carbonaceous matter and Gunflint
kerogen are both structurally complex ancient
organic materials. The lack of graphitic lattice
fringes in high-resolution TEM images and the
absence of the characteristic σ*1 peak in ELNES
and XANES spectra indicate they do not con-
tain long-range graphitic ordering. However,
2 μm
both materials contain abundant aromatic car-
bon, which may give rise to a small graphitic
resonance in laser Raman spectra of Apex car-
C D bonaceous matter observed by other researchers
(Brasier et al., 2002; Schopf et al., 2002, 2007).
Polyaromatic moieties <~30 Å in diameter
could still give rise to small graphitic Raman
signatures, but appear ungraphitized in ELNES
and XANES spectra. On the other hand, both
Apex carbonaceous matter and Gunflint kero-
gen are structurally distinct from amorphous
carbon, since they contain a higher abundance of
aromatic carbon and more σ* intensity at lower
energies than the latter. These observations are
consistent with typical structural models of ker-
50 nm 10 nm ogen consisting of randomly oriented polyaro-
matic domains connected by aliphatic hydrocar-
bon chains (Behar and Vandenbroucke, 1987).
Figure 1. A: Transmission electron microscopy (TEM) image mosaic of string-like Apex car- In addition, Apex carbonaceous matter and
bonaceous matter. B: Synchrotron-based scanning-transmission X-ray microscopy (STXM)
image of same piece acquired at 290 eV, surrounded by nearby strongly absorbing quartz Gunflint kerogen are chemically complex
grains. C: Higher-resolution TEM image mosaic of amorphous Apex carbonaceous matter organic materials rather than simple hydrocar-
from the string-like section (white box in A). D: High-resolution TEM image of highly disor- bon materials. Both ancient materials appear
dered graphite powder showing characteristic 3.4 Å lattice fringes. to contain similar relative abundances of aro-
matic carbon and oxygenated functional groups
presence of randomly oriented polyaromatic al., 2002). Nitrile functional groups (C≡N) according to their XANES spectra. The pos-
domains. At higher energies the spectra are also have a π* absorption in this region of the sible presence of phenol in XANES spectra is
dominated by various 1s → σ* (anti-bonding) carbon near-edge spectrum, but Apex carbona- also consistent with structural polyaromatic
electronic transitions from covalent σ bonds. ceous matter is not rich in nitrogen nor do the domains. Furthermore, both Apex carbona-
In general, the C-ELNES spectra appear simi- energy absorption spectra indicate the presence ceous matter and Gunflint kerogen contain
lar to those of amorphous carbon (Fig. 2F) of other N-containing moieties. C-XANES similar amounts of nitrogen, sulfur, and phos-
with additional contributions from sp2-bonded spectra acquired from Gunflint kerogen (Figs. phorus, although the abundances of these ele-
aromatic carbon and a corresponding subtle 2J and 2K) show spectral features similar to ments in the ancient carbonaceous matter are
redistribution of intensity at the lower energy those of Apex carbonaceous matter, including small. Nitrogen and sulfur are most likely pres-
side of the σ* peak. Kerogen from ultramicro- the presence and relative intensities of the car- ent within heteroatomic cycles in polyaromatic
tomed sections of Gunflint chert also appears boxyl and phenol peaks. domains, although sulfur may also be present as
amorphous in TEM images and has C-ELNES Abundances of biotic elements preserved in disulfide bonds in bridging hydrocarbon chains.
spectra nearly identical to Apex carbonaceous kerogens tend toward a relatively narrow range The location of phosphorus atoms in this ancient
matter (Fig. 2E). of values. SIMS negative ion ratios of biotic organic matter is unknown, but further implies a
STXM imaging and XANES spectroscopy elements sputtered from polished thin sections biogenic origin.
are performed on the same samples as TEM of Apex chert and microfossiliferous Gunflint Apex carbonaceous matter has undergone
analysis (Fig. 1B). As seen in C-ELNES spec- Chert show similar ranges (Fig. 3) despite dif- regional prehnite-pumpellyite metamorphism to
tra, C-XANES spectra of Apex amorphous ferences in metamorphic history between the temperatures as high as 350 °C (Van Kranen-
carbon contain aromatic π* peaks at 285 eV, two units. Since no submicrometer carbonate, donk et al., 2007), while Gunflint kerogen has
but no graphitic σ*1 peak at 292 eV (Figs. 2H sulfide, nitrate, or phosphate minerals associ- only undergone low-grade subgreenschist meta-
and 2I), consistent with ungraphitized polyaro- ated with carbonaceous matter were observed morphism to temperatures no higher than 150 °C
matic carbon. In addition, the higher energy in ultramicrotomed samples by TEM or STXM, (Klein, 1983). This difference in metamorphic
resolution of the synchrotron radiation source the biotic elements observed by SIMS originate history may likely cause subtle differences in
reveals two intermediate peaks due to oxygenic from the ancient carbonaceous matter rather the size and abundance of polyaromatic domains
functional groups (containing a carbon-oxygen than other mineral material. Although the abso- between the two ancient carbonaceous materi-
bond). Carboxylic acid groups (–COOH) give lute abundances of these biotic elements could als (Wopenka and Pasteris, 1993). However,
rise to the peak at 288.5 eV (Urquhart and Ade, not be calibrated due to inadequate standard both units have not undergone metamorphism
2002), while the less intense peak at 286.8 eV materials, ion proxies for atomic N/C, S/C, and exceeding greenschist grade, when graphitiza-
is most likely due to phenol or enol functional P/C are similar for both Apex carbonaceous tion becomes extensive. As sedimentary carbo-
groups (Caromatic –OH) (Cody, 2000; Boyce et matter and Gunflint kerogen. naceous matter matures, oxygen and hydrogen

632 GEOLOGY, July 2009


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ELNES σ*1 XANES produced by laboratory experiments appear to


σ*1 π* σ*2 depend strongly on the particular mineral cata-
σ*2 lyst used, and many of these potential catalysts
π*
would be present in an ancient hydrothermal
vent within the Apex Basalt. Although FTT
A σ* G σ* synthesis has been shown to fractionate carbon
- COOH
isotopes (McCollom and Seewald, 2006) to the
same degree as those measured in Apex carbo-

Optical density (arbitrary units)


Carom. - OH
naceous material (Brasier et al., 2002), only rel-
Intensity (arbitrary units)

B H atively simple organic molecules are produced


during laboratory FTT experiments that do not
approach the structural complexity of macromo-
lecular kerogen (i.e., aromatic domains and ali-
C I phatic bridging chains). These simple FTT mol-
ecules would likely be degraded and removed
during diagenesis and metamorphism. More-
over, FTT products are dominated by carbon
D J and hydrogen, and significant amounts of other
elements represent components of organic pre-
cursor reactants (Rushdi and Simoneit, 2005).
Simple inorganic aqueous species, such as HS–
E or NH4+, are far less likely to be incorporated
K into FTT products. Much is still unknown con-
cerning the details, diagenesis, and ubiquity of
FTT products and processes on the early Earth,
F L yet it appears unlikely that FTT reactions as we
understand them could produce carbonaceous
275 280 285 290 295 300 305 310 275 280 285 290 295 300 305 310
material with both the structural and composi-
tional complexity of kerogen.
eV eV
The structure and composition of Apex car-
Figure 2. Electron energy loss near-edge structure spectroscopy (ELNES) and X-ray absorp- bonaceous matter are strikingly similar to those
tion near-edge structure spectroscopy (XANES) spectra of carbonaceous materials. A, G: of Gunflint kerogen, even though these two
Poorly crystalline graphitic carbon shown in Figure 1D. B, H: Apex carbonaceous matter
shown in Figure 1A. C, D, I: Other Apex carbonaceous matter. E, J, K: Gunflint kerogen. F, chert units were deposited at vastly different
L: Amorphous carbon film. Some ELNES spectra (A, D, F) were previously published in De times and locations with distinct diagenetic and
Gregorio and Sharp (2006). metamorphic histories. The compositional simi-
larities imply a common origin and allow the
accepted biogenic origin of Gunflint kerogen
incorporation into aromatic heterocycles until to be considered for Apex carbonaceous mat-
methane and other gas formation begins (Van- ter. Since fluxes of dissolved molecular species
denbroucke and Largeau, 2007). During low- are highly variable even within nearby active
grade metamorphism, the nitrogen, sulfur, and hydrothermal vents, an independent mechanism
phosphorus abundances in Apex and Gunflint controlling the incorporation of biotic elements
Ion ratio

carbonaceous matter may be similar. into reduced carbonaceous matter would be nec-
Fischer-Tropsch–type reactions are often essary. Biological processes easily meet these
introduced as a possibility for abiotic organic conditions, generating similar biomolecules and
synthesis in ancient hydrothermal environ- cellular material despite variable environmental
ments. This type of organic synthesis requires conditions and incorporating relatively constant
hydrothermal fluid conditions, sources of H2, levels of necessary biotic elements into these
CO, or CO2, and an appropriate catalyst mate- biomolecules regardless of environment.
28Si-/18O- 12C14N-/12C2- 32S- / 12C2- 31P-/12C2- rial. Several common minerals in mafic and If the ancient carbonaceous matter preserved
ultramafic rocks have been shown to catalyze in the Apex black cherts is indeed biogenic, it
Figure 3. Secondary ion ratios of biotic el- FTT reactions, including magnetite (Yoshida was most likely transported into the hydrother-
ements in Apex (diamonds) and Gunflint et al., 1993), hematite (Reymond et al., 1982), mal vent from a surficial microbial community.
(circles) chert measured by secondary ion chromite (Foustoukos and Seyfried, 2004), Since known modern hyperthermophiles cannot
mass spectrometry.
and potentially olivine (Berndt et al., 1996; survive in the highest fluid temperatures present
McCollom and Seewald, 2001), as well as within hydrothermal systems, presumably early
minerals common in hydrothermal environ- microorganisms would also have been similarly
loss increases with metamorphism (Tissot and ments, including siderite (McCollom, 2003) intolerant, but early hyperthermophilic chemo-
Welte, 1978). However, most nitrogen, sulfur, and pyrite (Cody, 2005). Weathering products autotrophs could have thrived near the mouths
and presumably phosphorus loss occurs dur- such as clay minerals may also catalyze FTT of vents. Because the Apex cherts are brecci-
ing early diagenesis, with the remaining biotic reactions (McCollom et al., 1999; Williams ated, the ancient vents most likely went through
elements protected from further depletion by et al., 2005). The types of organic molecules cycles of activity with multiple injections of

GEOLOGY, July 2009 633


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hydrothermal fluids (Jébrak, 1997; Van Kranen- De Gregorio, B.T., and Sharp, T.G., 2006, The disulfide under hydrothermal conditions: As-
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