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Earth-Science Reviews 76 (2006) 259 – 300

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The origin of carbonaceous matter in pre-3.0 Ga greenstone terrains:


A review and new evidence from the 3.42 Ga Buck Reef Chert
Michael M. Tice ⁎, Donald R. Lowe 1
Department of Geological and Environmental Sciences, Stanford University, Stanford, California 94305, USA
Received 4 October 2005; accepted 17 March 2006
Available online 11 May 2006

Abstract

The geological record of carbonaceous matter from at least 3.5 Ga to the end of the Precambrian is fundamentally continuous in terms
of carbonaceous matter structure, composition, environments of deposition/preservation, and abundance in host rocks. No abiotic
processes are currently known to be capable of producing continuity in all four of these properties. Although this broad view of the
geological record does not prove that life had arisen by 3.5 Ga, the end of the early Archean, it suggests a working hypothesis: most if not
all carbonaceous matter present in rocks older than 3.0 Ga was produced by living organisms. This hypothesis must be tested by studies
of specific early geological units designed to explore the form, distribution, and origin of enclosed carbonaceous matter.
The carbonaceous, environmentally diverse 3416 Ma Buck Reef Chert (BRC) of the Barberton greenstone belt, South Africa,
provides an opportunity for such a study. Upward facies progressions in the BRC reflect deposition in environments ranging from
shallow marine evaporitic brine ponds to a storm- and wave-active shelf to a deep, low-energy basinal setting below storm wave base.
Abundances and ratios of Al2O3, Zr, TiO2, and Cr track inputs of various types of volcaniclastic and terrigenous clastic materials. In
particular, Zr/Al2O3 and Zr serve as proxies for concentration of windblown dust and, indirectly, as proxies for sedimentation rate. Cu,
Zn, Ni, and FeO were concentrated in the most slowly deposited transitional and basinal sediments, inconsistent with a hydrothermal
setting but consistent with a normal marine setting. The distribution of microfacies defined by associations and layering of clastic,
ferruginous, and carbonaceous grains correlates with facies transitions. Fine carbonaceous laminations, which occur only in shallow
platform settings, represent photosynthetic microbial mats. These were ripped up and the debris widely redistributed in shallow and
deep water by waves and storms. The isotopic composition of carbonaceous matter ranges from −35‰ to −30‰ in shallow-water
settings and to −20‰ in deep-water units. The heavier δ13C in deep-water carbonaceous matter is thought to reflect microbial
processing, possibly by fermentation and methanogenesis, of organic matter originally produced in shallow water.
Hydrothermal origins for BRC carbonaceous matter are clearly excluded by the inferred depositional setting of the rocks as a whole,
an inference supported by field, petrographic, and geochemical analysis. We suggest that the biological model proposed here for BRC
carbonaceous matter is the best currently available. The hypothesis that “at least some carbonaceous matter present in rocks older than
3.0 Ga was produced by living organisms” should be regarded as likely until extraordinary contradictory evidence is presented.
© 2006 Elsevier B.V. All rights reserved.

Keywords: carbonaceous matter; Archean; photosynthesis; microbial mat; chert

⁎ Corresponding author. Current address: Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California
91125, USA. Fax: +1 626 683 0621.
E-mail addresses: mtice@gps.caltech.edu (M.M. Tice), lowe@pangea.stanford.edu (D.R. Lowe).
1
Fax: +1 650 725 0979.

0012-8252/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.earscirev.2006.03.003
260 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

1. Introduction es leading to similar isotopic fractionations (Horita and


Berndt, 1999; van Zuilen et al., 2002) has called the most
Recent re-evaluation of the geologic record of the straightforward applications of this approach into
earliest life on Earth has led to suggestions that some of question.
the oldest putative microfossils (Schopf and Packer, The “list of criteria” approach is exemplified by
1987) and carbonaceous matter formed through abiotic Schopf and Walter (1983) and Buick (1984). The
hydrothermal processes (Brasier et al., 2002; Garcia- biogenicity criteria for microfossils proposed by Schopf
Ruiz et al., 2003). Similarly, many early Archean cherts and Walter (1983) are here analyzed as representative of
have been re-interpreted as hydrothermal exhalites this approach. Each criterion is classified as either a
rather than products of normal marine sedimentary positive test (one which some or all true microfossils
processes (Paris et al., 1985; Westall et al., 2001; Brasier should pass), a negative test (one which some or all false
et al., 2002). This controversy, together with new microfossils should fail), or both.
questions about the biogenicity of isotopically light
carbon in ∼ 3.8 Ga Isua rocks (van Zuilen et al., 2002), 1. True microfossils should “be of relatively abundant
has cast a haze on the earliest history of life. occurrence” and “be members of a multi-component
The difficulty at the root of the problem of ancient biologic assemblage.” This criterion is a positive test
life detection in general is that there is no “vital force,” of biogenicity; Schopf and Walter (1983) make an
i.e. there is, in principle, no biological product which implicit comparison to modern microbial populations
cannot be produced abiotically. Therefore, there is no set and apply some assumptions about preservation to
of measurements which could definitively distinguish make a prediction about fossil microbes. Some
biological from abiological materials. While this abiotic products could pass this test and some true
theoretical statement is stretched to the point of breaking microfossils could fail it, but most true microfossils
when applied to well-preserved metazoan fossils or should pass it.
complex organic materials (e.g. ribosomes), it takes on 2. True microfossils should “be of carbonaceous
particular force when considering relatively homoge- composition or, if mineralic, be a result of biolog-
neous carbonaceous matter (CM) in metamorphic ically mediated mineral encrustation or a product of
terrains or hypothetical steps in the transition from mineral replacement.” This criterion is another
prebiotic to biotic systems. positive test of biogenicity. It is potentially more
There have been three major recent approaches in stringent than the first criterion: although some
identifying biological carbonaceous matter in ancient abiotic processes produce CM, all microbial fossils
rocks. (1) Researchers looked for CM having an isoto- should start out as CM.
pic composition less than about − 15‰ vs. PDB (the 3. True microfossils should “exhibit biological mor-
“isotopic” approach). Such fractionation was believed to phology—be characterized by a range of variability,
reflect a kinetic isotope effect associated with enzymatic including life-cycle variants, comparable to that
processing of carbon. (2) Researchers sought to test exhibited by morphologically similar modern and/
carbonaceous matter or associated deposits against or fossil microorganisms.” The nature of this
predetermined lists of biogenicity criteria (the “list of criterion depends on the structure analyzed. A sphere
criteria approach”). Each criterion was designed to either is a biological morphology, for instance, but it is also
identify features likely to be produced by living orga- an extremely simple shape that could potentially
nisms or unlikely to be produced by abiotic processes. result from a host of abiological processes. In this
(3) Most recently, Brasier et al. (2002, 2004) have sug- sense, this criterion is a stringent positive test that
gested that the search for early life would best proceed by nearly all microbial fossils should pass but which
systematically testing competing abiotic hypotheses (the many potential abiotic products could also pass. On
“falsification” approach). the other hand, internal membranous structures such
The “isotopic” approach, represented in the work of as nuclei characterize only a subset of known
Schidlowski (1988, 2001) and Mojzsis et al. (1996), microbes, but are unlikely to be produced in abiotic
finds greatest prominence in cases where intense structures. In the case of this biological morphology,
metamorphism and deformation have erased potential this criterion functions as both a positive and a
textural and morphological evidence. Sufficiently large negative test.
depletions of 13C are identified with not only a biological 4. True microfossils should “occur in a geologically
origin, but with specific enzymes associated with known plausible context.” This criterion functions mostly as
carbon fixation pathways. Discovery of abiotic process- a negative test. It eliminates, for instance, misleading
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 261

structures in highly metamorphosed rocks or carbo- the falsificationist critique is probably best viewed as a
naceous linings in cross-cutting hydrothermal veins. valuable re-evaluation of the actual practice of investi-
5. True microfossils should, “to the extent feasible gators following the “list of criteria” approach and of the
(depending on existing data), fit within a well- breadth of abiotic hypotheses tested.
established evolutionary context.” This criterion In this sense, the “falsification” approach is subject to
functions as a caution against apparent microfossils its own criticism of the “list of criteria” approach. This
significantly more complex than known microfossils point is best seen when it is realized that the “null
of the same age. hypothesis” of abiological origins is effectively an infi-
6. True microfossils should “be dissimilar from poten- nite set of hypotheses. No criteria have been proposed by
tially coexisting abiological organic bodies.” This which these endlessly possible hypotheses can be
criterion functions explicitly as a negative test. Carbo- narrowed down to finite sets of practically testable hy-
naceous products of known abiotic processes fail this potheses, so it is not clear that testing of any number of
test, whereas not all true microfossils would pass it. specific “null hypotheses” will ever be enough to clearly
establish the past existence of life from geological
The “list of criteria” approach thus applies both posi- evidence. In fact, it is generally true of historical hypo-
tive and negative tests of varying strength to the problem theses that the number of possible explanations for
of biogenicity. Structures satisfying all criteria are interesting geological phenomena is limited only by the
labeled “probable microfossils,” and structures satisfy- imaginations of the investigators. It is for this reason that
ing most criteria are labeled “possible microfossils.” geologists and other historical scientists typically
The “list of criteria” approach is fundamentally de- proceed by searching for “smoking guns,” pieces of
signed to filter a small number of convincingly biolo- evidence so characteristic of one particular hypothesis as
gical structures from a large number of potentially to make invocation of other hypotheses superfluous
misleading abiological structures. As such, it is likely to (Cleland, 2001). In the case of testing for early life, this
be helpful in the analysis of material from geologic approach would amount to searching for a unique
terrains in which diagenetic and metamorphic alteration fingerprint of life in the early geologic record.
is minor enough to allow for preservation of abundant Unfortunately, no such smoking gun or fingerprint is
fine-scale carbonaceous structures, and which represent currently known. As already discussed, carbon isotopic
depositional environments likely to allow taphonomic fractionation is not unique to life (Horita and Berndt,
preservation of pristine fossils. Unfortunately, such 1999; van Zuilen et al., 2002). Despite recent sugges-
terrains become increasingly sparse toward the early tions (Schopf et al., 2002), Raman scattering spectra are
part of the preserved geologic record, and are exceed- not useful for unique identification of biologically
ingly rare in the critical early-to-middle Archean. The produced CM (Pasteris and Wopenka, 2003). Identifi-
great bulk of carbonaceous material in this interval is cation of carbonaceous filaments is not necessarily
relatively structureless, and candidate structures for the sufficient for the identification of microfossils (Garcia-
“list of criteria” approach are correspondingly rare. This Ruiz et al., 2003). Multiple supporting lines of evidence
does not imply that the search for evidence of early life is must therefore be employed, each one incrementally
destined to fail in N 3.0 Ga metamorphic terrains, nor that decreasing the likelihood of abiotic hypotheses and
the “list of criteria” approach has no value for analyzing increasing the likelihood of a biotic hypothesis. This is
putative microfossils, but that another approach must be essentially the procedure embodied by the “list of cri-
used to analyze the most ancient available material. teria” approach, although such lists as of yet have had
The “falsification” approach proposed by Brasier et only limited applicability (spectacularly preserved mi-
al. (2004) is less an independent approach than a critique crofossils and stromatolites, both exceedingly rare prior
of the “list of criteria” approach. The criteria approach is to 3.0 Ga). It is less clear how to proceed in investigating
criticized as proceeding primarily by deduction and the CM found abundantly in N3.0 Ga rocks. It is even
inappropriate comparison to modern organisms, without less obvious how to treat evidence that is necessarily less
serious consideration of alternative abiotic hypotheses. compelling than the idealized “smoking gun” in light of
Brasier et al. (2004) suggest that a more falsificationist current debates.
approach would be appropriate, and that investigation
must proceed by testing the null hypothesis of abiolo- 1.1. Reframing the debate
gical origins for relevant structures and material. Yet the
“list of criteria” approach explicitly includes negative We must have a way of approaching the problem of
tests designed to falsify known abiotic hypotheses. Thus, early life that respects the nature of historical science,
262 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

respects the current lack of any single smoking gun, and rocks overall than in younger rocks. Since such prebiotic
is more generally applicable to the sparse materials processes may have been primarily associated with
available for study N3.0 Ga. Recognizing the need for a certain environments, prebiotic CM might have been
new approach does not require that we disregard pre- environmentally restricted in ways not found in younger
vious results, however. On the contrary, we must take rocks. Prebiotic processes might be recorded in CM
account of what is already known about the very early having differing molecular structure or composition
geologic record to place the debate in context. from later biological CM. In contrast, if a globe-
Detection of past life on Earth is frequently seen as an encompassing biota was present during deposition of
analogous problem to detection of past life on Mars, a the entire geologic record, it seems likely that many of
fair comparison since Martian paleobiologists will work these properties would exhibit continuity over time.
with many of the same materials as terrestrial paleobiol-
ogists (e.g., McKay et al., 1996). But, like all analogies, 1.1.1. Carbonaceous matter structure
it has its limits. It has been suggested, for instance, that Laser Raman spectroscopy and XRD studies (Hayes
we should be as skeptical of evidence for early Archean et al., 1983; Wedeking and Hayes, 1983; Brasier et al.,
terrestrial life as of evidence for ancient Martian life 2002; Schopf et al., 2002; Tice et al., 2004) indicate that
(Brasier et al., 2004). It is a scientific truism that “extra- early Archean CM belongs to a structural class of car-
ordinary hypotheses require extraordinary evidence.” bonaceous compounds termed “graphite-like carbon” by
Given our current state of knowledge, is the hypothesis Pasteris and Wopenka (2003). This classification is
of early Archean life on Earth really as extraordinary as based on the predominance of sp2 C–C bonds, distin-
the hypothesis of early life on Mars? Or put in the guishing this material from other insoluble carbonaceous
language of Bayesian analysis (see Jefferys and Berger, matter dominated by sp3 C–C bonds (“diamond-like
1992, for a readable discussion of Bayesian analysis), carbon”). Graphite-like carbon can exhibit a range of
should the hypotheses of early Archean life on Earth and structural order, from disordered CM to fully ordered
early Martian life be assigned similar prior probabilities, graphite (Pasteris and Wopenka, 2003). Continuing with
a measure of relative confidence in a hypothesis given the terminology of Pasteris and Wopenka (2003), CM
known data, relative to competing abiotic hypotheses? from the 3.5–3.2 Ga Barberton greenstone belt and the
At a very basic level, the answer has to be no. Life is 3.5–3.3 Ga Pilbara Block is classified as “transitional to
known to have evolved on Earth; it is yet to be deter- graphite,” a level of order structurally intermediate to
mined if life ever evolved on Mars. On this basis alone, these two endmembers. Since graphite-like carbon can
the prior probability that life was present on Earth at be produced by abiological processes as well as thermal
nearly any given point in the past must be considered alteration of biological materials, structural information
greater than the prior probability that life was present on currently available for early Archean CM alone is not
Mars at any given point in its history. Just how much useful for determining its origins.
greater for specific points in time, such as the early The degree of structural ordering in graphite-like
Archean, remains to be seen. In other words, on Earth it carbon as reflected in its Raman scattering spectra is
is legitimate to rephrase the life-detection question as potentially informative about the thermal history of the
“How far into the past does the record of life extend?” material, however. In particular, disordered CM hosted
Such a question would be meaningless on Mars. in rocks metamorphosed to prehnite–pumpellyite facies
How should what is known about geological CM set or higher undergoes a characteristic loss of non-carbon
the stage for discussions of specific new data relevant to atoms (e.g. hydrogen) and organization of aromatic
the detection of early Archean life? We suggest that the components into increasingly large graphitic domains
record of CM may be evaluated for continuity or (Wedeking and Hayes, 1983), all reflected in Raman
discontinuity in four properties: (1) CM molecular or spectral characteristics (e.g. Wopenka and Pasteris,
crystalline structure; (2) CM elemental and isotopic 1993; Yui et al., 1996). It is therefore significant that
composition; (3) CM distribution in rocks formed under CM hosted by cherts of the Barberton greenstone belt
different conditions; and (4) CM abundance in rocks. If yield spectra consistent with lower greenschist grade
life had originated at some point in time represented in metamorphism (Tice et al., 2004), in agreement with
the geologic record, we might expect to see some sort of chlorite geothermometry of associated volcanic rocks
basic shift in the record of geologic CM. For instance, (Xie et al., 1997). In a more qualitative sense, Buseck et
since prebiotic processes of CM formation are unlikely al. (1988) used HRTEM (High Resolution Transmission
to have been as productive as later biological processes, Electron Microscopy) to demonstrate that Precambrian
it is possible that less CM would be found in ancient CM exhibits a continuum of structural order. The least
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 263

crystalline material studied was essentially structureless


CM from relatively unmetamorphosed Neoproterozoic
and Mesoproterozoic terrains, followed by transitional
CM from the greenschist-metamorphosed Barberton
greenstone belt. The most crystalline material was fully
ordered graphite from the amphibolite-metamorphosed
early Archean Isua Sequence.
While this continuity does not rule out most abiotic
origins for early Archean CM, it does preclude those
processes that deposit fully crystalline graphite or any
CM of significantly higher structural order. It would also
be remarkably coincidental if all early Archean CM was
produced by abiotic processes with direct products
having crystallinity similar to greenschist CM, such as
precipitation from high-temperature methane-rich fluids
(Pasteris and Chou, 1998). It is most likely that at least
some and probably most early Archean CM, like CM in
younger greenschist terrains, originated as less ordered
material.

1.1.2. Carbonaceous matter composition


CM stored in sedimentary rocks 3.5 Ga and younger
has carbon isotopic compositions almost universally
between − 15‰ and − 35‰ vs. PDB (Schidlowski,
1988, 2001). Schidlowski (2001) even suggests that the
average isotopic composition of sedimentary CM has
varied by no more than about 5‰ over the last
Fig. 1. Precambrian CM N/C ratios. (A) All samples from Hayes et al.
3.5 billion years. Although it is now recognized that (1983) and Strauss and Moore (1992). There is an apparent increase in
such carbon isotopic fractionation can be produced by N/C beginning at about 2.0 Ga. (B) Samples from (A) with H/C b0.3,
purely abiotic processes (Horita and Berndt, 1999; van controlling for thermal alteration. Except for one carbonate-hosted
Zuilen et al., 2002), the apparent continuity of the early sample near 0.6 Ga, N/C is similar for samples of all ages.
Archean record with later times when CM was produced
primarily by biological processes is impressive. thoroughly serpentinized ultramafic rocks, where oxi-
CM N/C ratios show an apparent increase beginning at dation of olivine to magnetite would have provided the
about 2.1 Ga (Fig. 1). However, almost all of this increase most likely driver for the Fischer–Tropsch-type synthe-
is probably due to better preservation of young CM. sis reactions favored by Brasier et al. (2002) as the source
Comparing only CM with H/C b 0.3 to control for thermal for their hypothesized hydrothermal organic matter.
alteration reveals almost no significant variation in N/C Within 3.5–3.0 Ga sedimentary rocks, CM occurs in
during the Precambrian. It is most likely that CM depo- facies deposited in paleoenvironments including shallow
sited N 2.1 Ga originally had N/C ratios higher than are evaporitic lagoons (Barley et al., 1979; Lowe, 1983;
currently preserved. Again, while it would be naïve to Buick and Dunlop, 1990; Lowe and Fisher Worrell,
suggest that significant primary quantities of nitrogen in 1999), current-active platform settings (Lowe, 1999),
ancient CM implies a biological origin, the apparent and basin settings below storm wave base (Lowe, 1999).
continuity of the compositional record must ultimately CM-rich sediments were deposited atop felsic, mafic,
place constraints on any abiological hypotheses proposed and ultramafic volcanic rocks (Lowe, 1999). In general,
as an explanation for early Archean sedimentary CM. CM appears to have been a ubiquitous component of
clastic-poor marine sediments, much as it was in younger
1.1.3. Carbonaceous matter distribution sedimentary sequences.
One of the most basic observations that can be made
about 3.5–3.0-Ga CM is that it, like nearly all younger 1.1.4. Carbonaceous matter abundance
CM, is found almost exclusively in sedimentary rocks. Perhaps the most notable characteristic of the distri-
CM is rare in igneous rocks. This is true even in bution of CM abundance in early Archean sedimentary
264 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

rocks is how unremarkable it appears in comparison to essentially identical to that formed by biological
younger distributions (Fig. 2). Even without controlling processes in younger strata. For instance, it is not at
for metamorphic alteration or lithology, early Archean all clear that a primarily hydrothermal source could have
CM abundances fall well within the range of abundances produced CM in the quantities and distribution found in
observed in younger rocks. Average CM abundances the early record, or that the CM produced would
in rocks of all lithologies N3.0 and b 3.0 Ga having consistently have isotopic compositions in the range
H/C b 0.3 are statistically indistinguishable. The geolog- observed. It is more plausible that a global atmospheric
ic record of CM abundance therefore exhibits funda- photochemical source in an atmosphere with a high C/O
mental continuity at least as far back in time as ∼3.5 Ga ratio could have replicated the quantities and distribu-
and possibly as far as 3.7 Ga. tion of CM in the early record (Tian et al., 2005), but it is
not yet known if the isotopic record would be replicated.
1.1.5. Continuity in the carbonaceous matter record Moreover, the same photochemical source would have
Although the continuity of the geologic CM record is produced a dense hydrocarbon haze resulting in a strong
not a strong evidence for the emergence of life by anti-greenhouse effect and a cold early Earth (Pavlov et
3.5 Ga, it is at least striking that a broad view of the al., 2001b), inconsistent with evidence for a hot climate
record provides no compelling motivation to consider between 3.5 and 3.2 Ga (Knauth and Lowe, 2003). At
abiological origins. Indeed, while the record permits present there is no better explanation for the early CM
abiological hypotheses, it is difficult to conceive of record than that life had emerged by at least 3.5 Ga.
abiotic processes capable of generating a record Such reasoning from the geologic record provides no
proof that like had evolved by 3.5 Ga, nor is it intended
to. Instead, we suggest that such reasoning about the
geologic record of CM in general must frame necessary
debates over the origin of particular pieces of N 3.0 Ga
CM. In particular, we propose that the best working
hypothesis based on knowledge currently available is
that most if not all carbonaceous matter present in rocks
older than 3.0 Ga was produced by living organisms. We
judge this hypothesis to be more likely than null hypo-
theses postulating an abiotic origin for all CM older than
3.0 Ga. The emergence of life before 3.0 Ga therefore
should not be regarded as an extraordinary hypothesis,
and at the least should not be considered as of similar
probability to the hypothesis that life existed on Mars at
some point in its history.

1.2. A geological approach

In light of what is currently known about the early


geologic record, we suggest that future studies focus
more generally on developing models describing the
origins of CM in particular geologic units. Because there
is not currently a “smoking gun” associated with CM by
which we can definitively determine biogenicity, such
models must ultimately be judged by how coherently
they account for all CM in the study material in terms of
processes operating in the inferred depositional envir-
onments of the host rocks. Environmental reconstruc-
Fig. 2. Precambrian CM abundance in sedimentary rocks. (A) All tion is key: given the large number of possible
samples from Strauss and Moore (1992), this study, and Rosing explanations for ancient CM, comprehensive deposi-
(1999). Samples N3.0 Ga have similar abundances to samples
b3.0 Ga. (B) Samples from (A) with H/C b0.3, controlling for
tional models must be used to eliminate physically
thermal alteration. Abundances in samples N3.0 Ga are statistically implausible hypotheses from a number of physically
indistinguishable from abundances in samples b3.0 Ga. possible mechanisms of formation.
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 265

Two prominent critiques of previous Archean paleo- deposition is considered to occur in a marine sedimen-
biological work have gained significant support in part tary, not hydrothermal, environment. A modern analog
through re-evaluations of depositional models. The illustrates the need for such a distinction. While most
reinterpretation of Apex Chert “microfossils” as abiotic marine dissolved calcium is derived from continental
hydrothermal precipitates is supported in part by the weathering, carbonate reefs are not generally classified
inference that the host rocks are part of a hydrothermal as “continental deposits.” Such a classification would be
vein (Brasier et al., 2002, 2005). Isotopically light only minimally informative as to the physical and
graphite grains in the Isua Sequence (Mojzsis et al., chemical environments in which reefs actually form.
1996; Schidlowski, 2001) are of questionable biological In the stratigraphic record, this division between
origin because the enclosing rocks appear to be metas- marine and hydrothermal systems may be expressed in a
omatically altered volcanic rocks rather than sediments number of ways. Mixing of hydrothermal and marine
(Rosing et al., 1996). fluids would result in geochemical trends identifiable in
Unfortunately, much recent discussion of early suites of precipitated materials. Mixing of hydrothermal
Archean rocks has been clouded by testing between and marine fluids and accompanying mineralization ge-
depositional models that are only implicitly stated and nerally occurs within a short distance of the hydro-
represent an inadequate range of alternatives for des- thermal source, resulting in deposition of vent stocks,
cribing the likely complexity of actual surface environ- chimneys, and mounds (Hannington et al., 1995).
ments on the early Archean earth. For instance, Deposits of limited aerial extent (hundreds to a few
hydrothermal origins for early Archean cherts have thousands of meters) result from this restriction and the
been inferred from their geochemical similarity to mo- geologically brief periods of typical vent activity
dern hydrothermally deposited sediments or hydrother- (Hannington et al., 1995). Deposits would be expected
mal fluids, such as a slightly positive europium anomaly, to interfinger with and grade into normal marine or non-
the absolute abundances and relative ratios of heavy marine sediments. Internal facies changes would reflect
metals, or correlations between heavy metals and iron progradation of mounded deposits and/or debris aprons
abundances (Sugitani, 1992; Kato and Nakamura, 2003). of hydrothermal precipitates. Interpreting rocks as hy-
However, these similarities could also have resulted from drothermal deposits requires identification of features
precipitation in a normal marine setting, physically far such as these consistent with precipitation from mixing,
removed from any local hydrothermal source, in an cooling, or depressurizing fluids.
ocean compositionally controlled by hydrothermal input
(Veizer et al., 1989). It has also been suggested that 2. The Buck Reef Chert as a test case
pervasive early silicification of sediments required
hydrothermal fluids as a silica source (Westall et al., 2.1. Suitability of the Buck Reef Chert
2001). This suggestion ignores the possibility that
normal marine water was saturated with respect to The 3416 Ma Buck Reef Chert (BRC) is the basal
amorphous silica in the Precambrian (Siever, 1992; member of the Kromberg Formation in the Onverwacht
Lowe, 1999). While observations such as these are Group of the Swaziland Supergroup, South Africa
informative about the composition of fluids involved in (Fig. 3). It consists of 250–400 m of carbonaceous and
precipitation and diagenesis of these rocks, they contri- ferruginous chert exposed continuously along N 30 km of
bute little to discrimination between hydrothermal strike in the west limb of the Onverwacht anticline,
settings and normal sedimentary marine environments discontinuously in the east limb of the Onverwacht
in an ocean compositionally similar to hydrothermal anticline and in the Kromberg syncline, and locally about
fluids. 50 km to the northeast in Swaziland (Lowe and Fisher
In this study, “hydrothermal system” will be used to Worrell, 1999). At its base, the BRC interfingers with the
refer specifically to an environment in which sedimen- felsic volcaniclastic sandstone of the underlying member
tation and early diagenesis are controlled by precipita- H6 of the Hooggenoeg Formation. In the central part of
tion from emerging, subsurface hydrothermal fluids due the west limb of the Onverwacht anticline, this sandstone
to chemical saturation induced by decreasing tempera- has been interpreted as coastal and braidplan deposits
ture or pressure, or by mixing with ambient surface (Lowe and Fisher Worrell, 1999). The lowest 0–80 m of
fluids to form insoluble precipitates (ex. ferric hydro- the BRC, including lenses of chert interbedded with
xides, barite, sulfides, etc.). Once hydrothermal fluids felsic volcaniclastic sediments of the top of H6, contain
have mixed significantly with marine fluids and pre- silicified evaporites (Lowe and Fisher Worrell, 1999).
cipitation is no longer controlled by these processes, The overlying 200–300 m of carbonaceous and
266 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Fig. 3. Location maps. (A) General map of South Africa showing location of Barberton greenstone belt. (B) Map of the southern part of the Barberton
greenstone belt showing outcrops of the Buck Reef Chert (BRC). Principal outcrops lie around the Onverwacht anticline (OA) and the Kromberg
syncline (KS). (C) Simplified stratigraphy of the Onverwacht Group (dark gray) and Fig Tree Group (light gray) in the southern domain of the
Barberton greenstone belt. Section height above the base of the Komati Formation indicated on the left. Note scale change above Kromberg
Formation. BRC is the basal unit of the Kromberg Formation. (D) Map of the BRC in the central part of the west limb of the Onverwacht anticline.
Measured sections (Fig. 4) are indicated by thick lines at A and B. Qc = Quaternary cover; fi = felsic intrusive rock; ev = evaporite and black chert
facies; bwc = black-and-white banded chert facies (both contorted and laminated); bfc = banded ferruginous chert facies.

ferruginous cherts of the BRC shows a progressive up- yielded possible microfossils and preserved microbial
ward transition from current-worked, particulate carbo- biofilms (Westall et al., 2001). The abundance of poten-
naceous detritus into finely and continuously laminated tially biological carbonaceous material, together with
units, suggesting a transition to deeper water. Carbona- orthochemical deposits and features suggesting well-
ceous cherts from unspecified locations in the BRC have developed transitions from evaporitic to shallow
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 267

platformal to deep-water depositional environments Swaziland Supergroup is divided into the basal, predo-
makes the BRC an ideal unit for examining the relat- minantly volcanic Onverwacht Group and the succeed-
ionship between carbonaceous matter abundance and ing sedimentary Fig Tree and Moodies Groups. Around
morphology and depositional conditions and environ- the Onverwacht anticline, the two lowest units of the
ment, and for possibly establishing the root origins and Onverwacht Group, the Theespruit and Sandspruit For-
controls on the distribution of CM in these ancient rocks. mations (Viljoen and Viljoen, 1969), are in fault contact
with the rest of the group or occur only as isolated
2.2. Geologic setting xenoliths in surrounding plutons, respectively. The other
four formations of the Onverwacht Group (Komati,
The stratigraphy of the Barberton greenstone belt has Hooggenoeg, Kromberg, and Mendon Formations) and
been summarized by Lowe and Byerly (1999). The the Fig Tree Group form a continuous stratigraphic

Fig. 4. Measured sections through the Buck Reef Chert. See Fig. 3 for locations. ss = current deposited felsic sandstone of H6; ev = black chert with
silicified evaporites, evaporite solution collapse features, and wave ripples; cng = conglomerate; bwc = black-and-white banded chert; sfbc = slightly
ferruginous banded chert; bwsf = interstratified black-and-white banded chert and slightly ferruginous chert; bfc = banded ferruginous chert. EV =
evaporite and black chert facies; LBW = lower black-and-white banded chert facies; UBW = upper black-and-white banded chert facies; BFC =
banded ferruginous chert facies. Dark gray layers are mafic intrusive rocks. Thin horizontal lines along left of columns indicate laminated intervals.
268 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

sequence (Fig. 3C). The Komati Formation is a 3.7-km- to the sample. This instrument had a spot size of ∼1 μm
thick accumulation of komatiitic volcanic rocks with no when focused through a 100× objective lens, an
major sedimentary units. The Hooggenoeg Formation, effective 4000 channels, and 4 cm− 1 resolution. An
3.8 km thick, consists predominantly of units of basaltic average power of ∼40 mW was applied at the sample
and komatiitic volcanic rocks capped by thin sedimen- surface. Spectra were typically collected for 100 s or
tary units. The formation is capped by member H6, a longer to obtain acceptable signal-to-noise ratios.
complex of shallow dacitic intrusions, flow rocks, and Spectral features were interpreted by comparison with
volcaniclastic units that was emplaced and erupted at known reference materials including disordered carbo-
3445 ± 3 Ma (Kröner et al., 1991). naceous matter, quartz, calcite, dolomite, magnesite,
The overlying Kromberg Formation includes ankerite, and siderite.
∼ 1.7 km of mostly mafic volcanic and volcaniclastic
rocks with the BRC at its base. A thin detrital layer at the 2.4. Lithofacies of the Buck Reef Chert
base of the BRC has yielded a single zircon age date of
3416 ± 5 Ma (Kröner et al., 1991). A felsic tuff in the Along the west limb of the Onverwacht anticline,
Footbridge Chert at the top of the Kromberg Formation, the BRC includes four main lithofacies (Fig. 4): (1) a
1.3 km above the BRC, has been dated at 3334 ± 3 Ma basal silicified evaporite and black chert facies 0–80 m
(Byerly et al., 1993, 1996). The overlying Mendon thick that interfingers with the underlying felsic
Formation, about 0.3–1 km thick, is composed of cycles sandstone of the Hooggenoeg Formation (Lowe and
of komatiitic volcanic rocks capped by thin cherty Fisher Worrell, 1999); (2) an overlying lower black-
sedimentary units. and-white banded chert facies up to 60 m thick; (3) an
upper black-and-white banded chert to slightly ferrugi-
2.3. Materials and methods nous chert facies about 100 m thick; and (4) an upper
banded ferruginous chert facies 50–100 m thick. A
A 220-m-thick section of the BRC was measured on capping unit, up to 60 m thick, of black-and-white
the central west limb of the Onverwacht anticline (Fig. banded chert was not studied.
4). A total of 46 samples was collected for slabbing and
thin-sectioning. 22 of these samples, along with 13 2.4.1. Evaporitic facies
supplementary samples collected in a smaller section
1.4 km to the west, were analyzed for major and trace 2.4.1.1. Description. The silicified evaporite facies of
element abundances by X-ray fluorescence at the the BRC was described by Lowe and Fisher Worrell
Washington State Geoanalytical Laboratory, Pullman, (1999). It is composed of laminated and wave rippled
Washington. 19 samples were analyzed for total organic chert (Fig. 5A), silicified evaporitic layers originally
carbon and δ13CCM at the Stanford University Stable composed of nahcolite (NaHCO 3, Fig. 5B) and
Isotope Laboratory. Photomicrographs of more than 400 evaporite solution and solution collapse layers. Large
carbonaceous and mineral grains were collected and solution cavities may be filled with megaquartz, massive
used to establish a morphological and compositional black chert, or locally cave-type formations, including
classification scheme of grain types for point-counting. silicified geopedal soda straws (Fig. 5C). Wave ripples
Thin sections of 38 relatively unweathered samples were have small, ∼ 20 cm, wavelengths, indicating formation
point-counted, including five samples from the evapo- in shallow water. They are defined by interlayered thin,
ritic facies, 18 samples from the carbonaceous cherts of lenticular black-and-white layers (Fig. 5A).
the lower BRC, and 15 samples from visibly ferruginous
cherts of the upper BRC. Principal component analysis 2.4.1.2. Interpretation. Lowe and Fisher Worrell
of point-count data (Wackernagel, 1995) was used to (1999) interpret the volcaniclastic sands of H6 as
define distinct groups of grain and texture assemblages, braidplan and coastal deposits, and the evaporite facies
or microfacies. as the deposits of shallow protected coastal lagoons and
In order to identify opaque materials and mineral evaporitic brine ponds. Evaporite crystals grew during
grains too small to identify optically and to distinguish wetting and drying cycles. Wave ripples with wave-
between different carbonate minerals, mainly calcite, lengths as short as those observed in this facies typically
dolomite, and siderite, Raman spectra were collected in indicate deposition under less than a meter of water
situ from polished thin sections. The instrument used depth (Evans, 1942). Evaporite solution features reflect
was a Kaiser Hololab D5000 Raman microscope a period of exposure and evaporite dissolution. Soda
equipped with a 785 nm diode laser oriented normal straws representing hollow stalactites also reflect
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 269

developed clast-supported conglomerate composed of


clasts of silicified komatiite, black-and-white banded
chert, silicified felsic volcaniclastic sandstone, clear
translucent silica, and cavity-fill quartz in a matrix of
microquartz. The base of the conglomerate is locally
scoured.
The black-and-white banded chert facies crops out for
N 50 km along strike and is composed largely of bands of
black carbonaceous chert b 1 to ∼ 15 cm thick alternating
with bands of pure, white-weathering, translucent chert
from 1 mm to 10 cm thick (Fig. 6A, B). Black and white
bands form subequal parts of the rock. Slightly weath-
ered black bands display massive to crudely laminated
layers of sand and granule size particles. In the lower
∼ 60 m of this facies, major disrupted units of black-and-
white banded chert are interbedded with intact layers. In
the disrupted units, white bands are disrupted to form
rounded or contorted masses (Fig. 6A) or angular plates

Fig. 5. Evaporite and black chert facies. (A) Wave ripples (arrows) in
silicified sediments of the evaporite facies. (B) Upward-radiating
silica-replaced evaporite crystals (a) cutting across and draped by
laminated chert (b). C) Quartz-filled soda straw structures developed
during evaporite solution events.

exposure diagenesis in the vadose zone (Esteban and


Klappa, 1983).

2.4.2. Lower black-and-white banded chert facies


Fig. 6. Soft-sediment deformation features in black-and-white banded
chert of lower black-and-white banded chert facies. (A) White bands
2.4.2.1. Description. The contact between the evapo- showing periodic disruption and soft-sediment foundering in a matrix
rite and the overlying black-and-white banded chert of deformed laminated black chert. (B) White chert plate breccia in a
facies is marked by a thin, 50–100-cm-thick, regionally matrix of black chert. Pens are 15 cm long.
270 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

(Fig 6B). These masses and plates float in a black chert grains. The absence of hydraulically coarse sediment
matrix. Some white bands show plastic deformation and makes it unlikely that this environment was subject to
disruption but little overall displacement. Other masses any vigorous wave or current activity, which would
are thoroughly mixed. Black material flowed plastically have suspended and transported the sand-sized, low-
around disrupted chunks of white chert precursor. Round density carbonaceous material. Deposition was outside
and contorted masses of white chert are most common in of the high-energy beach or near-shore environment
the lower part of this zone, while plates are more com- that might be predicted at this point in stratigraphy by
mon in the upper part. relationship to the underlying evaporitic facies.
Coarse megaquartz-filled cavities are widely devel- Instead, any high-energy near-shore environments
oped in the lower black-and-white banded chert facies. are probably represented by the underlying unconfor-
In undisrupted units, cavities are stratiform and most mity and conglomerate. Water depth was probably
underlie white bands. In disrupted units, cavities are N∼ 15–20 m, the depth to which average waves
typically lenticular, bounded above and on the sides by generate cross-bedding and scour in the modern ocean
white chert plates or masses (Fig. 7). (Allen, 1970).
Most banded sediment was disrupted by early soft-
2.4.2.2. Interpretation. The regional extent of the sediment flowage and deformation to form breccias
basal conglomerate, its erosive contact with the under- originally composed of rigid plates to irregular soft
lying evaporite unit, and the lack of similar conglom- plastically deformed masses of white chert within a fluid
erates throughout the rest of the unit suggest that it matrix of black chert. Soft-sediment disruption is inter-
marks an unconformity. It is most likely a transgressive preted to reflect the effects of storm events, which set up
lag formed in the high-energy wave-active zone and internal stresses and mixing within the still soft, gela-
stranded during marine flooding. The scoured base may tinous silica-and organic-rich bottom materials (Lowe,
have formed during a period of exposure, possibly 1999). Modern storm waves can mobilize sediment to
during the time that evaporite solution collapse features about 200 m water depth (Komar et al., 1972); it is likely
and related structures developed in the underlying that the lower black-and-white banded chert facies was
evaporitic unit. deposited on a shelf under water depths between about
Scour, cross-bedding, and other evidence of high- 15–200 m.
energy current activity are absent in the overlying The consistent location of megaquartz-filled cavities
black-and-white banded chert. Black bands contain below white chert bands and masses suggests that these
abundant carbonaceous grains up to 3–5 mm in are geopedal features formed by fluid escape, either gas
diameter, but no sand-sized detrital volcaniclastic or water, after the white chert precursor was solid but
before lithification of the black bands.

2.4.3. Upper black-and-white banded chert facies

2.4.3.1. Description. In the upper black-and-white


banded chert and slightly ferruginous banded chert
facies, black bands are finely and evenly laminated and
particulate layers are rare (Fig. 8). Black and white bands
are b1 to 3 cm thick. Toward the top of this zone, black
bands take on a dull, slightly ferruginous appearance in
outcrop. White band disruption and brecciation and
megaquartz-filled cavities are less common than in the
lower black-and-white chert facies.

2.4.3.2. Interpretation. The near absence of particulate


layers and soft-sediment disruption and brecciation in
the upper black-and-white banded chert facies reflects
Fig. 7. Geopedal megaquartz-filled cavity (a) underlying a deformed
deposition in a very low-energy environment only rarely
white plate (b). Druzy quartz fills cavities formed by escape of buoyant
fluids, probably water, from still fluid black chert. Rising fluid was affected by currents, waves, or storms. The setting re-
locally trapped beneath impermeable layers and plates of white chert. presented by this facies was near or just below storm
Hammer handle is 20 cm long. wave base.
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 271

2.5. Carbonaceous matter and other microfacies


elements

Carbonaceous matter in the BRC is composed of sub-


micron inclusions in a chert matrix. Raman spectral
characteristics of BRC CM (Tice et al., 2004) are
consistent with organization into graphite crystallites
with in-plane diameters of a few nanometers (Wopenka
and Pasteris, 1993). Each inclusion thus represents
disordered clumps of hundreds of millions of crystallites.
Inclusions are organized into micron to millimeter
scale regions of concentrated CM and intergrown chert.
At this scale, BRC CM occurs as discrete masses,
laminations, networks, and diffuse masses. Walsh and
Lowe (1999) classified CM from throughout the
Barberton greenstone belt and found that CM mor-
Fig. 8. Black-and-white banded chert of the upper black-and-white phology correlates with depositional environment.
banded chert facies in which black bands are finely laminated and BRC CM was reclassified for this study into four
some white bands consist of several thin, distinct layers or laminations. major morphological groups (Fig. 10): carbonaceous
Black bands are slightly ferruginous. Hammer is 40 cm long.
grains, laminations, networks and diffuse masses, and
cavity fill CM.

2.4.4. Banded ferruginous chert facies 2.5.1. Carbonaceous grains

2.4.4.1. Description. The overlying banded ferrugi- 2.5.1.1. Definitions. Four types of discrete carbona-
nous chert facies is composed of alternating bands of ceous grains were identified in the current study: (Kgf)
relatively pure white-weathering chert, 1 mm to 2 cm wispy grains with aspect ratios N 10 (Fig. 11A), (Kgs)
thick, and dark rust-colored, iron-oxide-rich material, simple grains, (Kgl) grains composed of contorted
b 2 cm thick (Fig. 9). The dark ferruginous bands are carbonaceous laminations, and (Kgc) compound grains.
highly weathered, and in places are completely replaced Kgf, Kgs, and Kgc grains correspond to grain types of
by boxwork masses of goethite or hydrous ferric oxide. In the same names of Walsh and Lowe (1999). Kgs grains
less weathered examples, dark bands are finely laminated are composed of one or two domains of concentrated
and contain siderite. Subsurface samples of banded CM (Fig. 11B), Kgc grains are composed of three or
ferruginous chert contain siderite and no ferric minerals.
Primary goethite is unlikely to have been preserved at the
∼300 °C peak metamorphic temperatures experienced by
the BRC and throughout the rest of the Barberton
greenstone belt (Xie et al., 1997; Tice et al., 2004).
Instead, primary goethite would today be represented by
hematite, which is absent. The primary ferruginous
mineral was most likely siderite that has now been
oxidized by modern weathering (Lowe and Byerly, 2003).
Band disruption and brecciation are rare to absent.

2.4.4.2. Interpretation. Like the upper black-and-


white banded chert facies, the banded ferruginous
chert facies was deposited in an extremely low-energy
environment. The near absence of band disruption and
particulate layers and the ubiquity of fine laminations
imply deposition well below storm wave base in a deep
basinal setting. Sedimentation was by gentle settling of Fig. 9. Banded ferruginous chert. Note even banding and fine,
fine material from the overlying water column. continuous laminations. Pen is ∼ 10 cm long.
272 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Fig. 10. Flow chart for classifying Buck Reef Chert carbonaceous matter (CM) by morphology.

more domains of concentrated CM (Fig. 11C), and Kgl Kgc grains show substantial variation in structure.
grains are composed of contorted carbonaceous lamina- Some are clearly recognizable as ripped up chunks of
tions (Fig. 11D). carbonaceous sediment, such as grains composed of
Klr network. Others are composed of multiple
2.5.1.2. Descriptions. Kgs, Kgl, and Kgc grains occur smaller carbonaceous and silica grains bound by
in massive and graded layers, generally mixed with isopachous rims of silica. This subclass corresponds
detrital, sand-sized volcaniclastic or silica grains. They most closely to the “lobate compound” class of
represent detrital particles composed of organic matter. Walsh and Lowe (1999). Still other Kgc grains are
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 273

Fig. 11. Carbonaceous grains. (A) Kgf post-depositionally compacted carbonaceous grains (arrows) with high aspect ratios. Scale bar is 0.2 mm. (B)
Kgs simple carbonaceous grain (arrow) with b3 internal clots or chunks of denser CM. Scale bar is 0.1 mm. (C) Kgc compound carbonaceous grain
with N3 internal zones of concentrated carbonaceous matter. Scale bar is 0.5 mm. (D) Kgl complex carbonaceous grain with N3 internal zones of
concentrated carbonaceous matter and composed of contorted laminations. Scale bar is 4 mm.

composed of tightly packed smaller carbonaceous 2.5.2. Carbonate, silicified carbonate, and carbonate/
and silica grains bound by a diffuse carbonaceous CM grains
matrix, similar to material composing layers in the
evaporite facies. 2.5.2.1. Definitions. Four types of carbonate and re-
Kgl grains are composed of laminations or network placed carbonate grains are recognized in the present
interpreted below to represent microbial mats when study. Cp grains are small, ∼ 10 μm grains of siderite
found in situ. Kgf grains form layers in which their long (Fig. 12A). Crh grains are larger, 10–200 μm well-
axes are aligned parallel to bedding. formed rhombic siderite grains (Fig. 12B). Cp and Crh
grains are commonly replaced by goethite or hydrous
2.5.1.3. Interpretations. Kgs, Kgl, and Kgc grains all ferric oxide in surface samples as a result of modern
appear to represent ripped up carbonaceous and sili- surface oxidation (Lowe and Byerly, 2003). Cg grains
ceous sediment. Kgl grains most likely represent ripped are 1–2 mm, silica-replaced rhombic minerals (Fig.
up microbial mats. Kgc grains were ripped up from a 12C). KF grains are composed of siderite and diffuse CM
variety of sediments, including microbial mats and (Fig. 12D). While KF grains are thus composite carbo-
partially silicified detrital layers. Kgs grains are nate and CM grains, siderite is the major component so
generally smaller than the other grain types with simpler they are here classified with carbonate grains.
morphologies that make their origins more difficult to
infer, but they may represent transported and broken 2.5.2.2. Descriptions. Cp and Crh grains occur iso-
larger rip up grains. lated within a chert matrix and form thin flat laminations,
Kgf grains appear to represent soft carbonaceous layers, and lenses. Particularly in the lower black-and-
grains compacted by burial (Walsh and Lowe, 1999). white banded chert facies, where carbonate grains are
274 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Fig. 12. Carbonate, silicified carbonate, and carbonate/CM grains. (A) Fine Cp siderite grains. Scale bar is 30 μm. (B) Large Crh rhombic siderite
grain. These grains are frequently oxidized, forming goethite-filled rhombic cavities after siderite. Scale bar is 0.2 mm. (C) Cg grains. Quartz-filled
rhombs after twinned dolomite(?). Scale bar is 1 mm. (D) KF grains (arrows). Silt-sized grains composed of disseminated siderite crystals (now in part
oxidized to goethite and hydrous ferric oxide) and diffuse carbonaceous matter. Scale bar is 70 μm.

only a trace constituent of the rock, Cp and Crh grains formed by direct precipitation rather than by reduction
tend to occur in thin laminae without associated carbo- of ferric oxides by organic matter. Moreover, the
naceous grains. In the upper black-and-white banded paucity of clastic material throughout most of the BRC
chert and the banded ferruginous chert facies, where implies that reduced iron was not supplied by
carbonate is commonly a major constituent of the rock, mobilization within the sediment. Instead, the overly-
Cp and Crh grains are typically mixed with fine carbo- ing water column must have been saturated with
naceous grains although thin layers composed only of siderite. There is no evidence that crystal growth within
carbonate grains still occur. Cp grains are usually locally the sediment displaced CM, and etched faces on Crh
of very uniform size. Neither type of grain was observed grains may actually suggest some degree of local
to have displaced or distorted neighboring carbonaceous undersaturation. It seems likely, therefore, that at least
grains. Crh crystal margins are commonly corroded or some siderite formed within the water column and
etched. No crystallographic twinning was observed in constituted part of a background hemipelagic rain.
Crh grains. Concentration of siderite grains in thin laminae that
In contrast, Cg grains observed in this study have lack sand-sized detrital carbonaceous grains that are
dense, black borders, probably representing CM dis- common in the lower black-and-white banded chert
placed during crystal growth. One of four examples facies could indicate that deposition of siderite was
observed possessed a crystallographic twin, suggesting slow, and that detectable abundances accumulated in
that twinning was not uncommon in the replaced shallow-water environments only during breaks in CM
mineral. sedimentation. In contrast, it is not clear if siderite in
KF grains was precipitated in a mobile or suspended
2.5.2.3. Interpretations. Occurrences of Cp and Crh carbonaceous grain, or if precipitation occurred in the
grains isolated from CM indicate that the siderite was sediment.
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 275

microquartz, although some contain extremely diffuse


CM (Fig. 13A). Sd grains are microquartz grains
containing regions of concentrated CM which comprise
b 50% of the grain (Fig. 13B).

2.5.3.2. Descriptions. Sa grains display a limited


range of morphologies and compositions. Well-
rounded grains are common and widespread. They
occur individually or associated with detrital carbo-
naceous grains and commonly in graded layers.
Others occur compacted in layers with Kgf grains.
Rarer Sa grains display cores or rims containing CM
(Fig. 14A), or have complex, wandering boundaries
(Fig. 14B).
Sd grains are commonly associated with complex
carbonaceous grains (Kgl and Kgc) and are much less
common than Sa grains.

2.5.3.3. Interpretations. Sa grains represent relatively


soft, possibly gelatinous detrital siliceous sediment.

Fig. 13. Silica grains. (A) Sa grain composed of nearly pure


microquartz. Scale bar is 0.2 mm. (B) Sd grain. Silica grain
containing b50% concentrated carbonaceous matter. Scale bar is
0.2 mm.

Cg grains are far less common than Cp, Crh, or


KF grains. While no relict carbonate is present to
directly determine the original composition, it is likely
that Cg grains represent silica-replaced dolomite.
Twinning is uncommon in siderite but common in
dolomite. Displacement of surrounding CM suggests
that these grains precipitated diagenetically. If dis-
solved calcium ultimately limited calcite and dolomite
precipitation in the early Archean oceans (Grotzinger
and Kasting, 1993; Lowe and Fisher Worrell, 1999),
then formation of Cg grains may have been a
response to transient local enhancement of calcium
in pore fluids. Calcium depletion during later burial
could have resulted in dissolution and subsequent
replacement by silica.

2.5.3. Silica grains


Fig. 14. Silica grains. (A) Sa grain with nearly pure silica core and
large rim containing diffuse carbonaceous matter. Scale bar is 0.1 mm.
2.5.3.1. Definitions. Two types of silica grains are (B) Very coarse Sa grain showing highly irregular, possibly corroded
distinguished. Sa grains are composed almost entirely of boundary. Scale bar is 0.4 mm.
276 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Some probably represent grains of silica gel eroded from


partially silicified sediment, although composite grains
suggest that carbonaceous matter accretion and silica
precipitation occurred at least occasionally at the
sediment surface. The few examples of Sa grains with
wandering boundaries that have been identified were
associated with Kn mat-like laminations, often
appearing to rest at unstable angles on top of mat
surfaces (Fig. 14B). It is possible that they were
originally formed as siliceous concretions within
microbial mats, and that their complex boundaries
result from aggregation in a diffusion-limited envi-
ronment. It is also possible that they represent silica
grains deposited on mat surfaces which were
subsequently corroded.
Sd grains most likely represent ripped up chunks of
partially silicified sediment. The rarity of this grain type
relative to Sa grains (nearly pure silica) and Kgc grains
(mostly carbonaceous matter) suggests that segregation
of predominantly carbonaceous and predominantly
silica sediment, possibly within black-and-white
“proto-bands”, occurred at very shallow depths in the
sediment column.

2.5.4. Other grains


Fig. 15. Other grains. (A) P grain composed of disseminated
2.5.4.1. Definitions. Four types of other grains were carbonaceous matter and very fine phyllosilicates. Scale bar is
distinguished in this study. P grains are aggregates of 0.2 mm. (B) Lv grain composed of very fine phyllosilicates, probably
diffuse carbonaceous matter, silica, and very fine phyl- after feldspar or a volcaniclastic particle. Scale bar is 0.3 mm.
losilicates (Fig. 15A). Lv grains are micromosaics of
microquartz and phyllosilicates, probably sericite (Fig.
15B), H grains are chlorite clots, and R grains are Klm and Klr laminations anastomose and bifurcate.
pyrite. Klm laminations have constant intra-lamination thick-
ness and bifurcate around lenses of pure chert and
2.5.4.2. Descriptions and interpretations. Micas in P around carbonaceous grains (Fig. 16B). The thickness
grains are typically aligned, suggesting that these of Klr laminations varies laterally over very short
grains represent chips of carbonaceous mud. Lv grains distances (Fig. 16C). These laminations bifurcate
represent altered dacitic volcaniclastic material derived around lenses of pure chert, but not around carbona-
from the underlying felsic sands of member H6 of the ceous grains.
Hooggenoeg Formation (Lowe and Fisher Worrell,
1999). No chlorite grains preserve detrital shapes, and 2.5.5.2. Descriptions. Outsized detrital carbonaceous
most probably represent alteration products of detrital grains (typically Kgc) are ubiquitous in Klm lamina-
grains eroded from komatiitic or basaltic volcanic tions. Laminations drape large grains, forming tent-like
rocks. or “open eyelet” structures that tend to subdue
underlying topography. When eroded, they occasionally
2.5.5. 2-D carbonaceous laminations produced roll-up structures, or folded chips of lamina-
tions (see Kgl grains above).
2.5.5.1. Definitions. Three types of carbonaceous Individual Klb laminations are only 1–5 μm thick
laminations have been identified in the BRC, termed and separated by chert laminations 1–10 μm thick.
Klb, Klm, and Klr. Klb laminations are simple They wrap tightly around detrital grains and other
undivided carbonaceous layers separated by thin topographic elements rather than draping them and do
layers of pure chert (Fig. 16A). In contrast, both not form the large “open eyelet” structures around the
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 277

Lowe (1999), who interpreted them as fossil microbial


mats on the basis of their morphological similarity to
modern mats and their tendency to form roll-up
structures when eroded. Because they are thinner and
modify underlying topography less than other mat-like
features identified in this study, they are interpreted here
to represent microbial biofilms.
The ubiquitous presence of outsized carbonaceous
detrital grains but not smaller grains approaching the
thickness of individual laminae makes it unlikely that
Klm laminations originated as very fine carbonaceous
grains. The bifurcating habit of Klm laminations also
indicates that they were not formed by settling of
fine carbonaceous grains out of suspension or by
current deposition. They formed roll-up structures
(see Kgl grains above), implying cohesive strength at
or near the sediment surface. It is significant that
only Klb and Klm laminations and Kn networks
(definition follows) formed roll-up structures, sug-
gesting that the necessary cohesive strength was a
property of these particular carbonaceous laminations
and networks rather than the encasing silica. Their
carbonaceous composition and cohesiveness suggest
that Klm laminations represent microbial mats
(Simonson et al., 1993; Sumner, 1997; Walsh and
Lowe, 1999).
The crenulated, irregular, bifurcating habit of Klr
laminations likely has its origin by a different
mechanism. Darker regions of these laminations occur
preferentially below clear spaces. Where these spaces
are less common or locally absent, CM forms a less
differentiated, diffuse matrix. It is likely that Klr

Fig. 16. Carbonaceous laminations. (A) Klb laminations showing fine,


undivided layering. Scale bar is 0.5 mm. (B) Klm laminations showing
anastomosing and bifurcating habit and constant intra-lamination
thickness. Scale bar is 1 mm. (C) Klr laminations showing
anastomosing and bifurcating habit and varying intra-lamination
thickness. Scale bar is 0.2 mm.

sides of carbonaceous particles characteristic of Klm


laminations.
Klr laminations are crenulated and highly irregular,
varying substantially in darkness and thickness. Larger
irregular carbonaceous grains are distributed randomly
throughout layers of Klr laminations, but never within
bifurcations.
Fig. 17. Kn network composed of a web of very fine strands of
2.5.5.3. Interpretations. Klb laminations correspond carbonaceous matter. Top of network is a smooth, dense surface. Scale
to the “fine carbonaceous laminations” of Walsh and bar is 0.2 mm.
278 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Fig. 18. Two Kn networks. Top network forms laminations which drape an underlying coarse detrital layer (a) and show internal anastomosing
character (b). The bottom network (gray band at d) grew around detrital grains resting on its surface (c) and down into the interstices between detrital
grains (d). Two well-sorted layers of CM and silica detritus (e and f) separated by a thin and discontinuous layer of carbonaceous network (g). The
upper layer is composed of very coarse sand- to granule-sized Kgc, Sa, and Sc grains stacked only a few grains thick (e). The lower layer is composed
of medium to coarse sand-sized Kgc and Sa grains (f). Scale bar is 1 mm. From microfacies III, 30 m in section (Fig. 4).
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 279

commonly cut across carbonaceous laminations, indi-


cating that the lattice structure was not formed in
response to displacement of carbonaceous matter during
quartz crystallization. Indeed, the uniqueness of this
structure considered relative to other types of Buck Reef
Chert carbonaceous material strongly suggests that
networks were not formed as a result of any stage of
silica crystallization or precipitation since silicification
was ubiquitous. Chunks of network have been locally
ripped up and deformed plastically, indicating that they
were cohesive (Fig. 19). Kn grew around and draped
detrital grains deposited on underlying network sur-
faces. Open, 3-D network often extends downward
between the uppermost grains in detrital layers (Fig. 18).

2.5.6.3. Interpretation. The carbonaceous composi-


tion, draping habit, and cohesiveness suggest that these
lamination-forming networks represent microbial mats.
Growth of mats to only shallow depths in underlying
detrital layers suggests that the sediment surface was the
optimal growth location for the constructing microbes,
potentially because of access to nutrients or light.

2.5.7. Diffuse carbonaceous matter


Fig. 19. Roll-up structures in CM. Rolled up segments of mat-like
laminations demonstrate that these laminations possessed cohesive 2.5.7.1. Definition. Kd is extremely fine, diffuse,
strength at the sediment surface. (A) Multiply folded example from the massive CM with variations in concentration and a
lower disrupted black-and-white banded chert facies. (B) Two mat few outsized particles (Fig. 20).
segments almost enclosing multiple carbonaceous and silica grains
from the upper evaporite and black chert facies.
2.5.7.2. Description and interpretation. Kd CM
typically contains isolated simple carbonaceous grains
and forms massive to crudely laminated layers. It is
laminations represent a matrix of fine carbonaceous interpreted to represent a well-mixed, soft organic and
material compacted between harder silica grains. siliceous ooze.

2.5.6. 3-D carbonaceous networks

2.5.6.1. Definition. Kn is composed of very fine


strands that interconnect to form a web-like network
(Fig. 17).

2.5.6.2. Description. Kn layers commonly include


two network structures: (1) open, three-dimensional
lattices of carbonaceous strands that fill interstices
between grains; and (2) fine, dense laminations that cap
layers, drape detrital grains or other bottom irregular-
ities, and form discontinuous flat-to-concave-upward
laminations (Fig. 18). Lattices and laminations grade
into one another, and laminations probably represent
compacted or collapsed network. Openings in the Fig. 20. Diffuse CM. Kd finely dispersed, structureless carbonaceous
network lattice do not correspond to individual quartz matter with isolated simple carbonaceous grains (dark). Scale bar is
crystals or optical domains, and optical domains 0.2 mm.
280 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Fig. 21. Carbonaceous cavity fill. (A) Kcv cavity fill carbonaceous matter. Scale bar is 0.1 mm. (B) Sm grain. Silica grain with internal cavity filled by
carbonaceous matter and silica microspheres. Scale bar is 0.5 mm.

2.5.8. Carbonaceous cavity fill has been suggested for other Archean pore- and fracture-
filling CM (Buick et al., 1998; England et al., 2002;
2.5.8.1. Definition. Kcv fills or lines cavities, many of Rasmussen, 2005).
which show an initial stage of filling by silica as lepi-
spheres (Fig. 21A). Sc grains are ripped up chunks of 2.6. Microfacies
CM-cavity-filled silica (Fig. 21B).
The results of point-counting of CM types and asso-
2.5.8.2. Description and interpretation. Kcv linings ciated grains in black bands (Table 1) were analyzed
frequently form isopachous layers around all sides of using principal component analysis to identify groups of
cavities, indicating that the CM precursor was fluid similar grain, lamination, and network associations.
rather than particulate. Occurrence with diagenetic silica These groupings were used to define microfacies. For a
phases suggests that this fluid was also diagenetic, more complete discussion of principal component anal-
possibly early hydrocarbons. The same type of origin ysis see Wackernagel (1995).

Table 1
Point-count data and microfacies assignments

TSA5- TSA5- TSA5- SAF475- SAF475- SAF475- TSA5- SAF475- TSA5- SAF475- TSA5- SAF475- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5-
1 2 3 10 11 12 24 13 4 14 6 15 10 26 7 27 28 29

Position 3 4 9 14 15 16 16 17 19 21 21 24.5 30 30.5 41 42 46 47


(m)
Klb 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 16.6 49.8 40.0 0.0 0.0
Klm 0.0 0.0 0.0 0.8 0.0 0.0 0.0 0.0 49.0 0.0 11.1 0.0 1.1 0.0 0.0 2.9 0.0 0.0
Klr 0.0 0.0 0.0 0.8 0.0 0.7 17.9 0.0 0.0 0.0 0.0 0.7 0.0 13.4 0.0 2.9 0.0 0.0
Kd 0.0 0.0 80.3 74.2 19.3 17.1 10.7 80.8 2.0 29.9 0.0 27.7 9.7 0.0 11.5 2.9 12.0 0.0
Kn 0.0 0.0 0.0 0.0 0.0 0.0 5.4 0.0 0.0 0.0 0.0 0.0 4.3 0.0 0.0 0.0 0.0 0.0
Kcv 5.3 2.7 0.0 0.0 0.9 0.7 5.4 0.0 0.0 0.0 0.0 1.5 0.0 0.0 0.0 0.0 0.0 0.0
Kgf 0.0 0.0 0.0 0.0 0.0 0.0 7.1 3.0 0.0 2.3 0.0 0.7 0.0 43.9 1.6 0.0 1.3 0.0
Kgs 3.5 73.2 19.1 16.7 44.0 42.1 12.5 12.1 4.1 33.3 13.9 30.7 10.8 16.3 19.0 21.8 17.3 1.4
Kgl 0.0 0.0 0.0 2.5 5.5 0.0 0.0 0.0 22.4 1.1 5.6 0.0 2.2 0.0 1.6 0.0 1.3 0.0
Kgc 0.0 0.0 0.0 2.5 10.1 16.4 16.1 2.0 20.4 5.7 61.1 13.9 34.4 3.7 14.8 26.5 65.3 0.0
Cp 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 35.2
Crh 0.0 0.0 0.0 0.0 0.0 0.0 5.4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 60.0
Cg 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
KF 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 3.4
Sa 0.0 0.9 0.0 0.8 14.7 20.7 19.6 2.0 2.0 24.1 5.6 21.9 31.2 6.1 0.0 2.9 1.3 0.0
Sd 0.0 0.0 0.0 1.7 0.9 2.1 0.0 0.0 0.0 3.4 2.8 2.9 3.2 0.0 1.6 0.0 1.3 0.0
Sc 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 3.2 0.0 0.0 0.0 0.0 0.0
P 87.6 2.7 0.0 0.0 2.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Lv 3.5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
H 0.0 19.6 0.6 0.0 1.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
R 0.0 0.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Microfacies I II II II II II II II III II III II III II III III III V

All data are reported as percentages normalized to 100. Number of grains counted was typically 80–120.
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 281

2.6.1. Principal component analysis variables. Eq. (2) implies that any pair of weightings
Principal component analysis is a data-transforma- for a single variable (e.g. amj, anj where m ≠ n) plots
tion technique used to convert sets of correlated vari- within the unit circle. As a consequence of the way
ables (x1, x2, x3, …, xN, where N is the number of in which the weightings are derived, such plots place
variables) into equivalent sets of uncorrelated principal weighting pairs for correlated variables close togeth-
components (PC1, PC2, PC3, …, PCN). Each component er, those for uncorrelated variables 90° apart, and
is a linear combination of the original variables, and those for anticorrelated variables on opposite sides of
there are as many components as variables. the circle. For instance, if x1 was highly correlated
with x2, then a plot of the weightings for the first
PCi ¼ Rj aij xj ð1Þ two principal components applied to x1 and x2, (a11,
Here, i and j vary from 1 to N, and aij are weightings a21) and (a12, a22), would consist of two points very
which convert correlated variables into uncorrelated close to each other near the edge of the unit circle.
components. These weightings are scaled such that Eq. Plots of weighting pairs along with a unit circle are
(2) holds. called circle of correlation diagrams, and are useful
for visualizing correlations and for determining what
Ri ðaij Þ2 ¼ 1 ð2Þ data behavior is captured by sets of principle
components.
These weightings, and through them the principal Point-count data are included in Table 1. For
components, are the output of principal component principal component analysis, some classes of CM
analysis. and other grain types were combined. Since they
By convention, components are listed in order of tended to occur together, Kgf and Klr were combined
decreasing significance, i.e. each succeeding component to define Kf. Kgl, Kgc, and Sd were combined to
accounts for less of the total variance of the set of define Kc, a class of complex, ripped up grains. Klb,
measurements than the component before it. By Klm, and Kn were combined to define Km, a class of
discarding the components that represent very small biofilm- and mat-like laminations and networks. P, Lv,
amounts of the total variance, a large initial set of and H were combined to define Cl, a class of clastic
variables can be converted into a smaller set of grains. KF, Crh, and Cp were combined to define Fe, a
components that captures the key information of the class of sideritic grains. These classes, together with
original system. Kgs (simple carbonaceous grains), Sa (silica grains),
Principal component analysis also provides a and Kd (diffuse CM), composed more than 80% of the
useful technique for visualizing correlations between carbonaceous matter and associated grain types of each

TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5-
37 30 9 8 38 11 40 12 22 31 13 14 15 16 17 33 18 34 36 23

48 50.5 52 61 71 80 83 87 89.5 90 91 99 111 120 138 140 143 153 173 182

0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
15.6 9.4 17.1 0.0 4.1 0.0 41.2 2.3 2.3 48.9 59.5 0.7 9.0 0.0 0.0 37.7 0.7 7.0 0.0 0.0
0.0 0.0 6.1 2.9 0.0 1.9 8.8 0.0 4.7 0.0 12.2 4.2 0.0 0.0 0.0 3.3 3.5 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 3.1 0.0 2.9 1.0 0.0 0.0 0.0 3.9 0.0 1.5 0.0 0.0 0.0 0.0 0.8 19.1 0.8 0.0 0.0
2.2 12.5 0.0 0.0 2.1 31.2 30.7 0.0 55.0 8.9 9.9 83.1 2.2 0.0 0.0 14.8 67.4 46.9 0.0 0.0
0.0 20.3 12.2 13.2 21.6 11.5 7.9 2.3 27.1 0.0 16.0 10.6 0.0 0.0 0.0 12.3 6.4 0.8 0.0 0.0
0.0 0.0 4.9 1.5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.8 0.0 0.0 0.0 0.0
0.0 12.5 56.1 77.9 55.7 0.0 0.9 0.0 0.8 0.0 0.0 0.7 0.0 0.0 0.0 19.7 1.4 0.0 0.0 0.0
71.1 28.1 0.0 0.0 5.2 0.0 0.0 83.7 0.0 8.9 0.0 0.0 10.1 0.0 29.0 0.8 0.0 5.5 0.0 0.0
2.2 12.5 0.0 0.0 0.0 29.3 0.0 0.0 0.0 0.0 0.0 0.0 9.0 0.0 0.0 0.0 0.0 38.3 64.2 100.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.8 0.0 0.0
8.9 0.0 0.0 0.0 1.0 12.7 8.8 11.6 0.0 33.3 0.0 0.0 69.7 100.0 71.0 4.1 0.0 0.0 35.8 0.0
0.0 1.6 2.4 0.0 8.2 12.1 0.9 0.0 6.2 0.0 0.8 0.7 0.0 0.0 0.0 3.3 1.4 0.0 0.0 0.0
0.0 0.0 1.2 1.5 1.0 0.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.5 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
V IV III III III IV IV V IV IV IV IV V V V IV IV IV V V
282 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

sample, and typically more than 96%. The set of


compiled data (Kgs, Kc, Km, Kf, Fe, Sa, Cl, Kd) was
renormalized to sum to 100%.
So that variations in categories that are never more
than minor components of any sample would not be
obscured by variations in major components, this reno-
rmalized data set was transformed by renormalizing
each category by the category mean and standard
deviation to produce a set of eight variables having
means of 0 and standard deviations of 1. Principal
component analysis was applied to the transformed set.
The eight derived principal components accounted for
27.0%, 17.0%, 14.7%, 13.5%, 11.7%, 9.0%, 7.0%, and
0.0% of the total data variance, respectively. Of these
components, the first three captured 58.7% of the
variance. Circle of correlation diagrams (Fig. 22)
illustrate the weightings of the first three principal
component, a1j, a2j, and a3j. The first principal
Fig. 23. First three principal components (PC1, PC2, and PC3). These
component discriminates between grain assemblages components were used to divide point-counted samples into five
with abundant ferruginous grains and those with microfacies, labeled I through V. Microfacies II clusters in the
abundant simple carbonaceous grains, silica grains, southwest quadrant of the plot of the first and second principal
and complex carbonaceous grains. The second principal components. Likewise, microfacies III clusters in the northwest
quadrant, microfacies IV clusters in the southeast quadrant, and
component emphasizes assemblages with abundant
microfacies V clusters in the northeast quadrant. Microfacies I is
complex grains and microbial structures. The third distinguished by an extremely negative third principal component, a
principal component discriminates between assem- consequence of high clastic grain abundances.
blages with abundant clastic grains and those with
abundant carbonaceous compacted features. These three
components were used to divide counted samples into
five distinct assemblages or microfacies (Fig. 23): (1)
microfacies I (represented by one sample) has PC1 N 0,
PC2 b 0, and PC3 b 0; (2) microfacies II has PC1 b 0.2PC2
and PC2 b 0; (3) microfacies III has PC1 b 0 and PC2 N 0;
(4) microfacies IV has PC1 N 0.2PC2, PC2 b 0, and
PC3 N 0; and (5) microfacies V has PC1 N 0 and PC2 N 0.

2.6.2. Microfacies I

2.6.2.1. Description. Microfacies I is characterized by


its high clastic component. This component is primarily
P grains, or amalgamations of carbonaceous matter and
phyllosilicates. Microfacies I is also the only micro-
facies containing Lv felsic volcaniclastic grains. Carbo-
naceous grains are simple in morphology. No visible
siderite grains are present. The only sample composed
of microfacies I is from the base of the evaporite facies
(Fig. 24).

Fig. 22. Circle of correlation diagrams. Weightings for the first three 2.6.2.2. Interpretation. Microfacies I is an association,
principal components (a1, a2, and a3) are plotted against each other. in order of abundance, of mud chips, felsic volcaniclastic
Unit circles are also plotted. Features with closely correlated
distributions plot next to each other in these diagrams. For instance,
sand grains, and simple carbonaceous grains. This
Kc (complex carbonaceous grains) and Km (mats) plot close to each assemblage suggests deposition in an environment
other because they tend to occur together. subject to currents that mixed nearby clastic material
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 283

Fig. 24. Microfacies, elemental and CM abundances, elemental ratios, and CM isotopic composition vs. stratigraphic position in samples collected
from the Buck Reef Chert.

with carbonaceous grains. The same currents could have consistent with its known depositional setting of shallow
been responsible for ripping up microbial mats to brine ponds developed on a distal alluvial plane
produce the carbonaceous grains. This interpretation is constructed largely of felsic volcaniclastic debris.
284 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

2.6.3. Microfacies II 2.6.4. Microfacies III

2.6.3.1. Description. Microfacies II is an association 2.6.4.1. Description. Microfacies III is an association


of simple carbonaceous grains, silica grains, clastic of complex carbonaceous grains, simple carbonaceous
grains, and complex carbonaceous grains, although grains, silica grains, and mat-like laminations. It is
most samples contain little or no clastic component. distinguished by a high abundance of complex carbo-
Simple carbonaceous grains (Kgs) and silica grains (Sa) naceous grains relative to simple carbonaceous grains,
are much more abundant than complex carbonaceous silica grains, and compacted carbonaceous features. It is
grains. Kd diffuse carbonaceous matter is particularly the only microfacies with samples containing abundant
abundant in this microfacies. No visible siderite grains microbial structures (Klb, Klm, and Kn). Some samples
are present. contain trace abundances of siderite grains. Clastic
Layering in microfacies II sediments occurs in three terrigenous grains are absent.
modes: (1) thin, b 1 mm, layers of simple carbonaceous Four primary types of layers occur in microfacies III
grains alternating with pure silica layers of subequal sediments: (1) thin (generally b 2 cm) massive to
thickness; (2) relatively thick, 1 to N 5 cm, massive normally graded layers of complex carbonaceous grains
layers of simple carbonaceous grains and silica grains; and silica grains (Figs. 18 and 26); (2) layers of Klm
and (3) thick, N5 cm, massive to crudely laminated laminations with trapped simple and complex carbona-
layers of diffuse carbonaceous matter (Kd) and simple ceous grains (Fig. 25); (3) layers of Kn network
carbonaceous grains. intergrown with or draping layers of simple and
Microfacies II sediments comprise most of the complex carbonaceous grains and silica grains (Fig.
evaporitic facies and much of the lower half of the 18); and (4) layers of Klb laminations with poorly sorted
lower black-and-white banded chert facies (Fig. 24). detrital carbonaceous grains (Fig. 26). Microfacies III
sediments comprise much of the lower black-and-white
2.6.3.2. Interpretation. The low abundance of com- banded chert facies (Fig. 24).
plex carbonaceous grains, such as in microfacies III, is
suggestive of a current-active environment that tended 2.6.4.2. Interpretation. Preservation of in-place mi-
to break apart carbonaceous particles and regularly crobial mats suggests that, unlike the environment that
disturb the sediment surface. Ripped up chips of Kn favored deposition of microfacies II, the microfacies III
carbonaceous laminations (Fig. 19) indicate the pres- setting was not frequently subjected to extreme current
ence of microbial mats, although none are preserved in or wave activity. The presence of ripped up chunks of
place. This is also consistent with a current-active carbonaceous sediment suggests that the sediment
setting for deposition of microfacies II sediments. surface was only episodically disturbed, leaving sedi-
Thicker massive, unsorted layers reflect deposition ment time to partially silicify and consolidate in place.
during the waning stages of energetic events, probably As in the microfacies II environment, silicification
storms. occurred early relative to burial and compaction.
Thin alternating layers of carbonaceous grains and Two particularly thick and well-preserved examples
chert could have formed as laminations of carbona- of mat-like laminations allow examination of the
ceous matter and particulate silica hydraulically processes involved in mat construction. Fig. 18 shows
separated by alternating currents, as laminations formed an example of a mat composed primarily of Kn network-
in an environment in which silica and carbonaceous constructed laminations draped over a detrital layer. Fig.
matter were alternately and rhythmically deposited, or 25 shows a thick stack of Klm laminations. In both
through an early diagenetic separation. Stacks of 20 or cases, anastomosing, lenticular, or cuspate elements are
more of these layers of relatively uniform thickness most frequently present in areas of topographic relief,
suggest one of the latter two alternatives. Layers of this typically generated by the presence of detrital grains.
type are found in association with silicified evaporites, This suggests that, instead of being formed by bubbles,
and may have formed as a result of wetting and drying diagenetic silica precipitation, or recrystallization, these
cycles. voids formed during mat growth. Rather than creating
The preservation of complex carbonaceous grains additional relief, these elements subdued it, creating
and equant simple carbonaceous grains against sedi- relatively flatter surfaces. It is possible that these
ment compaction implies silicification at shallow structures result from local biological responses that
depths in the sediment column (Walsh and Lowe, maximized mat surface exposure to sunlight. Structures
1999). similar in geometry but larger in scale have been
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 285

Fig. 25. Klm laminations and detrital layers. Klm laminations anastomose and bifurcate (a) around large detrital carbonaceous grains (b). Two distinct
layers of detrital carbonaceous grains (c, d) overly the basal Klm layer. The lower detrital layer is matrix-supported at its base (c). Grains in (c) display
a continuous range of shapes from rolled up mat chips (Kgl) to complex grains (Kgc) to simple grains (Kgs). Grains in (d) are predominantly very
coarse mat chunks. A slightly disrupted layer of Klm laminations overlies the detrital layers. Scale bar is 5 mm. From microfacies III, 19 m in section
(Fig. 4).
286 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Fig. 26. Layer composed of Klb laminations and poorly sorted detrital carbonaceous grains. Laminae drape grains without significantly modifying
topography (a). Layer was disrupted (b) when sediment was partially silicified, and resulting stratiform cavities were infilled by pure silica. Later
quartz vein (c) cuts early silicified CM layers and early disruptive silica. Scale bar is 1 mm. From microfacies III, 41 m in section (Fig. 4).

observed in late Archean cuspate microbialites (Sumner, occurring in 60–73 °C regions of modern Yellowstone
1997, 2000), where they frequently formed attachments hot springs (Walter, 1976; Lowe et al., 2001). In contrast
on the sides of vertical carbonaceous supports. to later stromatolite-dominated platforms (Beukes,
The presence of isolated outsized detrital grains 1987), the Buck Reef Chert shallow seafloor was
suggests that relatively thick mat growth (up to several structured primarily by abiotic physical and chemical
millimeters) occurred during intervals of low current processes despite the ubiquitous presence of biotically
activity. Particulate detritus was carried in by occasional produced organic matter and mats. Unlike mats growing
more energetic events, but more frequent background in lower-temperature regions, Synechococcus–Chloro-
currents kept the mat surface swept clear of finer, low- flexus mats are not known to silicify (Walter, 1976;
density material. Mats responded to the presence of Lowe et al., 2001). BRC mats may also not have
detrital grains locally, either by draping resulting silicified as rapidly as surrounding sediments. This may
topography or by developing low-density cuspate explain the scarcity of in-place mat deposits and thick
structures that allowed them to quickly reestablish a mat accumulations relative to the abundant eroded
flat surface. Currents may have locally ripped up mat detrital carbonaceous grains. It is possible that BRC
chunks, but they were generally not of sufficient organisms even produced organic acids or ligands that
strength to obliterate or bury entire mats. locally lowered silica activity in mat pore fluids
Klm and Kn microbial mats were thin and not relief- (Bennett and Siegel, 1987) as a mechanism to prevent
forming, similar to Synechococcus–Chloroflexus mats silicification during mat growth.
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 287

Fig. 27. Microfacies IV. Layers are composed of fine-to medium-grained carbonaceous grains showing strongly contrasting amounts of compaction.
Bases (a, c, e) are composed primarily of carbonaceous and silica grains compacted in place, although rare uncompacted grains are also present. Tops
are less compacted (b, d). Compacted grains are typically optically lighter than uncompacted grains, either because CM was concentrated during
compaction, grains silicified prior to burial resisted compaction, or both. Less compacted tops in rhythmic layers such as these strongly suggest
silicification by interaction with overlying marine fluids. Scale bar is 1 mm. From 89.5 m in section (Fig. 4).
288 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Table 2
Unnormalized bulk elemental compositions and carbon compositions of dark bands

TSA5-1 TSA5-3 TSA5-7 TSA5- TSA5- TSA5- TSA5-4 SAF475- SAF475- TSA5-9 TSA5- TSA5- TSA5- TSA5- TSA5- TSA5- TSA5-
13 17 20 11 12 18 11 34 29b 29r 32 35

SiO2 95.76 96.48 96.57 97.47 96.83 45.56 98.79 98.51 98.76 98.67 97.33 92.34 87.22 97.69 76.42 98.78 98.58
Al2O3 2.22 0.98 0.20 0.26 0.20 0.22 0.17 0.48 0.32 0.15 0.19 0.19 0.17 0.18 0.15 0.16 0.13
TiO2 0.076 0.035 0.001 0.005 0.000 0.001 0.000 0.006 0.006 0.000 0.000 0.004 0.000 0.000 0.000 0.000 0.000
FeO⁎ 0.288 0.820 0.037 0.072 1.048 49.247 0.051 0.389 0.250 0.043 1.889 6.044 9.962 0.661 18.377 0.175 0.086
MnO 0.000 0.006 0.000 0.001 0.009 0.083 0.000 0.004 0.003 0.000 0.049 0.132 0.663 0.038 0.804 0.004 0.001
CaO 0.05 0.04 0.02 0.04 0.03 0.06 0.01 0.01 0.00 0.00 0.01 0.00 0.01 0.01 0.04 0.01 0.00
MgO 0.06 0.17 0.00 0.02 0.04 0.05 0.00 0.06 0.05 0.01 0.03 0.04 0.19 0.15 0.73 0.00 0.00
K2O 0.61 0.07 0.02 0.02 0.01 0.01 0.02 0.04 0.02 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01
Na2O 0.03 0.00 0.00 0.00 0.02 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
P2O5 0.010 0.007 0.005 0.007 0.008 0.022 0.003 0.003 0.004 0.003 0.004 0.011 0.007 0.002 0.047 0.006 0.005
Ni 10 75 17 10 10 69 19 35 19 12 54 43 67 13 32 13 11
Cr 23 20 0 3 2 4 0 10 3 0 2 17 22 0 38 0 0
Sc 3 1 6 2 9 2 2 3 0 5 6 4 5 8 6 4 2
V 5 4 0 0 0 0 0 9 0 0 0 12 7 0 0 9 0
Ba 92 9 6 0 15 0 13 17 6 25 7 9 2 8 6 7 3
Rb 17 3 2 2 2 0 3 2 3 1 1 2 0 1 0 1 1
Sr 4 4 2 3 3 5 2 4 3 4 3 6 6 2 7 1 2
Zr 21 10 4 4 3 13 5 7 5 4 5 7 7 4 7 4 4
Y 3 4 2 4 11 17 1 3 2 1 8 4 4 2 7 6 7
Nb 2.6 0.8 2 0.3 1 3.8 1.3 2.5 1.7 2.2 2 2.8 2.9 3.4 3 3.7 1.7
Ga 2 2 1 0 1 4 2 4 0 0 2 2 1 0 3 3 0
Cu 5 17 3 1 3 44 0 12 5 2 3 7 6 0 12 2 0
Zn 3 4 0 1 4 19 3 88 1 0 0 0 7 0 8 0 0
TOC 0.12 0.44 0.11 0.16 0.11 n.d.† 0.09 0.19 0.16 0.07 0.17 0.19 0.34 0.05 0.27 0.07 0.03
δ13CCM −30.61 −35.87 −36.87 −34.21 −20.05 n.d. −31.83 −32.73 −32.12 −30.90 −29.90 −27.32 −25.73 −28.13 −23.24 −28.37 −28.51

Units are wt.% (oxides and TOC), ppm (Ni–Zn), and per mil (δ13CCM).
*
Iron abundances are reported as equivalents of FeO.
†n.d. = not determined.

The association of Klb laminations with poorly complex carbonaceous grains, simple carbonaceous
sorted, hydraulically fine grains (e.g. Fig. 26) suggests grains, silica grains, and ferruginous grains. Terrigenous
deposition in very low-energy environments. The fact and volcaniclastic grains are absent. Less common
that these laminations do not modify topography, in uncompacted carbonaceous grains are fine to very fine
contrast to Klm and Kn mats, may reflect construction and simple in shape. Some samples contain abundant
by different organisms, e.g. by coccoids rather than ferruginous grains.
filaments or by non-phototactic microbes, but could also Layers are thin, b 3–5 mm, and almost everywhere
be an effect of growth of the same microbes under lack post-depositional soft-sediment disturbance. While
lower-energy conditions. most carbonaceous grains are compacted, many layers
A matrix-supported base for a detrital layer above a have uncompacted tops (Fig. 27) and a few uncom-
set of Klm laminations (Fig. 25) implies either that pacted particles scattered among more compacted
there was a fine particulate silica phase present at the grains.
time of deposition of that layer, possibly like on the Microfacies IV is most common in the upper black-
floors of modern Yellowstone hot springs (Lowe and and-white banded chert facies (Fig. 24), and is only a
Braunstein, 2003), or that carbonaceous grains were minor component of the lower black-and-white banded
generally coated by thin coatings of silica. Periodic chert facies.
deposition of layers of a fine particulate silica phase
may account for thin silica layers in Klm and Klb 2.6.5.2. Interpretation. As in the microfacies III
laminations. environment there is no evidence for wave or current
activity during deposition of microfacies IV. Current
2.6.5. Microfacies IV structures and scour are absent. Deposition was out of
suspension, but in an even lower-energy setting than
2.6.5.1. Description. Microfacies IV is an association microfacies III subject to essentially no wave or current
of compacted carbonaceous matter, silica grains, and activity. Sedimentation of carbonaceous grains, silica
variable amounts of ferruginous grains. Typical assem- grains, and siderite was most likely by hemipelagic
blages contain abundant Kgf carbonaceous grains, Klf settling. There is no evidence for the growth of in situ
laminations, and Klr network and a low proportion of microbial mats.
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 289

TSA5-8 TSA5-2 TSA5- TSA12- TSA12- TSA12- TSA12- TSA12- TSA12- TSA12- SAF491- TSA12- TSA12- TSA5- TSA12- SAF131- BRCd TSA12-
10 16 6 7 15 17b 17s 10 1 13r 8 23 13b 5 1

99.48 96.65 98.82 86.93 98.41 99.64 97.56 99.19 92.71 99.52 62.31 92.32 95.82 41.54 98.35 96.48 62.81 87.06
0.14 1.36 0.21 0.25 0.89 0.17 0.24 0.23 0.38 0.22 0.21 0.19 0.18 0.19 0.12 0.15 0.35 9.12
0.000 0.065 0.000 0.002 0.027 0.004 0.004 0.005 0.001 0.000 0.000 0.007 0.000 0.000 0.003 0.004 0.000 0.237
0.020 1.176 0.041 10.840 0.191 0.120 1.339 0.224 5.835 0.034 33.155 6.188 3.626 55.509 1.378 2.736 34.253 0.351
0.000 0.007 0.000 0.407 0.003 0.000 0.085 0.011 0.133 0.000 0.530 0.017 0.013 0.087 0.003 0.015 0.204 0.000
0.00 0.01 0.00 0.06 0.04 0.03 0.02 0.01 0.01 0.02 0.03 0.03 0.02 0.04 0.01 0.04 0.00 0.01
0.00 0.17 0.00 0.18 0.10 0.06 0.11 0.05 0.10 0.05 0.04 0.06 0.07 0.06 0.07 0.10 0.17 0.35
0.01 0.02 0.01 0.02 0.21 0.03 0.04 0.04 0.05 0.06 0.04 0.03 0.01 0.02 0.02 0.02 0.04 2.77
0.00 0.00 0.00 0.06 0.07 0.05 0.05 0.05 0.06 0.05 0.01 0.06 0.05 0.04 0.05 0.07 0.05 0.09
0.004 0.003 0.003 0.006 0.009 0.003 0.002 0.002 0.002 0.001 0.477 0.008 0.010 0.057 0.004 0.008 0.020 0.028
11 47 18 22 14 12 17 11 21 6 73 9 10 93 11 17 61 9
0 61 0 26 43 6 6 14 33 0 66 16 8 93 2 2 69 12
3 4 0 1 2 1 0 4 1 3 5 0 2 4 0 2 4 0
0 10 0 1 12 0 0 8 2 0 1 4 1 8 0 0 3 21
12 3 7 14 56 15 30 33 14 15 11 10 6 0 8 8 2 516
2 1 2 1 5 2 2 2 1 3 0 2 0 0 1 2 0 56
4 4 5 4 4 5 4 2 7 3 5 2 3 7 3 5 4 19
4 17 5 6 10 5 5 5 5 3 10 6 5 15 5 3 13 70
2 4 2 1 1 2 21 2 3 1 28 3 3 20 3 2 9 10
3.8 2.8 1 1.7 0.5 0.8 0.8 0.9 1.3 0.7 2.7 1.8 0.4 4.7 1.7 1.2 2.9 6.3
0 1 3 1 2 0 1 1 3 0 4 2 0 6 2 1 3 9
1 23 4 47 22 22 15 21 24 18 55 30 22 105 13 31 76 32
0 2 0 29 14 11 10 13 19 12 91 20 14 79 13 20 61 18
0.18 0.31 0.09 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
−27.07 −31.94 −32.59 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Silicification of carbonaceous layers was not as early in Layers are very thin, b 1–2 mm, and contain variable
microfacies IV sediments as in those of microfacies I, II, amounts of carbonaceous matter that is typically
or III. Uncompacted grains are intermixed with com- compacted.
pacted grains throughout microfacies IV layers, most Because all banded ferruginous chert (BFC) samples
likely indicating that carbonaceous grains were already in were extensively weathered, none was point-counted.
various stages of silicification prior to deposition or that However, relatively unweathered enclaves in a few BFC
they exhibited varying resistance to compaction before samples preserve grain assemblages composed predom-
silicification. This inference is consistent with the inantly of tightly packed KF grains, suggesting that
observation that uncompacted grains typically appear banded ferruginous chert was originally composed of
less optically dense, although apparent density variations microfacies V.
could also result from varying degrees of compaction. The Microfacies V sediments are most common in the
sediment source was probably composed of heteroge- upper black-and-white banded chert facies and the
neously silicified carbonaceous material. In many cases, banded ferruginous chert facies (Fig. 24).
uncompacted grains are particularly concentrated near the
tops of layers, and compacted grains are rare. Silicifica- 2.6.6.2. Interpretation. While some euhedral rhombic
tion thus appears to have preferentially preserved the tops siderite is likely to have formed diagenetically, the
of thin layers against compaction, a pattern of diagenesis abundance of siderite inferred for the original microfacies
strongly suggesting rapid cementation of the uppermost V sediments suggests that it was a major primary sediment.
few millimeters of layers and the overlying water column Although siderite is present in composite grains with
as the source of dissolved silica. carbonaceous matter, it is widely developed in layers and
lenses lacking CM. It is thus unlikely to have formed by
2.6.6. Microfacies V reduction of iron oxyhydroxides. Siderite in this micro-
facies is thought to have precipitated in the water column.
2.6.6.1. Description. Microfacies V (banded ferrugi- The detrital population in microfacies V is composed
nous chert) is characterized by a greater abundance of of extremely fine, hydraulically light grains and
siderite grains (Crh and Cp) and siderite/carbonaceous precipitative mineral grains. Sedimentation was domi-
matter aggregates (KF) than any other grain types. Some nated by hemipelagic settling of very fine siderite and
samples contain a small amount of simple carbonaceous carbonaceous grains. Silicification was slow relative to
grains. Terrigenous and volcaniclastic grains are absent. compaction.
290 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

2.7. Clastic-derived elements (Al2O3, Zr, TiO2, Cr) carbonaceous and siliceous sediment. Decreased abun-
dances of Al2O3, Zr, TiO2, and Cr within the lower and
2.7.1. Description upper black-and-white banded chert facies relative to the
While bulk compositions of rocks from throughout evaporitic facies reflect, in part, negligible mixing of
the Barberton greenstone belt have been severely altered terrigenous and volcaniclastic detritus into the shallow
by metasomatism, relative abundances of comparatively and deep shelfal environments, most likely due to
immobile elements have frequently been preserved erosion, subsidence, and submergence of the underlying
(Duchac and Hanor, 1987; Hanor and Duchac, 1990; volcanic complex.
Lahaye et al., 1995; Byerly, 1999; Lowe, 1999). Zr is typically enriched relative to the other immobile
Relative ratios of Al2O3, Zr, TiO2, and Cr, in particular, elements in the lower and upper black-and-white banded
have proven useful for identifying the original composi- chert facies and in the banded ferruginous chert facies,
tions of highly silicified ashes (Lowe, 1999). with Zr/Al2O3 ratios generally greater than those found
In the area of the Buck Reef Chert studied, Al2O3, Zr, in any primary source rock, including felsic volcanic
Cr, and TiO2 abundances (Table 2) vary systematically and volcaniclastic rocks. Similar Zr enrichment is
with lithofacies and section height (Fig. 24). Abun- observed in loess deposits due to concentration of
dances are moderate in the evaporitic facies, decreasing zircons along with other heavy minerals during aeolian
upward into the lower black-and-white banded chert transport (Taylor et al., 1983; Gallet et al., 1998;
facies. Abundances are lowest in the lower and upper McLennan, 2001). High Zr/Al2O3 in Black Sea
black-and-white banded chert facies, with Zr and Cr sediments has been used to infer relative input of
becoming slightly more concentrated toward the top of windblown silt (Martinez-Ruiz et al., 2000). Zr/Al2O3
the upper black-and-white banded chert facies. While greater than about 20 in BRC cherts thus most likely
Al2O3 and TiO2 abundances remain low in the banded reflects a primarily windblown source of clastic
ferruginous chert facies, Cr and Zr are present in levels sediment. Rare cherts in lower and upper black-and-
that approach or even exceed those of the evaporitic white banded chert facies and in the banded ferruginous
facies. TiO2 levels are below detection limits in nearly chert facies with Cr/Zr greater than about 2 contain
all samples except those from the evaporitic facies. windblown sediment derived from a source terrain with
Ratios of Al2O3, Zr, and Cr also vary systematically at least some komatiitic component.
with lithofacies and section height (Fig. 24). Evaporitic Enrichment of Zr and Cr in the banded ferrugi-
facies cherts have compositions similar to that of dacite nous chert facies is best explained by concentration
or dacitic ash, although some have komatiitic ash of windblown sediment in slowly deposited basi-
affinities. Zr/Al2O3 ratios are 9–15, and increase upward nal sediments. A slow rate of deposition is consis-
into the platform facies. Cr/Zr ratios are 1–4. Platform tent with evidence for sedimentation by hemipelagic
and transitional facies cherts have compositions similar settling of very fine material in microfacies IV and V.
to dacite, but enriched in Zr. A few cherts have slight
komatiitic affinities. Zr/Al2O3 ratios are 15–45. Cr/Zr 2.8. Heavy Metals (FeO⁎, Cu, Zn, Ni)
ratios are generally 0–0.6, with isolated examples as
high as 5.4. Basin facies cherts are most enriched in Zr 2.8.1. Description
and Cr, with Zr/Al2O3 ratios between 35 and 80 and Cr/ No attempt was made to chemically determine
Zr between 0.3 and 6.2. relative amounts of FeO and Fe2O3 in this study, so all
iron abundances are reported as equivalents of FeO
2.7.2. Interpretation (FeO⁎). Nearly every chert examined for this study has
The similarity in immobile element ratios between measurable abundances of FeO⁎, Cu, Zn, and Ni (Table
evaporitic facies cherts and dacite and dacitic ash is 2). Abundances vary systematically between lithofacies
consistent with the presence of volcaniclastic and and with section height (Fig. 24). Abundances are
terrigenous material visible in samples from that facies. moderate in the evaporitic facies (0.2 b FeO⁎ b 1.2 wt.%;
The overall upward decreasing abundances of Al2O3, 5 b Cu b 25 ppm; 2 b Zn b 90 ppm; 10 b Ni b 80 ppm), low
Zr, TiO2, and Cr in this facies reflect the upward in the lower black-and-white banded chert facies and
decreasing content of terrigenous clastic and volcani- most of the upper black-and-white banded chert facies
clastic material. Immobile element abundances within (0.03 b FeO⁎ b 0.3 wt.%; 0 b Cu b 5 ppm; 0 b Zn b 3 ppm;
the evaporitic facies thus reflect mixing of volcaniclastic 10 b Ni b 20 ppm), and high in the banded ferruginous
detritus derived from the coastal system represented by chert facies (0.2 b FeO⁎ b 60; 0 b Cu b 110; 0 b Zn b
the underlying felsic sands of H6 into locally-produced 80 ppm; 10 b Ni b 100 ppm).
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 291

2.8.2. Interpretation In nearly every case, regressions for the Zr/Al2O3 b 20


Broadly, heavy metal distributions within the BRC group of samples, which contain moderate clastic
are similar to those of the clastic-derived immobile material, yielded no significant correlations (P N 5% for
elements, especially Zr and Cr. This observation t-tests on regression coefficients). The only exception is
suggests a statistical test for correlations between a marginally significant relationship between Cu and
metal and clastic abundances. However, simple regres- ΔCr (Fig. 29). However, because no significant
sion of metal abundance against Zr and Cr abundance relationship was detected between Cu and Zr, and
does not suffice to explore the relationship between because a correlation with Cr would be detected in this
metals and clastics since Cr is highly correlated with Zr case by a correlation with both Zr and ΔCr, this
(P = 9 × 10 − 6 for the regression coefficient). This correlation is likely to be coincidental. These results
relationship tends to mask significant correlations for samples with Zr/Al2O3 b 20 could suggest that there
between abundances of either clastic element and the was no direct relationship between clastic sedimentation
abundance of any other element. Moreover, clastic and deposition of metals in the BRC, i.e. that Fe, Cu, Ni,
elements in the upper BRC derive from a windblown, and Zn were not primarily deposited as constituents of
zircon-enriched source while those in the lower BRC dacitic or komatiitic material, or they could suggest that
derive from varying mixes of dacitic volcaniclastic at least two materials with very different metal/Zr ratios
material and komatiitic ash. were mixed to varying degrees. For instance, felsic rocks
For these reasons, cherts were divided into two typically have FeO/Zr ratios of about 0.01 wt.%/ppm,
groups, one with Zr/Al2O3 b 20 and one with Zr/ whereas ultramafic rocks have ratios of about 0.5 wt.%/
Al2O3 ≥ 20. For each group, Cr was regressed against ppm (Lodders and Fegley, 1998). The second possibility
Zr and the resulting regression relationship was used to gains support from petrographic observations of both
calculate a new quantity, ΔCr = Cr − Cr⁎(Zr), where dacitic and basaltic-to-komatiitic material in evaporitic
Cr⁎(Zr) is the Cr abundance predicted by the Zr facies rocks, and from the fact that nearly all samples
abundance. By definition, ΔCr is not correlated with from the Zr/Al2O3 b 20 group have metal abundances
Zr, making it a suitable substitute for Cr in multiple within the range for terrestrial materials with equal Zr
regressions. For each group, metal abundances were abundances (Figs. 28−31). It seems likely, therefore, that
regressed against Zr and ΔCr (Figs. 28−31). in BRC rocks containing a significant component of

Fig. 28. Metal/clastic correlations: FeO*. Results of t-tests for significance of coefficients in multiple regression of FeO* on Zr and ΔCr are indicated
in each panel. Dashed lines show range of expected FeO* if supplied by terrigenous material using ultramafic and granite compositions from Lodders
and Fegley (1998).
292 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

Fig. 29. Metal/clastic correlations: Cu. Results of t-tests for significance of coefficients in multiple regression of Cu on Zr and ΔCr are indicated in
each panel. Dashed lines show range of expected Cu if supplied by terrigenous material using ultramafic and granite compositions from Lodders and
Fegley (1998).

terrigenous or volcaniclastic material, the metals Fe, Cu, levels all b7 × 10− 6. It is not as clear if any significant
Ni, and Zn also have a clastic source. relationships exist with ΔCr, however. Both Cu and Zn
In contrast, regressions in the Zr/Al2O3 ≥ 20 group exhibit statistically significant correlations with ΔCr,
yield highly significant correlations. Correlations of all and plots of FeO⁎ and Ni vs. ΔCr seem to suggest a
metals with Zr are particularly strong, with confidence significant relationship if only one sample with

Fig. 30. Metal/clastic correlations: Ni. Results of t-tests for significance of coefficients in multiple regression of Ni on Zr and ΔCr are indicated in
each panel. Dashed lines show range of expected Ni if supplied by terrigenous material using ultramafic and granite compositions from Lodders and
Fegley (1998).
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 293

Fig. 31. Metal/clastic correlations: Zn. Results of t-tests for significance of coefficients in multiple regression of Zn on Zr and ΔCr are indicated in
each panel. Dashed lines show range of expected Zn if supplied by terrigenous material using ultramafic and granite compositions from Lodders and
Fegley (1998).

anomalously low ΔCr (TSA5-20) is excluded. To test dances would be highest in proximal vent deposits least
this possibility, the regression analysis was repeated enriched in windblown dust and lowest in background
without including data from TSA5-20 (results not marine deposits most enriched in windblown dust, and
illustrated here). After this exclusion, a significant an inverse correlation between metal and clastic abun-
relationship was detected between FeO⁎ and ΔCr dances would be observed. Metal enrichment is therefore
(P = 5 × 10− 4), but the apparent correlations for Cu and not an indicator of a hydrothermal origin for the BRC.
Zn were no longer significant (P = 0.10 and 0.18, Instead, metal enrichments are likely to reflect a
respectively). The most likely explanation for the background “rain” of precipitated minerals in an early
sensitive dependence of these apparent correlations on metal-rich ocean. If average surface temperatures were
the inclusion of one sample is that none of the metals is 70 ± 15 °C (Knauth and Lowe, 2003) and the early
directly related to Cr, but rather to an underlying Earth's surface was anoxic (e.g. Rasmussen and Buick,
variable correlated with both Zr and Cr. 1999; Canfield et al., 2000), then hydrothermally-
What is the underlying variable controlling metal derived metals would have been substantially more
abundances? In the group of samples for which mobile than in the modern oceans. In this case, the
significant correlation exists between metal and clasti- primary process removing metals from the ocean would
cally-derived element abundances, Zr/Al2O3 is greater have been precipitation of metal sulfides and carbonates.
than 20 implying that windblown dust is the primary This conclusion is consistent with suggestions that
source of Zr and Cr. Assuming a relatively constant rate positive europium anomalies in Archean chemical
of supply of windblown material, high Zr and Cr sediments reflect an early ocean composition controlled
abundances in these rocks correspond to concentration by high-temperature hydrothermal inputs (e.g. Derry
of dust in slowly deposited sediments; Zr and Cr would and Jacobsen, 1990; Kamber and Webb, 2001; Tice and
thus correlate inversely with overall sedimentation rate. Lowe, 2006).
The correlation of metal abundances with Zr would then
imply that metals were also concentrated in slowly 2.9. Carbonaceous matter abundance and isotopic
deposited sediments. composition
Concentration of metals in slowly deposited sedi-
ments is not consistent with a proximal hydrothermal 2.9.1. Description
source of metals. Indeed, if the BRC represented the CM preserved in the evaporitic and lower black-and-
exhalative deposits of a hydrothermal vent, metal abun- white banded chert facies (Table 2) has a mean carbon
294 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

isotopic composition of − 31.9 ± 2.9‰ (S.D.) relative to Deep-water sediments contain elevated levels of
PDB, while CM preserved in the upper black-and-white windblown dust as indicated by high bulk Zr/Al2O3,
banded chert and banded ferruginous chert facies is reflecting slow sedimentation and silicification rates
isotopically heavier with a mean composition of − 27.2 ± which would have resulted in slow burial of deposited
4.3‰ (Fig. 24). Total CM abundance is highest in the material. δ13CCM is positively correlated with Zr/Al2O3
evaporitic and upper black-and-white banded chert (Fig. 32), suggesting that organic matter was preferen-
facies and lowest in the lower black-and-white banded tially 13C-enriched in slowly buried sediments. This
chert and banded ferruginous chert facies (Fig. 24). relationship between δ13CCM and sedimentation rate
reinforces the conclusion that variations in δ13CCM were
2.9.2. Interpretation set before deep burial. The combination of greater trans-
13
C enrichment in organic matter deposited in deep- port distance and lower burial rates in the basin setting
water settings could be explained by primary isotopic would have subjected deep-water organic matter to
compositions that varied between environments, pref- longer periods of near-surface biological degradation
erential metamorphic alteration of carbonaceous matter than material deposited in shallow water. The magnitude
in basin facies rocks, or diagenetic, possibly microbial, of enrichment in 13C associated with slow burial indi-
alteration of carbonaceous matter deposited in different cates preferential loss of 12C, probably by generation of
settings. methane by methanogenesis. Typical biogenic metha-
CM in upper black-and-white banded chert and nogenesis today results in kinetic fractionation effects
banded ferruginous chert facies rocks is present as leading to methane δ13C values as much as 20–25‰
detrital grains that have undergone varying degrees of depleted relative to source acetate (Gelwicks et al.,
compaction. Carbonaceous grains become simpler in 1994). Methane loss by a combination of fermentation
morphology and finer in size with the transition from and methanogenesis would leave substantially less
shallow platform settings to deep platform and basin depleted residual simple organics such as acetate (Blair
settings, suggesting that deep-water carbonaceous and Carter, 1992). Loss of methane would proceed until
matter is detrital in origin and had a shallow water the sediment was silicified, drastically reducing perme-
source. It is therefore likely that all BRC carbonaceous ability and effectively producing a closed isotopic
matter had the same initial isotopic composition. system.
Although carbon loss during metamorphism tends to Some sulfate reducers produce biomass similarly less
preferentially remove 12C (McKirdy and Powell, 1974; depleted relative to substrate composition in closed
Des Marais et al., 1992), differential heating is unlikely systems (Londry and Des Marais, 2003), but the lack of
to have produced the variation observed here. One of the abundant pyrite, even in iron-rich deep-water sediments
most 13C-depleted samples (− 35.9‰) from the base of where fractionation is most extreme, suggests that
the section is located next to an igneous intrusion. The sulfate reduction was not significant.
isotopic composition of carbonaceous matter (δ13CCM)
does not correlate with distance from intrusive dikes and
sills. Partial equilibration with isotopically heavy siderite
during metamorphism would have resulted in correlation
between δ13CCM and iron abundance or iron-to-organic
carbon ratio independent of depositional setting. Instead,
δ13CCM does not correlate with either parameter in upper
black-and-white banded chert or banded ferruginous
chert facies rocks (P = 27.1% and 22.8%, respectively)
although iron abundance varies over nearly the same
range as in the BRC as a whole. Similar shallow- to deep-
water 13C enrichments in carbonaceous matter have been
observed in 2.5–2.3-Gyr-old sequences (Beukes et al.,
1990). Such trends are unlikely to be explained by
preferential metamorphic isotopic resetting of rocks
deposited under deep water. Instead, 13C enrichment in
deep-water carbonaceous matter most likely reflects
differences in composition prior to deep burial and Fig. 32. Correlation of CM isotopic composition and Zr/Al2O3.
metamorphism. δ13CCM is positively correlated with Zr/Al2O3 (P = 0.02).
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 295

2.10. Discussion of Buck Reef Chert results Klm or Kn microbial mats. The only non-detrital
carbonaceous structures observed were laminations
2.10.1. Depositional environments and networks representing microbial mats, suggesting
Sedimentary structures in the evaporitic facies and that most BRC CM was ultimately derived by current,
grain associations and layering styles in the microfacies I wave, and storm erosion of shallow-water benthic
and II sediments that compose it are consistent with microbial communities.
deposition in shallow coastal lagoons dominated by
wetting and drying cycles and periodic storms as 2.10.2. Causes of silicification
suggested by Lowe and Fisher Worrell (1999). Shallow Multiple generations of silica are evident in the BRC,
waves and occasional storms ripped up local microbial ranging from early white bands that lithified near the
mats and repeatedly reworked the sediment surface, sediment surface to late cross-cutting quartz veins.
preventing formation of complex carbonaceous grains or Several lines of evidence suggest that the earliest
chert banding. Instead, black cherts were deposited generations of silica precipitated from normal marine
consisting of mixtures of clastic material and simple water (Lowe, 1999; Knauth and Lowe, 2003) rather than
carbonaceous grains (microfacies I), or simple carbona- hydrothermal fluids (de Wit et al., 1982; Paris et al.,
ceous grains, evaporitic, and silica grains (microfacies 1985; Brasier et al., 2002). (1) Silicification in the BRC
II). White silica laminations developed in wave ripples occurred in sediments deposited along at least 50 km of
appear to represent silica grains and possibly evaporitic strike, and in marine environments ranging from
grains hydraulically separated from carbonaceous shallow-water evaporating ponds to a quiet, deep-water
matter. basin. Such persistence in space and depositional
Pervasive soft-sediment deformation and the abun- environment is unlikely for a hydrothermal system. (2)
dance of microfacies II and III sediments in the lower In shallow water, silicification occurred at extremely
black-and-white banded chert facies suggests deposition shallow sediment depths and may have been syndeposi-
under the influence of weak waves or currents. The tional. Regionally uniform silicification of shallow
unit's wide extent, abundance of hydraulically fine sediments by fluids flowing up through or along already
detrital grains, and absence of coarser particles and high- silicified sediments is unlikely. (3) In sediments
energy current structures indicate deposition on an open deposited at intermediate depths, probably ∼ 200 m,
marine, wave- and current-active shelf. Disruption of thinly stacked layers are silicified preferentially along
partially consolidated sediment by weak waves and their tops (Fig. 27). This pattern indicates that fluids
currents and by periodic storms allowed formation of physically above the sediment surface were the source of
abundant complex carbonaceous grains, but was not so dissolved silica rather than fluids seeping up through the
frequent that microbial mats could not be preserved in- sediment column. (4) No preserved vent stocks or
place (microfacies III). There is probably a widespread mounds have been identified in the BRC; in fact, no large
unconformity between the evaporite facies and this cross-cutting silica-rich features have been identified.
shelfal facies that would represent shallower shelf and No facies relationships in the BRC suggest the existence
shoreface settings. These areas had little or no coarse of local vent mounds or breccias. (5) Most of the BRC,
volcaniclastic sediments available and were subject to which has an age of b3416 ± 5 Ma (Kröner et al., 1991),
current and wave activity that eroded and removed any was deposited nearly 30 million years after emplacement
CM deposited here between high-energy events. and eruption of the underlying felsic volcanic complex,
The rarity of soft-sediment disruption and brecciation which has an age of 3445 ± 3 Ma (Kröner et al., 1991).
and abundance of microfacies IV and V sedimentation in While that event was associated with wide scale
the laminated black-and-white banded chert facies tonalite–trondhjemite–granodiorite intrusion that drove
reflect subsidence of the volcanic platform to a depth regional hydrothermal activity (Knauth and Lowe, 2003;
near or below storm wave base. Waves, currents, and Tice et al., 2004), there was no clear heat source available
larger-scale storm activity that affected the bottom were during BRC time to drive widespread hydrothermal fluid
infrequent. This facies represents a transitional environ- flow. The BRC is singularly lacking in volcanic or
ment between the underlying moderate-energy platform volcaniclastic components. (6) Metals were concentrated
facies and the overlying no-energy banded ferruginous in sediments which also concentrated windblown dust,
chert facies. i.e. those likely to have been deposited most slowly.
Virtually all CM appears to have formed originally This pattern of accumulation is inconsistent with a
within benthic microbial mats. Many complex carbo- hydrothermal metal source and most consistent with a
naceous grains preserve structures reflecting origins as normal marine setting. (7) Rare earth element (REE)
296 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

distributions in BRC rocks display a nearly constant Another very early generation of silica formed
heavy REE enrichment and slight positive europium isopachous rims around carbonaceous grains within
anomaly regardless of depositional environment (Tice the sediment column (Fig. 33). This generation is most
and Lowe, 2006). This constancy is inconsistent with extensively developed in microfacies III shallow
mixing between marine and locally-derived hydrother- platform sediments, and was probably responsible for
mal fluids. preserving equant complex carbonaceous grains against
The first generation of silica to form in the BRC was compaction. Conversely, its absence in sediments
most likely particulate silica sediment which mixed with formed below storm wave base allowed significant
detrital carbonaceous grains to form mixed carbona- compaction of CM in deep-water settings. Its formation
ceous/siliceous oozes, such as the partially matrix- probably reflects both high silica concentration in the
supported detrital layer in Fig. 25. As in modern overlying water column and the likely high permeability
Yellowstone hot springs (Lowe and Braunstein, 2003), of relatively coarse microfacies III sediments. Subse-
this silica probably precipitated directly from the water quent generations of silica filled remaining open pore
column. In this case, however, there was no evident local space in shallow-water sediments and prevented further
source of supersaturated dissolved silica other than compaction in deep-water sediments.
seawater. It is possible that supersaturation was enhanced
by evaporation in lagoons and shallow platform settings. 2.10.3. Source of carbonaceous matter
Such enhancement would have persisted during intervals Mat-like laminations and networks are preserved in-
between storms, which would have tended to partially place almost exclusively in microfacies III sediments in
mix these slightly evaporitic masses with ambient the lower black-and-white banded chert facies deposited
seawater. in a shallow platform setting. The near absence of mats
One of the next generations of silica formed the in microfacies IV sediments of the upper black-and-
precursor for white chert bands, which exhibited both white banded chert facies deposited in a deep platform
plastic and brittle deformation when black band to basin setting, even in relatively uncompacted
precursor was still soft and fluid. Lowe (1999) makes enclaves, suggests that BRC mat-constructing commu-
two arguments for an early diagenetic separation of black nities were restricted to water depths b200 m. Restric-
and white bands in the Barberton greenstone belt that tion of these laminations to shallow water probably
apply directly to the BRC. (1) White bands throughout reflects confinement to the euphotic zone, which
the Barberton greenstone belt are uniformly less than generally corresponds to depths of b 150 m (Lalli and
about 15 cm thick. If white bands are depositional Parsons, 1997). While UV-polymerization of simple
features, it is highly unlikely that conditions necessary to organics may also have been able to form carbonaceous
form the thousands of white bands found in the BRC, features restricted to shallow-water environments,
across tens of kilometers of the ocean floor, would not radiation in much of the UV spectrum should have
have persisted long enough in some environment to form been rapidly attenuated in the uppermost 10–15 m of the
thicker deposits. (2) With the exception of chemical
precipitates such as siderite, white bands are pure chert.
However rapidly white band precursor could have been
deposited, it is unlikely that carbonaceous grains would
have never been mixed in. These arguments point
compellingly to an early diagenetic origin for most BRC
white bands, which may explain a further observation
specific to the BRC. While black and white bands in the
lower and upper black-and-white banded chert facies and
the banded ferruginous chert facies are subequal in
thickness, maximum band thickness decreases system-
atically from about 15 cm in the lower black-and-white
banded chert facies to about 1 cm in the banded
ferruginous chert facies. This thickness change could
reflect lower permeabilities in fine-grained, laminated
deep-water sediments than in coarse-grained shallow- Fig. 33. Isopachous silica coatings in carbonaceous sediment. These
water sediments, and a consequent shorter characteristic layers represent the earliest generations of silica in black bands. Scale
transport length for silica-depositing pore fluids. bar is 0.5 mm.
M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300 297

water column (Kappler et al., 2005). Thus, UV- sedimentation that was dominated by biological and
dependent processes are unlikely to account for features chemical processes. The result was the accumulation of
inferred to have been formed abundantly under water an enormous thickness of carbonaceous and ferruginous
depths 15–200 m. An ecological restriction is more chert. There is no evidence that deposition was
plausible, and the depth restriction is most consistent influenced by local hydrothermal systems.
with a biological origin. The lack of nearby hydrother- The morphology of carbonaceous matter varies
mal inputs precludes the high-temperature fluid/metal systematically with depositional environment. Carbona-
interactions commonly proposed for hydrothermal ceous grains and mats were generally weak and easily
abiotic formation of reduced carbon compounds eroded by even low-energy waves and currents. Mat
(Huber and Wächtershäuser, 1997; Horita and Berndt, growth was restricted to shallow-water environments,
1999). It is possible that methane haze formation in an probably the euphotic zone. This distribution and the
atmosphere with CH4/CO2 ∼ 1 has resulted in deposition carbon isotopic composition of −35‰ to −30‰ suggests
of abundant carbonaceous matter not directly related to photosynthetic fixation. Detrital carbonaceous grains
local biological carbon fixation later in Earth history formed by erosion of microbial mats were distributed
(Pavlov et al., 2001b). Such haze would have also throughout shallow- and deep-water environments.
resulted in a strong anti-greenhouse effect (Pavlov et al., Thus, a close field, petrographic, and geochemical
2001a), inconsistent with evidence that surface tem- investigation of perhaps the largest accumulation of
peratures during deposition of the BRC were high carbonaceous chert in the geologic record supports the
(Knauth and Lowe, 2003; Lowe and Tice, 2004). working hypothesis developed through a broad exam-
Evidence for a hot early Earth thus argues for an ination of the geological CM record: the bulk of CM in
atmosphere with CH4/CO2 ≪ 1 and against a haze the BRC and rocks older than 3.0 Ga was produced by
origin for BRC CM. living organisms. Ultimately the strength of this support
The isotopic carbon composition of bulk carbona- derives not from identification of microfossils, nor from
ceous matter associated with mats is − 35‰ to − 30‰ any single conclusive piece of evidence or “smoking
compared to PDB, consistent with fixation by organisms gun”, but from the degree to which the model proposed
employing the Calvin cycle (Schidlowski, 2000). here satisfactorily accounts for all CM in the BRC
Organisms with a variety of physiologies use this within the context of the rocks themselves. We suggest
pathway, including some types of oxygenic and that future studies focus more generally on all CM found
anoxygenic photosynthesizers, and many chemoauto- within ancient geological units subject to the constraint
trophs such as sulfide, iron, and hydrogen oxidizers of detailed paleoenvironmental reconstructions, and less
(Madigan et al., 1997). The absence of ferric oxides in on restrictive analyses of exceedingly rare features like
the platform facies implies that carbon was not fixed possible microfossils and stromatolites.
predominantly by iron oxidation. Sulfide and hydrogen
oxidation both require free O2. The presence of siderite Acknowledgments
and absence of ferric oxides and the lack of primary
cerium anomalies throughout the BRC suggests that the This research was supported by NASA Exobiology
partial pressure of O2 was very low (Tice and Lowe, Program grants NCC2-721, NAG5-9842, NAG5-
2006), making both of these metabolisms unlikely as 13442, and NNG04GM43G to DRL, and by grants to
primary carbon fixation pathways. The restriction of DRL from the UCLA Center for Astrobiology. MMT
mats to the euphotic zone, the isotopic composition of was also supported by a William R. and Sara Hart
BRC CM, and the widespread distribution of siderite Kimball Stanford Graduate Fellowship and by a Harvey
and lack of hematite together suggest that BRC mat Fellowship. The authors are grateful to the Mpumalanga
communities were photosynthetic and anoxygenic. Parks Board and especially Louis Loock (Regional
Manager), Johan Eksteen, and Mark Stalmans, for
3. Conclusions allowing access to the Songimvelo Game Reserve. We
would also like to thank Sappi Limited and J.M.L. van
The Buck Reef Chert was deposited under progres- Rensburg, Forestry Manager, for permission to access
sively increasing water depths in environments that private forest roads and many key areas during this
ranged from shallow coastal lagoons to an open marine study and Mr. Collin Willie for permission to access
wave- and storm-dominated platform to a deep basin. It outcrops on Farm Schoongezicht. This manuscript
was cut off from sources of terrigenous and volcani- benefited from comments by Martin Brasier and John
clastic sediment for most of its history, resulting in Hayes.
298 M.M. Tice, D.R. Lowe / Earth-Science Reviews 76 (2006) 259–300

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