Precambrian Research 177 (2010) 73–87

Contents lists available at ScienceDirect

Precambrian Research
journal homepage: www.elsevier.com/locate/precamres

A systematic rare-earth elements and yttrium study of Archean cherts at the

Mount Goldsworthy greenstone belt in the Pilbara Craton: Implications for the
origin of microfossil-bearing black cherts
Haruna Sugahara a , Kenichiro Sugitani a,∗ , Koichi Mimura a , Fumiaki Yamashita b,1 , Koshi Yamamoto a
a
Graduate School of Environmental Studies, Nagoya University, Chikusa-ku, Nagoya 464-8601, Japan
b
Graduate School of Sciences, Nagoya University, Nagoya 464-8601, Japan

a r t i c l e i n f o a b s t r a c t

Article history: A systematic REE + Y study of Archean (ca. 3.0 Ga) cherts from the Mount Goldsworthy greenstone belt in
Received 25 December 2008 the northeastern Pilbara Craton, Western Australia was performed in order to understand their origin and
Received in revised form 22 October 2009 depositional environment. Analyzed samples include microfossil-bearing black cherts from the Farrel
Accepted 26 October 2009
Quartzite and a black vein chert from the underlying Warrawoona Group, and laminated to banded
chert including carbonaceous chert, jaspilite and banded iron-formation from the overlying, deepening-
Keywords:
upward Cleaverville Formation.
Archean
Laminated to banded cherts from the Cleaverville Formation show a clear stratigraphic trend upsection
Microfossil-bearing black chert
Rare-earth elements
of increasing Y/Ho and positive Eu-anomalies, with HREE-enrichment and positive La-anomalies. The
Non-marine data comprise a mixing array between two end-member components on a newly proposed Y/Ho–Eu-
Continental setting anomaly diagram. One end-member is interpreted to be Archean seawater, with a super-chondritic Y/Ho
ratio (∼100) and a weak positive Eu-anomaly (∼3). The other end-member with a chondritic Y/Ho ratio
and a negligible Eu-anomaly is assumed to be non-marine water such as continental run-off, ground
water, or geothermal water.
Black cherts containing microfossils in the Farrel Quartzite are characterized by a positive La-anomaly,
HREE-enrichment, negligible to a slight positive Eu-anomaly, and a chondritic to slightly super-chondritic
Y/Ho ratio. They are distinct from vein cherts with a distinct MREE-enrichment and contemporaneous
hydrothermal cherts with pronounced Eu-anomaly, and plot close to the supposed non-marine end-
member component on the Y/Ho–Eu-anomaly diagram. The black cherts were thus precipitated from a
water mass influenced significantly by for example continental run-off, ground water and/or geothermal
water, but not from high-T hydrothermal solution, increasing the credibility of microfossils contained
in them.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction has now become nearly compelling, supported by the follow-

A morphologically diverse assemblage of biological structures
(threads, films, spheroids, and lens-spindles) has recently been
reported from sedimentary carbonaceous black cherts of the ca.
3.0 Ga Farrel Quartzite of the Mount Goldsworthy greenstone
belt in the Pilbara Craton, Western Australia (Sugitani et al.,
2007) (Fig. 1). Their biogenicity was claimed from indigenousness,
syngenecity, narrow size distribution, carbonaceous composition,
evidence of flexible but breakable walls, apparent taphonomic
features and the presence of colony-like aggregations (Sugitani
et al., 2007). The credibility of the structures as microfossils
∗ Corresponding author. Fax: +81 52 789 4865.
E-mail address: sugi@info.human.nagoya-u.ac.jp (K. Sugitani).
1
Present address: Shinto Tsushin Co., Ltd. Nagoya 460-0002, Japan.
ing studies on highly elaborate structures and their complex
occurrences suggestive of life cycle (Sugitani et al., 2009b), paly-
nological extraction of the structures (Grey and Sugitani, 2009),
NanoSIMS chemical analyses of individual structures (Oehler et
al., 2009) and 3D reconstruction of morphological and textural
complexity (Sugitani et al., 2009a). These microfossils are outstand-
ing for their morphological diversity and complexity, excellent
preservation of some specimens, and large size, which are dis-
tinct from many of previously reported Archean microfossils that
are generally small and simple in morphology (e.g., Knoll and
Barghoorn, 1977; Dunlop et al., 1978; Rasmussen, 2000; Westall
et al., 2001). Furthermore, an association between the host chert
and an evaporite bed, which can be traced ca. 7 km along the strike
(Sugitani et al., 2009b), implies that there was a diverse micro-
bial ecosystem flourishing in a shallow-water environment at ca.
3.0 Ga.

0301-9268/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.precamres.2009.10.005
74 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87

Fig. 1. Photomicrographs of representative specimens of putative microfossils discovered from Mount Grant. Scale bar: 20 ␮m (a); 100 ␮m (b); 200 ␮m (c). Positions of
microfossils in thin section are described using an England Finder. “R-” of R-Q40/3, for example, indicates that the thin section is set on the stage with its label on right. (a)
Colony-like cluster of semi-hollow spheroids showing deformation to various degrees. The cluster appears to be enveloped with fluffy material. Slide GFWE-E11, Position
R-Q40/3. (b) Colony-like cluster of lenticular to spindle-like structures. Slide GFWE-F4, Position R-J47/4. (c) Fragmented film-like structure, with attached small sphere and
cluster of opaque particles. Slide GFWE-F2. Position R-B52/3.

However, the origin of the black cherts, which would potentially
place constraints on the phylogeny of the putative microfossils, has
not yet been specified. Specifically, it is still equivocal whether
the cherts were non-marine or marine, or whether they were
hydrothermal or non-hydrothermal. In this study, we attempt to
answer these questions through systematic rare-earth element and
yttrium (REE + Y) analyses.
REE + Y have long been used as a proxy to determine the ori-
gin and depositional environment of fine-grained sediments and
sedimentary rocks, especially those of chemical and biogenic ori-
gins (e.g., Murray et al., 1991; Webb and Kamber, 2000; Shimizu
et al., 2001). Its application to Precambrian carbonates, banded
iron-formations (BIFs) and cherts have also provided important
information about the origins and evolution of surface envi-
ronments on the early Earth (e.g., Derry and Jacobsen, 1990;
Danielson et al., 1992; Alibert and McCulloch, 1993; Bau and
Möller, 1993; Bau and Dulski, 1996; Kato and Nakamura, 2003;
Van Kranendonk et al., 2003; Kamber et al., 2004; Yamamoto et
al., 2004; Bolhar et al., 2005; Hofmann, 2005; Bolhar and Van
Kranendonk, 2007; Frei et al., 2008). For example, Danielson et al.
(1992) suggested based on REE patterns of BIF of various ages and
localities that the dominant type of sea-floor alteration changed
from high-temperature to low-temperature during the Protero-
zoic. Van Kranendonk et al. (2003) reported REE + Y data of ca.
3.40 Ga Strelley Pool Chert stromatolitic carbonates and concluded
that they were deposited from anoxic Archean shallow seawa-
ter.
In this study, we present a systematic dataset of REE + Y
from cherts of various lithologies from the Mount Goldswor-
thy greenstone belt, with the aim of placing constraints on
the origin of the black cherts that contain microfossils. Com-
parison of the microfossil-bearing black cherts with other
lithologies, including ferruginous cherts (jaspilite) and banded
iron-formation, laminated black chert that does not contain
microfossils, and black vein chert should provide us with crit-
ical information about the water chemistry from which the
microfossil-bearing black cherts were precipitated and thus shed
light on the habitable environment of the early life in the study
area.
2. Geological background
2.1. General geology
The 3.72–2.83 Ga Pilbara Craton (Fig. 2a) has three lithotectoni-
cally different granite-greenstone terrains; the 3.53–3.165 Ga East
Pilbara Terrane (EPT), the >3.18 Ga Kurrana Terrane (KT), and the
West Pilbara Superterrane (WPS), which includes the 3.27 Ga Kar-
ratha Terrane, the ca. 3.20 Ga Regal Terrane, and the 3.13–3.11 Ga
Sholl Terrane (Van Kranendonk et al., 2007). The EPT represents
the ancient nucleus of the Pilbara Craton (Fig. 2b) and comprises
the Pilbara Supergroup of volcano-sedimentary rocks and several
generations of intrusive granitic rocks. The Pilbara Supergroup is
divided into five groups; the 3.52–3.42 Ga Warrawoona Group,
the 3.42–3.35 Ga Strelley Pool Formation, the 3.35–3.31 Ga Kelly
Group, the 3.27–3.23 Ga Sulphur Springs Group and the ca. 3.19 Ga
Soanesville Group. The Supergroup is overlain unconformably by
the 3.02 Ga Gorge Creek Group of the late-tectonic De Grey Super-
group (Van Kranendonk et al., 2007; Hickman, 2008).
2.2. Local geology, depositional environment
The Mount Goldsworthy greenstone belt of the Pilbara Craton,
which is composed of Mount Goldsworthy and Mount Grant, is
located approximately 100 km east of Port Hedland (Fig. 2b). The
stratigraphic succession of this greenstone belt less than 1 km thick
is composed of a lower, dominantly volcanic sequence of rocks
that is part of the 3.53–3.17 Ga Pilbara Supergroup, and an upper,
dominantly sedimentary succession that is part of the 3.02–2.93 Ga
De Grey Supergroup (Hickman and Van Kranendonk, 2008). The
3.02 Ga Gorge Creek Group, a lower part of the De Grey Super-
group, comprises a clastic formation, the Farrel Quartzite, and an
upper formation of chert, banded iron-formation, black shale, and
siltstone, the Cleaverville Formation.
The Farrel Quartzite in the Mount Goldsworthy greenstone
belt is composed of moderately metamorphosed (greenschist
facies), pervasively silicified, fine to very coarse-grained sandstone
including quartzite with minor conglomerate, mafic to ultra-
mafic volcaniclastic layers, evaporite beds and black chert layers.
 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87 75

Fig. 2. (a) Location of the Pilbara Craton. (b) Geology of the north-eastern Pilbara Craton (after Smithies et al., 2004 and Sugitani et al., 2007). (c) Geological map of the Mount
Goldsworthy greenstone belt (Mt. Grant-Mt. Goldsworthy area) (after Smithies et al., 2004; Van Kranendonk et al., 2006, 2007; Sugitani et al., 2007; Hickman, 2008; Hickman
and Van Kranendonk, 2008). The open circles show sampling locations for LC (laminated to banded chert from the Cleaverville Formation) and CE1 and 2 (startiform massive
black chert from the Farrel Quartzite), whereas the stars do for VC (vein chert from the Warrawoona Group). (d) Simplified stratigraphic column at Mt. Grant (left column)
and Mt. Goldsworthy (right column).
76 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87

Fig. 3. Photomicrographs of representative chert specimens. Scale bars: 200 ␮m (a and b); 500 ␮m (c and d); 1 mm (e and f). (a) LC from Mount Grant. Granular minerals
forming aggregates are carbonates (the arrow), whereas very fine dark particles that comprise laminae are carbonaceous matter. (b) Fine carbonaceous laminations in LC from
Mount Grant, probably subjected to post-depositional reworking. (c) VC containing abundant carbonaceous grains. (d) CE1 characterized by fine carbonaceous laminations
and detrital carbonaceous grains. (e) Botryoidal structure within CE2. (f) Fenestrae-like irregularly shaped pure chert masses in CE2. The arrow shows a huge film-like
structure.

Although the thickness of this clastic unit is laterally variable from
several meters to 80 m, two beds of evaporite that occur in the
quartzite at Mount Grant, particularly the upper one in CE2 (Fig. 2d),
are laterally continuous. This upper evaporite bed can be traced
ca. 7 km along strike in the central and the western part of Mount
Grant.
The Farrel Quartzite is conformably overlain by the Cleaverville
Formation, which dominantly consists of finely parallel-laminated
variegated chert, including dark-grey shale, carbonaceous black
chert, jaspilite and banded iron-formation, with minor coarse-
grained terrigenous clastic rocks near the base. The terrigenous
clastic rocks occur as beds and lenses, in some places with abundant
platy chert clasts.
Sugitani et al. (2003, 2006a) suggested that the Farrel Quartzite
was deposited in a continental margin setting and that terrige-
nous detrital materials may have been partially derived from
older continental crust. Silicified evaporites probably originated
from nahcolite (Na2 HCO3 ), suggesting the development of shal-
low to sub-aerial conditions. This shallow to sub-aerial depositional
environment of the Farrel Quartzite was followed by a deeper
subaqueous environment, in which finely and parallel-laminated
cherts and banded iron-formation of the Cleaverville Formation
were deposited. The higher abundance of sandstone beds and
lenses in the lower part of this horizon suggests that the formation
represents a deepening-upward sequence (Sugitani et al., 2003).
2.3. Black chert occurrences
Several different occurrences of black chert have been identi-
fied. Black chert veins are less than 30 cm thick, and locally occur in
the Warrawoona Group altered volcanic and volcaniclastic rocks
(Sugitani et al., 2006b). In the Farrel Quartzite, stratiform black
cherts are less than 30 cm thick and occur in close association with
evaporite beds at two stratigraphic levels (Fig. 2d). These associ-
ations were designated as CE1 for the lower horizon and CE2 for
the upper horizon at the top of the Farrel Quartzite, respectively
(Fig. 2d). A cm-scale black vein chert locally occurs within sand-
stone of the Farrel Quartzite. Evaporite is occasionally replaced by
black chert. Stratiform black cherts are common in the Cleaverville
Formation, intercalated with other variegated chert layers. To date,
the microfossils have been found only in the stratiform black chert
of CE2 (Sugitani et al., 2007).
 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87
3. Sample descriptions
Fifty-two chert samples were collected for analysis. We catego-
rized the samples into four lithological types, including; laminated
to banded chert (LC), vein chert (VC), and stratiform chert associ-
ated with evaporites (CE1 and CE2). LC samples (n = 29) are from the
Cleaverville Formation at Mount Goldsworthy (n = 20) and at Mount
Grant (n = 9). VC samples (n = 5) are all from altered mafic volcanic
rocks of the Warrawoona Group at Mount Grant. CE1 samples (n = 4)
are from one locality at Mount Grant. CE2 samples (n = 13) are
from Mount Grant (n = 10) and Mount Goldsworthy (n = 3). Detailed
descriptions of these chert lithologies are given below.
3.1. LC: laminated to banded chert
Laminated to banded chert from the Cleaverville Formation
is characterized by parallel lamination or banding. Lamination is
mostly planar to undulating and occasionally anastomosing. It con-
tains very fine particles of carbonaceous matter, hematite and/or
carbonate, in addition to predominant microcrystalline to granular
quartz in the matrix (Fig. 3a). Very fine carbonaceous lamination
occasionally displays reworked features such as overturning and
fragmentation (Fig. 3b). At Mount Goldsworthy, hematitic lami-
nae are predominant and locally Fe-rich beds equivalent to banded
iron-formation are present, whereas at Mount Grant laminae com-
posed of carbonaceous matter or carbonate are predominant within
the stratigraphic interval (∼90m) from which we collected samples.
3.2. VC: vein chert
Vein chert from the Warrawoona Group does not display lami-
nation or bedding. Very fine carbonaceous particles are distributed
homogeneously in some samples, whereas they comprise floccu-
lated grains in others (Fig. 3c). Relatively large quartz grains, lithic
fragments and mica are rare. This type of chert commonly contains
abundant tabular crystals of secondary origin, which are assumed
to be a tourmaline-group mineral, based on XRD analyses.
3.3. CE1 and CE2: stratiform chert
Stratiform black chert from CE1 is characterized by parallel to
slightly undulating laminations and locally has abundant detrital
carbonaceous grains (Fig. 3d). Stratiform black chert CE2, on the
other hand, is mostly massive, with local cross or parallel lamina-
tion. It also contains a cavity-fill white chert layer with botryoidal
structures (Fig. 3e). Abundant putative microfossils of various mor-
phologies (thread, film, spheroid, and spindle) are found within the
massive portion of this unit, with thread-like structure found also in
the cavity-fill chert. The massive portion of this chert is composed
of a microcrystalline quartz matrix with disseminated carbona-
ceous material, unknown acicular crystals, and sulphide. Rare barite
and carbonate are also present. Carbonaceous particles in the mas-
sive matrix tend to be distributed heterogeneously, resulting in
the development of irregularly shaped pure chert masses that are
morphologically similar to fenestrae (Fig. 3f).
4. Analytical methods
4.1. Major elements
Concentrations of selected major elements (TiO2 , Al2 O3 , Fe2 O3
and P2 O5 ) were determined by X-ray fluorescence spectrometer
(XRF) (PANalytical Axios), using fused-glass discs made from a mix-
ture of sample powder and Li2 B4 O7 in the proportion of 1:8.
77
4.2. Rare-earth elements and yttrium (REE + Y)
Analyses of REE + Y followed the method of Yamamoto et al.
(2004). Black chert samples (150–350 g) were coarsely crushed
with a jaw crusher. Small chips (5 mm in size) were handpicked to
exclude visible detrital laminae and weathered parts. After pulver-
izing with an agate mortar, HF and HClO4 (HF:HClO4 = 2:1) were
added to sample powders (3 g) for digestion. The sample solu-
tions were dried on a hot plate (180 ◦ C). The dried samples were
dissolved with 1.7N-HCl and supernatants were collected after
centrifugation. This procedure from digestion with mixed acids
(HF:HClO4 = 2:1) to collection of supernatants was repeated three
times for complete decomposition of samples. REE + Y in the super-
natants were separated using a cation exchange column in order
to remove interfering elements such as Ba (Hirata et al., 1988).
The collected REE + Y solutions were dried on a hot plate (180 ◦ C)
and then dissolved in 2% HNO3 . REE + Y concentrations were deter-
mined by inductively coupled plasma mass spectrometer (ICP-MS).
Indium and Bi were used as internal standards. Interfering oxide
ions of LREE (light rare-earth elements) on HREE (heavy rare-earth
elements) were corrected by measuring 20 ppb LREE solutions.
4.3. Organic geochemistry
Insoluble carbonaceous material (kerogen) was extracted from
24 black chert samples (5 samples of VC, 2 of CE1, 7 of CE2, and 10
of LC). The carbon stable isotopic ratio of the extracted kerogens
was measured using a dual-inlet isotope ratio mass spectrometry
(IRMS). The carbon content of bulk rock samples was also deter-
mined, using an elemental analyzer. Detailed analytical procedures
are given below.
4.3.1. Isolation of kerogen
Black chert samples were pulverized with a stainless steel mor-
tar. Sample powders (150–350 g) were then treated with 6M-HCl.
A mixed acid (HF:HCl = 4:1) was added to sample powders for
digestion, followed by rinsing with distilled water. This mixed
acid treatment was repeated twice until silicates were decom-
posed completely. Then, the residue was cleaned with hot HCl
(80 ◦ C) for 48 h, yielding residues composed of kerogen and pyrite.
Kerogen was separated from pyrite using a heavy liquid (CHBr3 ;
2.9 g/cm3 ). The separated kerogens were washed with CHCl2 in
soxhlet extraction apparatus for 72 h, with the aim of removal of
possible contamination by organic matter introduced during the
experiment.
4.3.2. Stable carbon isotopic ratio (ı13 C)
The extracted kerogen (0.5–1.0 mg) was sealed in Vycor tubes
that were preheated at 950 ◦ C. Atmospheric CO2 gas was evacuated
during sealing. Then, samples were converted into CO2 at 900 ◦ C for
4 h, with CuO as an oxidizer. The sample CO2 gas was first trapped in
the Vycor tube in a liquid N2 bath (−196 ◦ C), and then released to the
second tube by replacing the liquid N2 bath with a liquid N2 -ethanol
bath (−95 to −90 ◦ C). The released CO2 gas was condensed again in
the second tube, which was subsequently sealed. Carbon isotopic
ratios analyzed by IRMS are written in conventional ı-notations for
the PDB scale. The precision of the IRMS analysis was ±0.05‰.
5. Results
The results of chemical analyses are shown in Table 1. Averages
and ranges for some indices are listed in Table 2. Shale (PAAS)-
normalized REE patterns are shown in Fig. 4.
Table 1

78
Result of rare-earth elements and yttrium analysis of black carbonaceous cherts in the study (Farrel Quartzite and Cleaverville Formation).

VC CE1 CE2

GFD2 SGH1 SGH2 SGH3 SGH4 GFTE1 GFTE3 GWXB-1 GWXB-2 GFSV1 GFSV2 GFSV3 GFSV4

(wt%)
TiO2 0.0623 0.0375 0.0453 0.0269 0.0163 0.0272 0.0413 0.0099 0.0206 0.0034 0.0089 0.0077
Al2 O3 1.13 0.842 0.913 0.3 0.227 0.467 0.994 0.237 0.357 0.07 0.195 0.104
Fe2 O3 0.228 0.11 0.147 0.094 0.173 0.098 0.38 0.346 0.092 0.049 0.072 0.036
P2 O5 0.0064 0.0069 0.0086 0.012 0.0072 0.0092 0.0086 0.0058 0.0064 0.0042 0.0046 0.0039
Ctotal 0.038 0.033 0.045 0.034 0.023 0.042 0.03 0.064 0.045
␦13 CPDB −29.40 −31.07 −30.81 −30.51 −30.21 −28.56 −31.83 −33.57 −33.00 −33.95

(ppm)
La 2.130 1.842 5.574 0.368 0.837 4.141 3.790 0.648 1.194 0.0784 0.0386 0.0528 0.0141
Ce 3.470 3.065 9.133 0.745 1.872 6.062 7.038 1.191 2.182 0.112 0.0636 0.0748 0.0207
Pr 0.395 0.377 1.117 0.102 0.243 0.674 0.785 0.132 0.244 0.0115 0.00657 0.00655 0.00229
Nd 1.643 1.497 4.337 0.515 1.091 2.820 2.853 0.490 0.921 0.0656 0.0232 0.0208 0.00944
(Pm)
Sm 0.299 0.300 0.753 0.131 0.224 0.486 0.409 0.0844 0.163 0.0098 0.00450 0.00389 0.00266
Eu 0.0866 0.0812 0.201 0.0407 0.0611 0.144 0.0933 0.0271 0.0450 0.00369 0.00184 0.00296 0.00122

H. Sugahara et al. / Precambrian Research 177 (2010) 73–87

Gd 0.267 0.260 0.668 0.142 0.169 0.350 0.249 0.0733 0.135 0.0114 0.00628 0.00470 0.00355
Tb 0.035 0.025 0.061 0.020 0.017 0.047 0.026 0.0088 0.017 0.0023 0.0011 0.00074 0.00056
Dy 0.173 0.122 0.315 0.126 0.0889 0.338 0.134 0.0481 0.0928 0.0142 0.00870 0.00555 0.00398
Ho 0.034 0.021 0.055 0.027 0.015 0.079 0.025 0.0093 0.019 0.0032 0.0019 0.0011 0.00077
Er 0.105 0.0690 0.168 0.0788 0.0407 0.222 0.0569 0.0289 0.0579 0.0101 0.00615 0.00352 0.00266
Tm 0.019 0.011 0.024 0.011 0.0054 0.029 0.0076 0.0041 0.0082 0.0017 0.0009 0.0005 0.0004
Yb 0.113 0.0719 0.164 0.0680 0.0345 0.193 0.0618 0.0295 0.0575 0.00899 0.00617 0.00333 0.00246
Lu 0.021 0.011 0.024 0.010 0.0049 0.027 0.0086 0.0045 0.0086 0.0016 0.00092 0.00041 0.00033
Y 1.061 0.576 1.458 0.862 0.369 2.714 0.715 0.305 0.590 0.114 0.0623 0.0427 0.0244

REE (ppm) 8.789 7.753 22.593 2.385 4.703 15.613 15.537 2.779 5.143 0.335 0.170 0.182 0.065
Y/Ho 31.3 26.8 26.5 31.9 25.3 34.3 29.0 32.8 31.2 35.3 32.0 39.2 31.7
Pr/Smpaas 0.830 0.790 0.933 0.490 0.682 0.872 1.21 0.981 0.942 0.737 0.918 1.06 0.543
Pr/Ybpaas 1.10 1.65 2.15 0.47 2.21 1.10 4.00 1.40 1.33 0.40 0.33 0.62 0.29
Sm/Ybpaas 1.33 2.09 2.30 0.965 3.24 1.26 3.31 1.43 1.41 0.548 0.365 0.585 0.541
[La/{Pr(Pr/Nd)2 }]paas 1.70 1.40 1.36 1.66 1.26 1.95 1.16 1.24 1.27 4.00 1.33 1.47 1.89
[Ce/Pr(Pr/Nd)]paas 1.13 1.00 0.98 1.14 1.07 1.17 1.01 1.04 1.05 1.72 1.06 1.12 1.15
Eu/(2/3Sm + 1/3Tb)PAAS 1.55 1.59 1.58 1.52 1.63 1.68 1.41 1.78 1.54 1.55 1.64 3.43 1.98
Distance from CE2 boundary (m)

CE2 LC-Mt. Grant


GFSV5 GFSV6 GFTE06-02 GFTE0604 GFWE1 GFWE2 MGTX2 GWM11A -1 GWM11A GFTU2 GFTU4 GFTU5 GFTU6

(wt%)
TiO2 0.0055 0.0053 0.0045 0.005 0.0037 0.0063 0.0113 0.0096 0.0091 0.0076
Al2 O3 0.072 0.125 0.065 0.079 0.086 0.117 0.208 0.102 0.169 0.122
Fe2 O3 0.048 0.053 0.019 0.024 0.134 0.51 0.416 0.659 0.2
P2 O5 0.0041 0.0048 0.004 0.0048 0.0045 0.0054 0.0045 0.0046 0.0051
Ctotal 0.054 0.024 0.064 0.035 0.042 0.073 0.036
␦ CPDB
13
−33.71 −31.74 −33.37 −28.35 −27.84 −28.84 −30.88

(ppm)
La 0.0397 0.205 0.0514 0.0708 0.0807 0.0317 0.0570 0.395 0.0437 0.465 0.285 0.273 1.141
Ce 0.0497 0.270 0.0877 0.127 0.134 0.0661 0.0928 0.432 0.0571 0.615 0.722 0.410 2.079
Pr 0.00713 0.0262 0.0100 0.0142 0.0154 0.00774 0.0101 0.0704 0.00860 0.0805 0.0528 0.0476 0.237
Nd 0.0255 0.106 0.0358 0.0553 0.0551 0.0274 0.0379 0.237 0.0342 0.303 0.204 0.202 0.945
(Pm)
Sm 0.00481 0.0164 0.00656 0.0111 0.0099 0.00462 0.00727 0.0391 0.00770 0.0540 0.0391 0.0393 0.180
Eu 0.00140 0.00491 0.00211 0.00449 0.00387 0.00348 0.00239 0.0124 0.00270 0.0152 0.0128 0.0118 0.0476
Gd 0.00508 0.0183 0.00843 0.0199 0.0101 0.00480 0.00844 0.0284 0.00850 0.0496 0.0329 0.0379 0.133
Tb 0.00077 0.0033 0.0014 0.0043 0.0015 0.00068 0.0015 0.0038 0.0014 0.0074 0.0042 0.0054 0.017
 CE2 LC-Mt. Grant

GFSV5 GFSV6 GFTE06-02 GFTE0604 GFWE1 GFWE2 MGTX2 GWM11A -1 GWM11A GFTU2 GFTU4 GFTU5 GFTU6

Dy 0.00557 0.0218 0.0100 0.0361 0.00973 0.00460 0.0102 0.0227 0.00920 0.0505 0.0253 0.0337 0.0907
Ho 0.0011 0.0048 0.0021 0.0077 0.0020 0.00084 0.0021 0.0043 0.0018 0.012 0.0053 0.0076 0.017
Er 0.00374 0.0149 0.00632 0.0209 0.00641 0.00265 0.00638 0.0131 0.00570 0.0362 0.0163 0.0246 0.0462
Tm 0.0005 0.0024 0.0009 0.0024 0.0009 0.0004 0.0009 0.0019 0.0008 0.0052 0.0023 0.0038 0.0059
Yb 0.00382 0.0132 0.00585 0.0133 0.00656 0.00249 0.00574 0.0136 0.00600 0.0346 0.0157 0.0238 0.0369
Lu 0.00053 0.0022 0.00083 0.0017 0.00092 0.00030 0.00080 0.0020 0.00080 0.0055 0.0024 0.0041 0.0055
Y 0.0348 0.153 0.0679 0.266 0.0689 0.0330 0.0771 0.112 0.0643 0.456 0.196 0.333 0.619

REE (ppm) 0.149 0.709 0.229 0.389 0.337 0.158 0.244 1.275 0.188 1.733 1.421 1.124 4.980
Y/Ho 30.7 31.5 32.7 34.4 34.6 39.1 36.9 25.8 35.7 39.3 37.0 43.6 36.7
Pr/Smpaas 0.932 1.01 0.964 0.808 0.983 1.05 0.873 1.13 0.703 0.938 0.850 0.763 0.829
Pr/Ybpaas 0.59 0.62 0.54 0.34 0.74 0.98 0.55 1.64 0.45 0.73 1.06 0.63 2.01
Sm/Ybpaas 0.630 0.618 0.560 0.418 0.752 0.929 0.633 1.44 0.642 0.780 1.25 0.825 2.43
[La/{Pr(Pr/Nd)2 }]PAAS 1.30 2.31 1.17 1.36 1.21 0.93 1.44 1.15 1.46 1.48 1.46 1.87 1.39
[Ce/Pr(Pr/Nd)]PAAS 0.77 1.29 0.96 1.07 0.96 0.93 1.07 0.64 0.82 0.89 1.64 1.13 1.09
Eu/(2/3Sm + 1/3Tb)PAAS 1.41 1.31 1.38 1.29 1.93 3.76 1.42 1.79 1.61 1.43 1.79 1.53 1.52
Distance from CE2 boundary (m) 3.5 7.0 8.0 8.5

H. Sugahara et al. / Precambrian Research 177 (2010) 73–87

LC-Mt. Grant LC-Mt. Goldsworthy

SGH5 SGH6 SGH7 SGH8 SGH9 GW98-1-48 GW98-1-49 GW98-1-50 GW98-1-51 GW98-1-52 GW98-1-53 GW98-1-54 GW98-1-55

(wt%)
TiO2 0.0049 0.0047 0.0055 0.0045 0.0055 0.047 0.021 0.006 0.008 0.008 0.012 0.008 0.005
Al2 O3 0.084 0.095 0.029 0.075 0.019 0.91 0.52 0.29 0.35 0.25 0.27 0.234 0.16
Fe2 O3 0.168 0.188 0.219 13.416 0.029 1.26 0.2 2.77 3.13 5.22 21.04 21.848 1.11
P2 O5 0.0058 0.0058 0.0045 0.0135 0.0049 0.004 0.009 0.021 0.007 0.005 0.018 0.015 0.005
Ctotal 0.068 0.035 0.115
␦13 CPDB −34.51 −26.45 −28.96 −29.37 −26.83

(ppm)
La 0.265 0.499 0.172 0.458 0.00928 1.379 3.971 4.629 0.399 0.697 1.74 1.261 0.161
Ce 0.216 0.447 0.166 0.794 0.0137 1.456 4.346 4.748 0.369 1.103 3.298 2.346 0.381
Pr 0.0504 0.0474 0.0199 0.0873 0.00162 0.285 0.577 0.783 0.048 0.141 0.41 0.28 0.028
Nd 0.200 0.158 0.0751 0.392 0.00743 1.141 2.221 3.193 0.189 0.657 1.835 1.321 0.114
(Pm)
Sm 0.0388 0.0309 0.0114 0.0743 0.00189 0.231 0.395 0.523 0.038 0.143 0.383 0.313 0.027
Eu 0.0155 0.0120 0.00610 0.0349 0.00093 0.071 0.117 0.141 0.017 0.05 0.138 0.124 0.011
Gd 0.0482 0.0331 0.0158 0.0866 0.00354 0.291 0.433 0.37 0.049 0.154 0.479 0.444 0.043
Tb 0.0073 0.0035 0.0019 0.011 0.00069 0.048 0.06 0.044 0.007 0.022 0.065 0.064 0.008
Dy 0.0523 0.0196 0.0124 0.0738 0.00539 0.334 0.374 0.239 0.046 0.142 0.39 0.41 0.056
Ho 0.011 0.0035 0.0030 0.018 0.0014 0.076 0.084 0.045 0.01 0.032 0.082 0.091 0.014
Er 0.0343 0.0100 0.0101 0.0563 0.00473 0.237 0.241 0.121 0.032 0.099 0.223 0.252 0.043
Tm 0.0045 0.0013 0.0014 0.0083 0.0007 0.034 0.031 0.016 0.004 0.015 0.029 0.031 0.005
Yb 0.0280 0.00857 0.00916 0.0570 0.00452 0.225 0.182 0.107 0.028 0.1 0.174 0.181 0.031
Lu 0.0040 0.0013 0.0015 0.010 0.00076 0.034 0.026 0.016 0.004 0.016 0.027 0.028 0.004
Y 0.449 0.123 0.162 0.790 0.0708 2.713 3.583 1.455 0.41 1.214 2.84 3.767 0.572

REE (ppm) 0.976 1.275 0.505 2.161 0.057 5.842 13.058 14.975 1.240 3.371 9.273 7.146 0.926
Y/Ho 40.2 34.5 53.5 44.4 51.8 35.7 42.7 32.3 41.0 37.9 34.6 41.4 40.9
Pr/SmPAAS 0.816 0.966 1.09 0.739 0.540 0.776 0.919 0.942 0.795 0.620 0.674 0.563 0.653
Pr/YbPAAS 0.57 1.74 0.68 0.48 0.11 0.40 1.00 2.30 0.54 0.44 0.74 0.49 0.28
Sm/YbPAAS 0.693 1.80 0.625 0.652 0.209 0.513 1.09 2.44 0.679 0.715 1.10 0.865 0.435
[La/{Pr(Pr/Nd)2 }]PAAS 1.50 2.12 2.23 1.92 2.18 1.41 1.85 1.78 2.33 1.94 1.54 1.82 1.73
[Ce/Pr(Pr/Nd)]PAAS 0.53 0.97 0.98 1.26 1.20 0.63 0.90 0.77 0.94 1.13 1.11 1.22 1.71
Eu/(2/3Sm + 1/3Tb)PAAS 1.81 2.10 2.56 2.30 1.62 1.34 1.46 1.58 2.05 1.71 1.70 1.74 1.50
Distance from CE2 boundary (m) 91.0 80.5 68.5 37.0 22.0 4.2 4.3 6.2 7.6 10.4 11.0 11.7 14.4

79
 80
Table 1 (Continued )
LC-Mt. Goldsworthy

GW98-1-56 GW98-1-57 GW98-1-58a GW98-1-58b GW95-1-35 GW95-1-36 GW95-1-37 GW98-1-59a GW98-1-59b GW98-1-60 GW98-1-62 GW98-1-63

(wt%)
TiO2 0.002 0.003 0.007 0.005 0.038 0.014 0.026 0.017 0.014 0.015 0.013 0.010
Al2 O3 0.05 0.07 0.17 0.17 0.560 0.230 0.374 0.242 0.200 0.230 0.210 0.300
Fe2 O3 5.66 10.16 28.89 52.03 41.420 1.706 36.592 2.234 3.900 57.450 8.620 3.210
P2 O5 0.02 0.015 0.009 0.007 0.029 0.009 0.134 0.027 0.047 0.048 0.057 0.042

H. Sugahara et al. / Precambrian Research 177 (2010) 73–87

Ctotal
␦13 CPDB

(ppm)
La 0.531 0.262 0.42 0.52 2.62 0.925 2.44 0.876 4.17 1.93 4.64 5.63
Ce 1.178 0.572 0.85 1.19 3.28 1.11 3.32 1.48 4.58 2.39 5.58 5.84
Pr 0.118 0.056 0.1 0.12 0.348 0.115 0.397 0.146 0.450 0.240 0.420 0.620
Nd 0.548 0.239 0.41 0.51 1.39 0.434 1.63 0.574 1.78 1.01 1.67 2.35
(Pm)
Sm 0.12 0.052 0.09 0.11 0.294 0.078 0.304 0.124 0.340 0.170 0.230 0.380
Eu 0.066 0.019 0.03 0.04 0.115 0.038 0.147 0.050 0.170 0.080 0.120 0.170
Gd 0.225 0.056 0.1 0.14 0.372 0.095 0.386 0.161 0.570 0.250 0.310 0.460
Tb 0.035 0.008 0.02 0.02 0.053 0.012 0.052 0.022 0.090 0.040 0.040 0.050
Dy 0.269 0.05 0.11 0.16 0.364 0.087 0.359 0.148 0.640 0.260 0.290 0.330
Ho 0.074 0.011 0.03 0.04 0.088 0.021 0.089 0.034 0.180 0.070 0.080 0.080
Er 0.246 0.032 0.08 0.13 0.280 0.065 0.288 0.101 0.550 0.230 0.280 0.260
Tm 0.036 0.005 0.01 0.02 0.041 0.008 0.042 0.012 0.070 0.030 0.040 0.030
Yb 0.246 0.031 0.09 0.14 0.285 0.052 0.295 0.080 0.350 0.200 0.260 0.180
Lu 0.045 0.005 0.01 0.02 0.048 0.007 0.052 0.012 0.050 0.030 0.050 0.030
Y 3.217 0.389 0.96 1.49 3.69 0.961 4.68 1.56 11.450 3.530 5.470 4.900

REE (ppm) 3.737 1.398 2.350 3.160 9.578 3.047 9.801 3.820 13.990 6.930 14.010 16.410
Y/Ho 43.5 35.4 32.0 37.3 41.9 45.8 52.6 45.9 63.6 50.4 68.4 61.3
Pr/SmPAAS 0.619 0.678 0.699 0.686 0.745 0.928 0.822 0.741 0.833 0.888 1.15 1.03
Pr/YbPAAS 0.15 0.57 0.35 0.27 0.38 0.70 0.42 0.57 0.40 0.38 0.51 1.08
Sm/YbPAAS 0.244 0.839 0.500 0.393 0.516 0.750 0.515 0.775 0.486 0.425 0.442 1.06
[La/{Pr(Pr/Nd)2 }]PAAS 1.76 1.54 1.28 1.42 2.18 2.08 1.88 1.68 2.63 2.58 3.16 2.36
[Ce/Pr(Pr/Nd)]PAAS 1.43 1.35 1.08 1.30 1.16 1.13 1.06 1.23 1.25 1.30 1.63 1.10
Eu/(2/3Sm + 1/3Tb)PAAS 2.04 1.79 1.41 1.67 1.80 2.39 2.28 1.87 1.95 1.94 2.44 2.31
Distance from CE2 boundary (m) 17.5 19.7 24.6 24.6 37.0 40.0 44.0 58.0 58.0 59.2 69.0 74.0
 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87 81

Fig. 4. Shale-normalized (PAAS; Post-Archean Australian Shale, Taylor and McLennan, 1985) REE + Y patterns of cherts of different occurrences: (a) VC (vein chert); (b)
CE1 (stratiform black chert associated with evaporite containing no microfossil); (c) CE2 (stratiform black chert with evaporite containing microfossils); (d) LC-Mt. Grant
(laminated to banded chert from Mt. Grant); (e) LC-Mt. Goldsworthy (laminated to banded chert from Mt. Goldsworthy).

5.1. Major elements
All chert samples are characterized by low concentrations of
TiO2 and Al2 O3 (TiO2 = 0.002–0.062%, Al2 O3 = 0.02–1.13%)(Table 1).
Fe2 O3 (as total iron) concentrations range widely from 0.019 to
57.45%, reflecting the wide range of lithology. Total carbon content
is from 0.023 to 0.073%, with an exception of SGH8 (0.12%) that
probably is attributed to higher abundance of carbonate.
5.2. Rare-earth elements
Fig. 4a). Y/Ho ranges from 25.3 to 31.9, representing chondritic
(Y/Ho = 26–27; Pack et al., 2007) to slightly super-chondritic val-
ues. The samples show slight to moderate positive anomalies of La
and Eu (1.26–1.70 for La and 1.52–1.63 for Eu), but Ce-anomalies
are negligible (0.98–1.14).1 CE1 samples are characterized by
relative enrichment of LREE (Pr/YbPAAS = 1.10–4.00) and MREE
(Sm/YbPAAS = 1.26–3.31), chondritic to super-chondritic Y/Ho ratios
(Y/Ho = 29.0–34.3), and slight to moderate positive anomalies of La
(1.16–1.95) and Eu (1.41–1.78) (Fig. 4b); Ce-anomalies are negligi-
ble (1.01–1.17).

VC samples are characterized by slight enrichment of light 1

La-anomaly, Ce-anomaly and Eu-anomaly are calculated by
REE (LREE) and middle REE (MREE) relative to heavy REE [La/{Pr(Pr/Nd)2 }]PAAS , [Ce/{Pr(Pr/Nd)}]PAAS (after Lawrence et al., 2006) and
(HREE) (Pr/YbPAAS = 0.47–2.21, Sm/YbPAAS = 0.965–3.24) (Table 2; [Eu/(2/3Sm+1/3Tb)]PAAS , respectively.
82 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87

Unlike VC and CE1, most CE2 samples have slightly HREE-

5.101

0.15

0.47
0.48
0.26
0.33
enriched patterns (Pr/YbPAAS = 0.29–1.64, Sm/YbPAAS = 0.365–1.44)

10.3

0.5
S.D.
and Y/Ho ratios are slightly super-chondritic (25.8–39.2). The
samples, except one, also have positive La-anomalies (1.15–4.00)

LC-Mt. Goldsworthy (n = 20)

7.203
Mean

0.79

0.74
1.95
1.17
1.85
and positive Eu-anomalies (1.29–3.76). Ce-anomalies range widely

44.2

0.6
from 0.64 to 1.72, although in most samples they are less than 1.0.
LC samples from Mount Goldsworthy and Mount Grant are com-

16.410

1.15

3.16
1.71
2.44
1.10
Max.
monly enriched in HREE, except for several samples. Y/Ho ratios of

68.4

2.3
Mt. Goldsworthy samples tend to be larger (32.0–68.4) than Mt.
Grant samples (36.7–53.5). Most samples show positive anomalies
0.563

0.244
1.240

0.15

1.28
0.63
1.34
of La and Eu. In Mount Grant samples, the La-anomalies range from
Min.

32.0

1.39 to 2.23 and Eu-anomalies range from 1.43 to 2.56. In Mount

Goldsworthy samples, La-anomalies range from 1.28 to 3.16 and
1.418

0.16
0.62
0.69
0.34

0.39
0.30
S.D.

Eu-anomalies range from 1.34 to 2.44.

6.7
1.581

5.3. Carbon isotopes

Mean

0.84
0.89

1.85
1.03
1.80
1.08
42.3

Kerogen samples have significantly light isotopic values ranging

LC-Mt. Grant (n = 9)

from −34.5 to −26.5‰ (Table 1), although there are slight difference
4.980

1.74
2.43
2.23
1.64
2.56
1.09
Max.

53.5

in ı13 C values between different chert lithologies. CE2 samples tend

to have lighter values (from −29.4 to −31.07‰ with an average of
0.057

0.540

0.209

−33.2 ± 0.8‰) compared with the other lithologies. Two CE1 sam-
0.11

1.39
0.53
1.43
Min.

36.7

ples have values of −31.8 and −28.5‰, and VC samples range from
−31.1 to −29.4‰, with an average of −30.4 ± 0.6‰. LC samples tend
0.324

to have relatively heavier ı13 C values from −34.5 to −26.5‰, with

0.17
0.36
0.27

0.27
0.79
0.80
S.D.

3.7

an average of −29.0 ± 2.4‰.

0.341
Mean

0.62
0.67
1.62

1.89
0.90

1.04

6. Discussion
33.8

6.1. Evaluation of contamination of clastic material

1.275

1.13
1.64
1.44

1.72
3.76
4.00
Max.

39.2
CE2 (n = 13)

Prior to interpreting REE + Y characteristics of the chert samples

in the context of parental solution geochemistry, it is necessary to
0.149

0.543

0.365
0.29

0.93
0.64
1.29
Min.

25.8

evaluate the possible influence of clastic material contained within

them. This is because if the chert samples were significantly con-
taminated with clastic material with high REE abundances, then
6.775

0.14
1.37
0.97
0.37

0.16
0.07
S.D.

2.3

the REE characteristics of chemically precipitated phases would

be obscured. The cherts are interbedded with clastic rocks, such
9.768

as sandstones and volcaniclastic rocks, indicating that they are

Mean

1.96
1.85
1.40
1.07
1.60
1.00
31.8

potentially contaminated with clastic material. Therefore, careful

evaluation of possible clastic contamination is necessary.
15.613

In Fig. 5, the relationships of total REE, Pr/YbPAAS , Y/Ho, La-

1.21

3.31
1.95
1.17
1.78
4.00
Max.

34.3

anomalies ([La/{Pr(Pr/Nd)2 }]PAAS ), Ce-anomalies ([Ce/{Pr(Pr/

CE1 (n = 4)

Nd)}]PAAS ) and Eu-anomalies ([Eu/(2/3Sm + 1/3Tb)]PAAS ) with TiO2 ,

2.779

0.872

which represents the amount of contaminated clastic material,

1.26
1.16

1.41
1.10

1.01
Min.

29.0

are shown. The chert samples have relatively low concentrations

Summary of minimum, maximum and average values of REE features.

of TiO2 (<0.07%) and as a whole do not show clear correlation

10.276

0.22
0.88
1.14
0.19
0.07
0.06

between TiO2 and total REE. LC samples from Mount Goldsworthy,

3.3
S.D.

and VC and CE2 samples tend to be enriched in TiO2 and total

REE relative to other types of cherts. VC and CE1 samples also
9.245
Mean

0.74
1.52
1.99
1.48

1.57
1.06

show a positive correlation between total REE and TiO2 . How-

28.4

ever, REE + Y patterns of studied samples show almost parallel

patterns among the same sample group, despite variations of
22.593

0.933
2.21
3.24

1.14
1.63
1.70

TiO2 concentrations (Fig. 4). Additionally, there is no systematic

Max.

31.9

relationships of TiO2 concentrations with Pr/YbPAAS , Y/Ho ratios,

VC (n = 5)

La-anomalies, Ce-anomalies and Eu-anomalies. Consequently, it

2.385

0.965
0.49
0.47

1.26
0.98
1.52

can be reasonably assumed that contamination by clastic material

Min.

25.3

does not significantly obscure the REE signatures of the chemically

precipitated phase of chert in the analyzed samples.
Eu/(2/3Sm + 1/3Tb)PAAS
[La/{Pr(Pr/Nd)2 }]PAAS
[Ce/Pr(Pr/Nd)]PAAS

6.2. REE + Y characteristics of laminated to banded chert (LC)

REE (ppm)

Stratigraphic and lithological data suggest that the depositional

Sm/YbPAAS
Pr/SmPAAS
Pr/YbPAAS

setting of the sedimentary succession at the Mount Goldsworthy

Table 2

Y/Ho

greenstone belt changed from a shallow, closed to semi-closed

basin, in which black chert and CE1 and CE2 evaporite beds were
 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87
Fig. 5. Relationships of TiO2 concentration with total REE concentration (a), Pr/YbPAAS (b), Y/Ho (c), [La/{Pr(Pr/Nd)2 }]PAAS (La-anomaly) (d), [Ce/{Pr(Pr/Nd)}]PAAS (Ce-anomaly)
(e), and [Eu/(2/3Sm + 1/3Tb)]PAAS (Eu-anomaly) (f).
deposited, to relatively deeper water conditions under which lami-
nated to banded chert (LC) was deposited (Sugitani et al., 2003; also
see Fig. 2d). The geological context favours a marine origin for LC,
which can be tested by examination of their REE + Y characteristics.
6.2.1. Description of REE + Y features
The shale-normalized REE characteristics of most LC samples
are: (1) enrichment of HREE relative to LREE and MREE; (2) positive
La-anomalies; (3) a wide range of Y/Ho, from chondritic to super-
chondritic values (up to 70), positive Eu-anomalies (up to 2.56), and
a wide range of Ce-anomalies (Table 1 and Figs. 4 and 6). Among
these characteristics, HREE-enrichment, positive La-anomalies and
super-chondritic Y/Ho values characterize modern seawater, and
chemical and biogenic sediments of seawater origin (Masuda et
al., 1987; Lee and Byrne, 1993; Bau and Dulski, 1996; Webb and
Kamber, 2000). HREE-enrichment is explained by preferential cou-
pling of HREE with carbonate ions due to their smaller ionic
radius compared to LREE and MREE, resulting in selective reten-
tion of HREE in seawater and thus their relative enrichment (Lee
and Byrne, 1993). The positive La-anomaly, on the other hand,
is explained by the W-type tetrad effect that is observed in sea-
water and chemical sediments of seawater origin (Masuda and
83
Ikeuchi, 1979; Masuda et al., 1987; Ohta and Kawabe, 2000). HREE-
enrichment and positive La-anomalies have been reported from
Archean chemical sediments such as cherts, BIFs, stromatolites and
inter-pillow carbonates, and often taken as evidence for their sea-
water origin (Van Kranendonk et al., 2003; Yamamoto et al., 2004;
Kamber et al., 2004; Bolhar et al., 2004, 2005).
Y/Ho ratios range from 36.7 to 53.5 for Mount Grant LC sam-
ples, and from 32.0 to 68.4 for Mount Goldsworthy samples. About
one-half of samples have markedly higher Y/Ho (>45). Such frac-
tionated Y/Ho ratios have been observed for modern seawater and
is interpreted to reflect preferential scavenging of REE by particu-
late matter in the seawater column (Nozaki et al., 1997) and/or near
hydrothermal vent settings (Bau and Dulski, 1999). On the other
hand, no fractionations are expected between Y and Ho during high
temperature fluid–rock interaction (Bolhar et al., 2005), resulting
in chondritic values of hydrothermal water (Y/Ho = 26–27; Pack et
al., 2007). Data of Y/Ho for river waters are scarce and variable,
with commonly lower values than for seawater and with some
equal to upper continental crust (28) (Nozaki et al., 1997; Lawrence
et al., 2006). Like HREE-enrichment and positive La-anomalies,
Y/Ho ratios have recently been used as a proxy for a marine or
non-marine origin of Archean chemical sedimentary rocks (e.g.,
84 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87
Fig. 6. [La/{Pr(Pr/Nd)2 }]PAAS vs. [Ce/{Pr(Pr/Nd)}]PAAS plot, discriminating between
La-anomaly and Ce-anomaly (after Lawrence et al., 2006). Panorama Formation BIF
samples of hydrothermal origin (Archean) (Bolhar et al., 2005), and Strelley Pool
Chert carbonates (Archean) (Van Kranendonk et al., 2003) and Holocene micro-
bialites (Webb and Kamber, 2000) of seawater origin are also plotted. LC samples
and Strelley Pool Chert carbonates tend to have higher La-anomalies, compared
with the majority of CE1 and 2 and VC samples, Panorama samples and Holocene
microbialites.
Bolhar and Van Kranendonk, 2007).
6.2.2. Interpretation
It is noteworthy that Y/Ho ratios of LC samples show a clear
stratigraphic trend of increasing Y/Ho upsection (Fig. 7a). Like Y/Ho,
Eu-anomalies of LC samples also show an increase upsection from
1.3 to 2.5 (Fig. 7b). Positive Eu-anomalies often have been regarded
as the signature of a hydrothermal component in Archean chemical
sedimentary rocks (Danielson et al., 1992; Sugitani, 1992; Kato et
al., 1998; Bau and Dulski, 1999; Kato and Nakamura, 2003; Bolhar
et al., 2005), because modern high-T hydrothermal vent solutions
Fig. 7. Stratigraphic trends of Y/Ho ratio (a) and [Eu/(2/3Sm + 1/3Tb)]PAAS (Eu-anomaly) (b) in LC from Mount Grant and Mount Goldsworthy. Vertical axis indicates distance
from the boundary between the Farrel Quartzite and the Cleaverville Formation.
are commonly characterized by a distinct positive Eu-anomaly and
hydrothermal activity can be assumed to have been more active
in the Archean. This anomaly is attributed to the change of valence
state from Eu3+ to more soluble Eu2+ during water–rock interaction
under the strongly reducing and high temperature condition (Bau,
1991; Douville et al., 1999, and referenced therein). Even in the
reducing Archean atmosphere (e.g., Holland, 1994), surface weath-
ering could not have produced continental run-off with a significant
positive Eu-anomaly (Danielson et al., 1992).
From the stratigraphic change of lithology, we suggest that the
evaporite and black chert deposition in a closed to semi-closed
sedimentary basin was followed by the deposition of chemical sed-
iments that represent a deeper water depositional environment. It
is thus plausible that the basin water chemistry gradually changed.
The observed increasing upward stratigraphic trend of Y/Ho and
Eu-anomalies can be interpreted in the context of this model of the
basin evolution (Fig. 7). Whereas it is possible that the trend of Y/Ho
is a result of fractionation between particulate matter and solu-
tion, Y/Ho correlates neither with Fe2 O3 concentrations (Fig. 8a)
nor lithological variations (jaspilitic or carbonaceous) but in consis-
tent with the trend of Eu-anomalies independent of a fractionation
effect, as indicated by the lack of correlation with Fe2 O3 (Fig. 8b).
It is possible that REE + Y features in the Archean seawater were
depth-dependent, which however does not readily mean that the
features in chemical precipitates simply reflect the depth of depo-
sition. Rather we suggest that the changes can be interpreted as
inflow of water with a relatively strong positive Eu-anomaly and
super-chondritic Y/Ho into the basin, where it mixed with a water
mass with a negligible Eu-anomaly and chondritic Y/Ho, of proba-
ble non-marine origin. This introduced water represents seawater,
which is consistent with the HREE-enrichment of most LC samples.
Additionally, all LC samples have positive La-anomalies (1.28–3.16)
and samples from the upper horizons have higher values (1.92–2.23
for the uppermost four samples from Mount Grant and 2.36–3.16
for the uppermost four samples from Mount Goldsworthy), sup-
porting our inference of increasing influence of seawater inflow
during chert deposition of the Cleaverville Formation.
6.3. REE + Y systematics of cherts
Chert lithologies VC, CE1 and CE2 have somewhat different
REE + Y characteristics from LC samples, as summarized below.
(1) VC samples do not show HREE-enrichment relative to LREE
and MREE, but rather tend to be enriched in MREE (Fig. 4a).
They show positive La-anomalies (1.26–1.70) and no distinct
negative Ce-anomalies (0.98–1.14). Y/Ho ratios are chondritic
 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87 85

Fig. 8. Relationships of Fe2 O3 concentration with Y/Ho (a) and [Eu/(2/3Sm + 1/3Tb)]PAAS (Eu-anomaly) (b).

to slightly super-chondritic (25.3–31.9), with negligible Eu-
anomalies (Eu/Eu* < 1.7).
(2) CE1 samples do not show HREE-enrichment but are slightly
LREE-enriched. They have a positive La-anomaly (1.16–1.95),
no negative Ce-anomaly (1.01–1.17), slightly super-chondritic
Y/Ho ratios (29.0–34.3) and a slight Eu-anomalies (1.41–1.78).
(3) CE2 samples are commonly enriched in HREE, and are more
diverse in some other indices compared with VC and CE1 sam-
ples. La- and Ce-anomalies vary from 0.93 to 4.00 and 0.64
to 1.72, respectively. Positive Eu-anomalies are not significant
(<2), except for two samples. Y/Ho ratios are slightly super-
chondritic, at less than 40.
REE + Y characteristics of VC and CE1 samples are quite distinct
from LC samples that are assumed to have been deposited from
water mass influenced by seawater, whereas CE2 samples share
some common REE signatures with LC samples. This is not surpris-
ing because VC samples are from vein chert, indicating that their
formation process and source solution were different from LC sam-
ples of undoubtedly sedimentary origin. It also seems reasonable
that regardless of their similar occurrence (Fig. 2d), REE + Y charac-
teristics of CE1 and CE2 are not the same (for instance, see Fig. 4),
because deposition of CE1 represents an interruption of continuous
clastic sedimentation, whereas CE2 represents the end of clastic
sedimentation and a transition to facies dominated by chemical
precipitation.
In order to understand comprehensively and more simply the
source of these cherts, we introduce a new Y/Ho–Eu-anomaly dia-
gram, which provides some constraints on the composition of
Archean seawater, high-T hydrothermal solutions and other poten-
tial sources for the cherts.
Eu-anomalies in Archean chemical sedimentary rocks were once
interpreted to be of hydrothermal origin (e.g., Sugitani, 1992).
However, they were not necessarily directly precipitated from
high temperature hydrothermal solutions; Eu-enrichment is rather
considered a signature of the Archean oceans (Danielson et al.,
1992; Tice and Lowe, 2006a,b). In modern oceans, REE are scav-
enged by co-precipitation with Fe and Mn oxyhydroxides shortly
after emission from the vents, and the hydrothermal input to the
modern ocean is negligible (Bau and Dulski, 1999). By contrast,
in the Archean this scavenging process had not been in oper-
ation due to low levels of oxygen (Holland, 1994; Farquhar et
al., 2000). Thus, the influence of a hydrothermal input into the
Archean surface ocean was larger than today, considering much
higher hydrothermal fluxes from mid ocean ridges at that time
(Danielson et al., 1992). High temperature hydrothermal solutions,
on the other hand, would be inferred from data of jasper and siderite
of the Panorama Formation that is thought formed from high-T
hydrothermal fluids and shallow seawater in a volcanic caldera set-
ting (Bolhar et al., 2005). They comprise the array with chondritic to
slightly super-chondritic Y/Ho ratios and positive but variable Eu-
anomalies up to 4.5, which could be explained by mixing of high-T
hydrothermal solution and another end-member characterized by
chondritic Y/Ho and a slight positive Eu-anomaly.

6.3.1. Y/Ho–Eu-anomaly systematics

On an Y/Ho–Eu-anomaly diagram (Fig. 9) LC samples show
a positive correlation between these indices, because both the
Y/Ho ratios and Eu-anomalies generally increase upsection. As
previously discussed, REE + Y of LC samples were derived at least
partially to mostly from Archean seawater. Thus the trends towards
increasing values could plausibly lead to an Archean seawater
end-member. Although our data could not specify the Archean
seawater end-member, it would plausibly have Y/Ho value and
Eu-anomaly that are less than 100 and 3, respectively. This infer-
ence is not inconsistent with data from the carbonate rocks
of the Strelley Pool Chert (3.40 Ga) that is thought to be of
Archean seawater origin (Van Kranendonk et al., 2003) (Fig. 9)
Fig. 9. Binary plot of Y/Ho ratio and [Eu/(2/3Sm + 1/3Tb)]PAAS (Eu-anomaly). There
and other data from Archean chemical sediments (Bau and Dulski,
can be seen a positive correlation observed for LC from the Cleaverville Formation,
1996; Kato et al., 1998; Kamber and Webb, 2001; Bolhar et al., reflecting the stratigraphic co-variation of these two indices. This implies a change
2005). of basin water chemistry (also see text).
86 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87
6.3.2. Sources of VC, CE1 and CE2 cherts
On the Y/Ho–Eu-anomaly diagram, most VC, CE1 and CE2 sam-
ples plot within a relatively narrow area of slightly super-chondritic
Y/Ho ratios and small positive Eu-anomalies (Fig. 9). This area is
close to, or overlaps with some of LC samples from the lower part
of the Cleaverville Formation.
CE1 and CE2 cherts are closely associated with evaporite beds
(Fig. 2d), which suggests that the cherts were formed in a closed to
semi-closed basin most likely in a continental setting (Sugitani et
al., 2003, 2006a). In this setting, water mass was likely influenced by
non-marine water. Slight LREE-enrichment, slight super-chondritic
Y/Ho ratios and negligible Eu-anomalies of CE1 samples all refute
that they originated solely from seawater: rather, they are more
likely precipitated from a water mass whose REE + Y features were
significantly controlled by non-marine sources such as continental
run-off and ground water, and possibly geothermal water, con-
sidering it does not always have positive Eu-anomaly (e.g., Wood,
2006). CE2 samples except for two samples, on the other hand, have
more seawater-like REE + Y features as described above, suggest-
ing their precipitation from a water mass that was influenced by
seawater components to a larger degree.
Although REE + Y characteristics of VC samples are difficult to
explain, the results of our study suggest that black vein chert would
not be necessarily products of high-temperature deep hydrother-
mal activity (Van Kranendonk, 2006; Lindsay et al., 2007). Rather,
the origin of black vein chert studied here could be interpreted as
low-T hydrothermal activity or in an analogy with the carbona-
ceous vein chert in Barberton greenstone belt, which were thought
formed by hydraulic fracturing (Hofmann and Bolhar, 2007). In
either case, it can be emphasized that REE characteristics of VC are
distinct from microfossil-bearing CE2.
6.4. Implications of Archean non-marine ecosystem
Despite the similar occurrence with CE2 samples containing
abundant microfossils of diverse morphologies, CE1 black cherts do
not contain microfossils. However, this may be merely attributed
to their destruction during reworking and transportation, consid-
ering that sedimentary textures of the CE1 cherts indicate their
deposition under a higher energy environment compared with CE2
black chert (Sugitani et al., 2007). In either case, significantly light
carbon isotopic values are consistent with a biogenic origin of car-
bonaceous matter. Although light carbon isotopes cannot be “a
smoking-gun” for microbes (Brasier et al., 2005; McCollom and
Seewald, 2006; Lindsay et al., 2007), the presence of microfossils
in black chert of the similar occurrence (CE2) supports the biogenic
origin of CE1 carbonaceous matter.
CE2 black cherts are also believed deposited in the evapor-
itic basin to which both non-marine and marine waters could
have inflow as discussed above. Unfortunately, source of non-
marine water cannot yet be specified. It is, however, inferred from
the present results that microorganisms had already flourished
in shallow, evaporitic environment and even comprised complex
ecosystem, probably in the continental margin setting by at least
3.0 Ga. This is consistent with or supports some previous studies
suggesting the early evolution of shallow to sub-aerial and/or non-
marine ecosystem (e.g., Watanabe et al., 2000; Allwood et al., 2006;
Tice and Lowe, 2006a,b; Bolhar and Van Kranendonk, 2007).
7. Conclusions
Systematic REE + Y analyses were conducted to understand the
origins and depositional environments of Archean (ca. 3.0 Ga)
cherts of various lithologies and occurrences from the Mount
Goldsworthy greenstone belt in the Pilbara Craton, including black
carbonaceous cherts that contain morphologically diverse, abun-
dant microfossils (Sugitani et al., 2007). The chert samples for this
study include black vein chert (VC) in the Warrawona Group mafic
to ultramafic volcanic sequence, stratiform black chert associated
with evaporite (CE1 and CE2) in the Farrel Quartzite and varicolored
laminated to banded chert (LC) in the Cleaverville Formation. Lam-
inated to banded cherts (LC) of the Cleaverville Formation show
a clear stratigraphic trend of increasing Y/Ho and Eu-anomaly,
with HREE-enrichment and a positive La-anomaly. On the pro-
posed Y/Ho–Eu-anomaly diagram, LC samples comprise an array
showing mixing of the two end-member components; one is the
most likely Archean seawater with super-chondritic (∼100) Y/Ho
ratio and a weak positive Eu-anomaly (∼3) and the other charac-
terized by chondritic Y/Ho and negligible Eu-anomaly is assumed
to be non-marine water such as continental run-off, ground water,
or geothermal water, considering their supposed continental mar-
gin depositional setting for the Farrel Quartzite (Sugitani et al.,
2003, 2006a). Other chert samples including black cherts associ-
ated evaporite (CE1 and CE2) in the Farrel Quartzite, except two,
plot on the array defined by LC, clustering around the supposed
non-marine end-member component. The result suggests that the
water mass chemistry, from which CE1 and CE2 black cherts were
precipitated, was influenced significantly by non-marine water and
that formation of black vein chert (VC) is not necessarily attributed
to high-T hydrothermal activity. The microfossil-bearing black
cherts of the ca. 3.0 Ga Farrel Quartzite in the Mount Goldswor-
thy greenstone belt were formed in a moderate and habitable
condition.
Acknowledgements
This paper is a product of a grant-in-aid supported by the Japan
Society for the Promotion of Science (No. 19340150). We wish to
express our gratitude to Dr. K. Grey for her support to our fieldwork
in the Pilbara Craton and to Dr. M.J. Van Kranendonk for his help-
ful comments on interpretations of geology of Mount Goldsworthy
and Mount Grant area and for informal review and constructive
comments. We also acknowledge to Mike Tice and an anonymous
reviewer for their critical and constructive comments.
References
Alibert, C., McCulloch, M.T., 1993. Rare earth element and neodymium isotopic com-
positions of the banded iron-formations and associated shales from Hamersley,
western Australia. Geochim. Cosmochim. Acta 57, 187–204.
Allwood, A.C., Walter, M.R., Kamber, B.S., Marshall, C.P., Burch, I.W., 2006. Stroma-
tolite reef from the Early Archaean era of Australia. Nature 441, 714–718.
Bau, M., 1991. Rare-earth element mobility during hydrothermal and metamorphic
fluid–rock interaction and the significance of the oxidation state of europium.
Chem. Geol. 93, 219–230.
Bau, M., Dulski, P., 1996. Distribution of yttrium and rare-earth element in the Penge
and Kuruman iron-formations, Transvaal Supergroup, South Africa. Precambrian
Res. 79, 37–55.
Bau, M., Dulski, P., 1999. Comparing yttrium and rare earths in hydrothermal fluids
from the Mid-Atlantic Ridge: implications for Y and REE behaviour during near-
vent mixing and for the Y/Ho ratio of Proterozoic seawater. Chem. Geol. 155,
77–90.
Bau, M., Möller, P., 1993. Rare earth element systematics of the chemically precipi-
tated component in Early Precambrian iron formations and the evolution of the
terrestrial atmosphere-hydrosphere-lithosphere system. Geochim. Cosmochim.
Acta 57, 2239–2249.
Bolhar, R., Van Kranendonk, M.J., Kamber, B.S., 2005. A trace element study of
siderite-jasper banded iron formation in the 3.45 Ga Warrawoona Group, Pilbara
Craton-Formation from hydrothermal fluids and shallow seawater. Precambrian
Res. 137, 93–114.
Bolhar, R., Van Kranendonk, M.J., 2007. A non-marine depositional setting for the
northern Fortescue Group, Pilbara Craton, inferred from trace element geochem-
istry of stromatolitic carbonates. Precambrian Res. 155, 229–250.
Bolhar, R., Kamber, B.S., Moorbath, S., Fedo, C.M., Whitehouse, M.J., 2004. Character-
isation of early Archaean chemical sediments by trace element signatures. Earth
Planet. Sci. Lett. 222, 43–60.
Brasier, M.D., Green, O.R., Lindsay, J.F., McLoughlin, N., Steele, A., Stoakes, C., 2005.
Critical testing of Earth’s oldest putative fossil assemblage from the ∼3.5 Ga Apex
 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87
chert, Chinaman Creek, Western Australia. Precambrian Res. 140, 55–102.
Danielson, A., Möller, P., Dulski, P., 1992. The europium anomalies in banded iron
formations and the thermal history of the oceanic crust. Chem. Geol. 97, 89–100.
Derry, L.A., Jacobsen, S.B., 1990. The chemical evolution of Precambrian seawater:
evidence from REEs in banded iron formations. Geochim. Cosmochim. Acta 54,
2965–2977.
Douville, E., Bienvenu, P., Charlou, J.L., Donval, J.P., Fouquet, Y., Appriou, P., Gamo,
T., 1999. Yttrium and rare earth elements in fluids from various deep-sea
hydrothermal systems. Geochim. Cosmochim. Acta 63, 627–643.
Dunlop, J.S.R., Milne, V.A., Groves, D.I., Muir, M.D., 1978. A new microfossil assem-
blage from the Archaean of Western Australia. Nature 274, 676–678.
Farquhar, J., Bao, H., Thiemens, M., 2000. Atmospheric influence of earth’s earliest
sulfur cycle. Science 289, 756–758.
Frei, R., Dahl, P.S., Duke, E.F., Frei, K.M., Hansen, T.R., Frandsson, M.M., Jensen, L.A.,
2008. Trace element and isotopic characterization of Neoarchean and Paleopro-
terozoic iron formations in the Black Hills (South Dakota, USA): assessment of
chemical change during 2.9–1.9 Ga deposition bracketing the 2.4–2.2 Ga first
rise of atmospheric oxygen. Precambrian Res. 162, 441–474.
Grey, K., Sugitani, K., 2009. Palynology of Archean microfossils (ca. 3.0 Ga) from
the Mount Grant area, Pilbara Craton, Western Australia: further evidence of
biogenicity. Precambrian Res. 173, 60–69.
Hickman, A.H., 2008. Regional review of the 3426-3350 Ma Strelley Pool Forma-
tion, Pilbara Craton, Western Australia. Geological Survey of Western Australia,
Record 2008/15.
Hickman, A.H., Van Kranendonk, M.J., 2008. Archean crustal evolution and min-
eralization of the northern Pilbara Craton—a field guide. Geological Survey of
Western Australia, Record 2008/13.
Hirata, T., Shimizu, H., Akagi, T., Sawatari, H., Masuda, A., 1988. Precise determina-
tion of rare earth elements in geological standard rocks by inductively coupled
plasma source mass spectrometry. Anal. Sci. 4, 637–643.
Hofmann, A., 2005. The geochemistry of sedimentary rocks from the Fig Tree Group,
Barberton greenstone belt: implications for tectonic, hydrothermal and surface
processes during mid-Archaean times. Precambrian Res. 143, 23–49.
Hofmann, A., Bolhar, R., 2007. Carbonaceous cherts in the Barberton greenstone
belt and their significance for the study of early life in the Archean record.
Astrobiology 7, 355–388.
Holland, H.D., 1994. Early Proterozoic atmospheric change. In: Bengston, S. (Ed.),
Early Life on Earth. Columbia University Press, New York, pp. 237–244.
Kato, Y., Nakamura, K., 2003. Origin and global tectonic significance of Early Archean
cherts from the Marble Bar greenstone belt, Pilbara Craton, Western Australia.
Precambrian Res. 125, 191–243.
Kato, Y., Ohta, I., Tsunematsu, T., Watanabe, Y., Isozaki, Y., Maruyama, S., Imai,
N., 1998. Rare earth element variations in mid-Archean banded iron forma-
tions: Implications for the chemistry of ocean and continent and plate tectonics.
Geochim. Cosmochim. Acta 62, 3475–3497.
Kamber, B.S., Bolhar, R., Webb, G.E., 2004. Geochemistry of late Archaean stroma-
tolites from Zimbabwe: evidence for microbial life in restricted epicontinental
seas. Precambrian Res. 132, 379–399.
Kamber, B.S., Webb, G.E., 2001. The geochemistry of late Archean microbial carbon-
ate: implications for ocean chemistry and continental erosion history. Geochim.
Cosmochim. Acta 65, 2509–2525.
Knoll, A.H., Barghoorn, E.S., 1977. Archean microfossils showing cell division from
the Swaziland system of South Africa. Science 198, 396–398.
Lee, J.H., Byrne, R.H., 1993. Complexation of trivalent rare earth elements (Ce, Eu,
Gd, Tb, Yb) by carbonate ions. Geochim. Cosmochim. Acta 57, 295–302.
Lindsay, J.F., Brasier, M.D., McLoughlin, N., Green, O.R., Fogel, M., Steele, A., Mertz-
man, S.A., 2007. The problem of deep carbon—an Archean paradox. Precambrian
Res. 143, 1–22.
Lawrence, M.G., Greig, A., Collerson, K.D., Kamber, B.S., 2006. Rare earth element and
yttrium variability in South East Queensland waterways. Aquat. Geochem. 12,
39–72.
Masuda, A., Kawakami, O., Dohmoto, Y., Takenaka, T., 1987. Lanthanide tetrad effects
in nature: two mutually opposite types, W and M. Geochem. J. 21, 119–124.
Masuda, A., Ikeuchi, Y., 1979. Lanthanide tetrad effect observed in marine environ-
ment. Geochem. J. 13, 19–22.
McCollom, T.M., Seewald, J.S., 2006. Carbon isotope composition of organic com-
pounds produced by abiotic synthesis under hydrothermal conditions. Earth
Planet. Sci. Lett. 243, 74–84.
Murray, R.W., Buchholtz ten Brink, M.R., Gerlach, D.C., Russ III, G.P., Jones, D.J., 1991.
Rare earth, major, and trace elements in chert from the Franciscan Complex
and Monterey Gorup, California: assessing REE sources to fine-grained marine
sediments. Geochim. Cosmochim. Acta 55, 1875–1895.
Nozaki, Y., Zhang, J., Amakawa, H., 1997. The fractionation between Y and Ho in the
marine environment. Earth Planet. Sci. Lett. 148, 329–340.
Oehler, D.Z., Robert, F., Walter, M.R., Sugitani, K., Allwood, A., Meibom, A., Mostefaoui,
S., Selo, M., Thomen, A., Gibson, E.K., 2009. NanoSIMS: insights to biogenicity and
syngeneity of Archaean carbonaceous structures. Precambrian Res. 173, 70–78.
Ohta, A., Kawabe, I., 2000. Theoretical study of tetrad effects observed in REE distri-
bution coefficients between marine Fe–Mn deposit and deep seawater, and in
87
REE(III)-carbonate complexation constants. Geochem. J. 34, 455–473.
Pack, A., Russell, S.S., Shelley, J.M.G., Van Zuilen, M., 2007. Geo- and cosmochem-
istry of the twin elements yttrium and holmium. Geochim. Cosmochim. Acta
71, 4592–4608.
Rasmussen, B., 2000. Filamentous microfossils in a 3,235-million-year-old vol-
canogenic massive sulphide deposit. Nature 405, 676–679.
Shimizu, H., Kunimaru, T., Yoneda, S., Adachi, M., 2001. Sources and depositional
environments of some Permian and Triassic cherts: significance of Rb–Sr and
Sm–Nd isotopic and REE abundance data. J. Geol. 109, 105–125.
Smithies, R.H., Van Kranendonk, M.J., Hickman, A.H., 2004. De Grey, W.A. Sheet 2757
(Version 2.0): Western Australia Geological Survey, 1:100000 Geological Series.
Sugitani, K., 1992. Geochemical characteristics of Archean cherts and other sedi-
mentary rocks in the Pilbara Block, Western Australia: evidence for Archean
seawater enriched in hydrothermally-derived iron and silica. Precambrian Res.
57, 21–47.
Sugitani, K., Grey, K., Nagaoka, T., Mimura, K., 2009a. Three-dimensional mor-
phological and textural complexity of Archean putative microfossils from
the northeastern Pilbara Craton: indications of biogenicity of large (>15 ␮m)
spheroidal and spindle-like structures. Astrobiology 9, 603–615.
Sugitani, K., Grey, K., Nagaoka, T., Mimura, K., Walter, M.R., 2009b. Taxonomy and
biogenicity of Archaean spheroidal microfossils (c. 3.0 Ga) from the Mount
Goldsworthy–Mount Grant area in the northeastern Pilbara Craton, Western
Australia. Precambrian Res. 173, 50–59.
Sugitani, K., Mimura, K., Suzuki, K., Nagamine, K., Sugisaki, R., 2003. Stratigraphy and
sedimentary petrology of an Archean volcanic-sedimentary succession at Mt.
Goldsworthy in the Pilbara Block, Western Australia: implications of evaporite
(nahcolite) and barite deposition. Precambrian Res. 120, 55–79.
Sugitani, K., Yamashita, F., Nagaoka, T., Yamamoto, K., Minami, M., Mimura, K.,
Suzuki, K., 2006a. Geochemistry and sedimentary petrology of Archean clastic
sedimentary rocks at Mt.Goldsworthy, Pilbara Craton, Western Australia: evi-
dence for the early evolution of continental crust and hydrothermal alteration.
Precambrian Res. 147, 124–147.
Sugitani, K., Yamashita, F., Nagaoka, T., Minami, M., Yamamoto, K., 2006b. Geo-
chemistry of heavily altered Archaean volcanic and volcaniclastic rocks of the
Warrawoona Group, at Mt. Goldsworthy in the Pilbara Craton, Western Aus-
tralia: implications for alteration and origin. Geochem. J. 40, 523–535.
Sugitani, K., Grey, K., Allwood, A., Nagaoka, T., Mimura, K., Minami, M., Marshall,
C.P., Van Kranendonk, M.J., Walter, M.R., 2007. Diverse microstructures from
Archaean chert from the Mount Goldsworthy–Mount Grant area, Pilbara Craton,
Western Australia: Microfossils, dubiofossils, or pseudofossils? Precambrian
Res. 158, 228–262.
Taylor, S.R., McLennan, S.M., 1985. The Continental Crust: Its Composition and Its
Evolution. Blackwell, Oxford, 312 pp.
Tice, M.M., Lowe, D.R., 2006a. The origin of carbonaceous matter in pre-3.0 Ga green-
stone terrains: a review and new evidence from the 3.42 Ga Buck Reef Chert.
Earth Sci. Rev. 76, 259–300.
Tice, M.M., Lowe, D.R., 2006b. Hydrogen-based carbon fixation in the earliest known
photosynthetic organisms. Geology 34, 37–40.
Van Kranendonk, M.J., 2006. Volcanic degassing, hydrothermal circulation and the
flourishing of early life on Earth: a review of the evidence from c. 3490–3240 Ma
rocks of the Pilbara Supergroup, Pilbara Craton, Western Australia. Earth Sci. Rev.
74, 197–240.
Van Kranendonk, M.J., Webb, G.E., Kamber, B.S., 2003. Geological and trace element
evidence for a marine sedimentary environment of deposition and biogenicity of
3.45 Ga stromatolitic carbonates in the Pilbara Craton, and support for a reducing
Archaean ocean. Geobiology 1, 91–108.
Van Kranendonk, M.J., Hickman, A.H., Smithies, R.H., Williams, I.R., Bagas, L., Farrell,
T.R., 2006. Revised lithostratigraphy of Archean supracrustal and intrusive rocks
in the northern Pilbara Craton, Western Australia. Geological Survey of Western
Australia, Record 2006/15.
Van Kranendonk, M.J., Smithies, R.H., Hickman, A.H., Champion, D.C., 2007. Review:
secular tectonic evolution of Archaean continental crust: interplay between hor-
izontal and vertical processes in the formation of the Pilbara Craton, Australia.
Terra Nova 19, 1–38.
Watanabe, Y., Martini, J.E.J., Ohmoto, H., 2000. Geochemical evidence for terrestrial
ecosystems 2.6 billion years ago. Nature 408, 574–578.
Webb, G.E., Kamber, B.S., 2000. Rare earth elements in Holocene reefal microbialites:
a new shallow seawater proxy. Geochim. Cosmochim. Acta 64, 1557–1565.
Westall, F., de Wit, M.J., Dann, J., van der Gaast, S., de Ronde, C.E.J., Gerneke, D.,
2001. Early Archean fossil bacteria and biofilms in hydrothermally-influenced
sediments from the Barberton Greenstone Belt, South Africa. Precambrian Res.
106, 93–116.
Wood, S.A., 2006. Rare earth element systematics of acidic geothermal waters from
Taupo Volcanic Zone, New Zealand. J. Geochem. Explor. 89, 424–427.
Yamamoto, K., Itoh, N., Matsumoto, T., Tanaka, T., Adachi, M., 2004. Geochemistry of
Precambrian carbonate intercalated in pillows and its host basalt: implications
for the REE composition of circa 3.4 Ga seawater. Precambrian Res. 135, 331–
344.