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Precambrian Research 177 (2010) 73–87

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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-


ing studies on highly elaborate structures and their complex
A morphologically diverse assemblage of biological structures occurrences suggestive of life cycle (Sugitani et al., 2009b), paly-
(threads, films, spheroids, and lens-spindles) has recently been nological extraction of the structures (Grey and Sugitani, 2009),
reported from sedimentary carbonaceous black cherts of the ca. NanoSIMS chemical analyses of individual structures (Oehler et
3.0 Ga Farrel Quartzite of the Mount Goldsworthy greenstone al., 2009) and 3D reconstruction of morphological and textural
belt in the Pilbara Craton, Western Australia (Sugitani et al., complexity (Sugitani et al., 2009a). These microfossils are outstand-
2007) (Fig. 1). Their biogenicity was claimed from indigenousness, ing for their morphological diversity and complexity, excellent
syngenecity, narrow size distribution, carbonaceous composition, preservation of some specimens, and large size, which are dis-
evidence of flexible but breakable walls, apparent taphonomic tinct from many of previously reported Archean microfossils that
features and the presence of colony-like aggregations (Sugitani are generally small and simple in morphology (e.g., Knoll and
et al., 2007). The credibility of the structures as microfossils 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
∗ Corresponding author. Fax: +81 52 789 4865. (Sugitani et al., 2009b), implies that there was a diverse micro-
E-mail address: sugi@info.human.nagoya-u.ac.jp (K. Sugitani). bial ecosystem flourishing in a shallow-water environment at ca.
1
Present address: Shinto Tsushin Co., Ltd. Nagoya 460-0002, Japan. 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 2. Geological background
place constraints on the phylogeny of the putative microfossils, has
not yet been specified. Specifically, it is still equivocal whether 2.1. General geology
the cherts were non-marine or marine, or whether they were
hydrothermal or non-hydrothermal. In this study, we attempt to The 3.72–2.83 Ga Pilbara Craton (Fig. 2a) has three lithotectoni-
answer these questions through systematic rare-earth element and cally different granite-greenstone terrains; the 3.53–3.165 Ga East
yttrium (REE + Y) analyses. Pilbara Terrane (EPT), the >3.18 Ga Kurrana Terrane (KT), and the
REE + Y have long been used as a proxy to determine the ori- West Pilbara Superterrane (WPS), which includes the 3.27 Ga Kar-
gin and depositional environment of fine-grained sediments and ratha Terrane, the ca. 3.20 Ga Regal Terrane, and the 3.13–3.11 Ga
sedimentary rocks, especially those of chemical and biogenic ori- Sholl Terrane (Van Kranendonk et al., 2007). The EPT represents
gins (e.g., Murray et al., 1991; Webb and Kamber, 2000; Shimizu the ancient nucleus of the Pilbara Craton (Fig. 2b) and comprises
et al., 2001). Its application to Precambrian carbonates, banded the Pilbara Supergroup of volcano-sedimentary rocks and several
iron-formations (BIFs) and cherts have also provided important generations of intrusive granitic rocks. The Pilbara Supergroup is
information about the origins and evolution of surface envi- divided into five groups; the 3.52–3.42 Ga Warrawoona Group,
ronments on the early Earth (e.g., Derry and Jacobsen, 1990; the 3.42–3.35 Ga Strelley Pool Formation, the 3.35–3.31 Ga Kelly
Danielson et al., 1992; Alibert and McCulloch, 1993; Bau and Group, the 3.27–3.23 Ga Sulphur Springs Group and the ca. 3.19 Ga
Möller, 1993; Bau and Dulski, 1996; Kato and Nakamura, 2003; Soanesville Group. The Supergroup is overlain unconformably by
Van Kranendonk et al., 2003; Kamber et al., 2004; Yamamoto et the 3.02 Ga Gorge Creek Group of the late-tectonic De Grey Super-
al., 2004; Bolhar et al., 2005; Hofmann, 2005; Bolhar and Van group (Van Kranendonk et al., 2007; Hickman, 2008).
Kranendonk, 2007; Frei et al., 2008). For example, Danielson et al.
(1992) suggested based on REE patterns of BIF of various ages and 2.2. Local geology, depositional environment
localities that the dominant type of sea-floor alteration changed
from high-temperature to low-temperature during the Protero- The Mount Goldsworthy greenstone belt of the Pilbara Craton,
zoic. Van Kranendonk et al. (2003) reported REE + Y data of ca. which is composed of Mount Goldsworthy and Mount Grant, is
3.40 Ga Strelley Pool Chert stromatolitic carbonates and concluded located approximately 100 km east of Port Hedland (Fig. 2b). The
that they were deposited from anoxic Archean shallow seawa- stratigraphic succession of this greenstone belt less than 1 km thick
ter. is composed of a lower, dominantly volcanic sequence of rocks
In this study, we present a systematic dataset of REE + Y that is part of the 3.53–3.17 Ga Pilbara Supergroup, and an upper,
from cherts of various lithologies from the Mount Goldswor- dominantly sedimentary succession that is part of the 3.02–2.93 Ga
thy greenstone belt, with the aim of placing constraints on De Grey Supergroup (Hickman and Van Kranendonk, 2008). The
the origin of the black cherts that contain microfossils. Com- 3.02 Ga Gorge Creek Group, a lower part of the De Grey Super-
parison of the microfossil-bearing black cherts with other group, comprises a clastic formation, the Farrel Quartzite, and an
lithologies, including ferruginous cherts (jaspilite) and banded upper formation of chert, banded iron-formation, black shale, and
iron-formation, laminated black chert that does not contain siltstone, the Cleaverville Formation.
microfossils, and black vein chert should provide us with crit- The Farrel Quartzite in the Mount Goldsworthy greenstone
ical information about the water chemistry from which the belt is composed of moderately metamorphosed (greenschist
microfossil-bearing black cherts were precipitated and thus shed facies), pervasively silicified, fine to very coarse-grained sandstone
light on the habitable environment of the early life in the study including quartzite with minor conglomerate, mafic to ultra-
area. 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 cherts and banded iron-formation of the Cleaverville Formation
several meters to 80 m, two beds of evaporite that occur in the were deposited. The higher abundance of sandstone beds and
quartzite at Mount Grant, particularly the upper one in CE2 (Fig. 2d), lenses in the lower part of this horizon suggests that the formation
are laterally continuous. This upper evaporite bed can be traced represents a deepening-upward sequence (Sugitani et al., 2003).
ca. 7 km along strike in the central and the western part of Mount
Grant. 2.3. Black chert occurrences
The Farrel Quartzite is conformably overlain by the Cleaverville
Formation, which dominantly consists of finely parallel-laminated Several different occurrences of black chert have been identi-
variegated chert, including dark-grey shale, carbonaceous black fied. Black chert veins are less than 30 cm thick, and locally occur in
chert, jaspilite and banded iron-formation, with minor coarse- the Warrawoona Group altered volcanic and volcaniclastic rocks
grained terrigenous clastic rocks near the base. The terrigenous (Sugitani et al., 2006b). In the Farrel Quartzite, stratiform black
clastic rocks occur as beds and lenses, in some places with abundant cherts are less than 30 cm thick and occur in close association with
platy chert clasts. evaporite beds at two stratigraphic levels (Fig. 2d). These associ-
Sugitani et al. (2003, 2006a) suggested that the Farrel Quartzite ations were designated as CE1 for the lower horizon and CE2 for
was deposited in a continental margin setting and that terrige- the upper horizon at the top of the Farrel Quartzite, respectively
nous detrital materials may have been partially derived from (Fig. 2d). A cm-scale black vein chert locally occurs within sand-
older continental crust. Silicified evaporites probably originated stone of the Farrel Quartzite. Evaporite is occasionally replaced by
from nahcolite (Na2 HCO3 ), suggesting the development of shal- black chert. Stratiform black cherts are common in the Cleaverville
low to sub-aerial conditions. This shallow to sub-aerial depositional Formation, intercalated with other variegated chert layers. To date,
environment of the Farrel Quartzite was followed by a deeper the microfossils have been found only in the stratiform black chert
subaqueous environment, in which finely and parallel-laminated of CE2 (Sugitani et al., 2007).
H. Sugahara et al. / Precambrian Research 177 (2010) 73–87 77

3. Sample descriptions 4.2. Rare-earth elements and yttrium (REE + Y)

Fifty-two chert samples were collected for analysis. We catego- Analyses of REE + Y followed the method of Yamamoto et al.
rized the samples into four lithological types, including; laminated (2004). Black chert samples (150–350 g) were coarsely crushed
to banded chert (LC), vein chert (VC), and stratiform chert associ- with a jaw crusher. Small chips (5 mm in size) were handpicked to
ated with evaporites (CE1 and CE2). LC samples (n = 29) are from the exclude visible detrital laminae and weathered parts. After pulver-
Cleaverville Formation at Mount Goldsworthy (n = 20) and at Mount izing with an agate mortar, HF and HClO4 (HF:HClO4 = 2:1) were
Grant (n = 9). VC samples (n = 5) are all from altered mafic volcanic added to sample powders (3 g) for digestion. The sample solu-
rocks of the Warrawoona Group at Mount Grant. CE1 samples (n = 4) tions were dried on a hot plate (180 ◦ C). The dried samples were
are from one locality at Mount Grant. CE2 samples (n = 13) are dissolved with 1.7N-HCl and supernatants were collected after
from Mount Grant (n = 10) and Mount Goldsworthy (n = 3). Detailed centrifugation. This procedure from digestion with mixed acids
descriptions of these chert lithologies are given below. (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
3.1. LC: laminated to banded chert
to remove interfering elements such as Ba (Hirata et al., 1988).
The collected REE + Y solutions were dried on a hot plate (180 ◦ C)
Laminated to banded chert from the Cleaverville Formation
and then dissolved in 2% HNO3 . REE + Y concentrations were deter-
is characterized by parallel lamination or banding. Lamination is
mined by inductively coupled plasma mass spectrometer (ICP-MS).
mostly planar to undulating and occasionally anastomosing. It con-
Indium and Bi were used as internal standards. Interfering oxide
tains very fine particles of carbonaceous matter, hematite and/or
ions of LREE (light rare-earth elements) on HREE (heavy rare-earth
carbonate, in addition to predominant microcrystalline to granular
elements) were corrected by measuring 20 ppb LREE solutions.
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- 4.3. Organic geochemistry
nae are predominant and locally Fe-rich beds equivalent to banded
iron-formation are present, whereas at Mount Grant laminae com- Insoluble carbonaceous material (kerogen) was extracted from
posed of carbonaceous matter or carbonate are predominant within 24 black chert samples (5 samples of VC, 2 of CE1, 7 of CE2, and 10
the stratigraphic interval (∼90m) from which we collected samples. of LC). The carbon stable isotopic ratio of the extracted kerogens
was measured using a dual-inlet isotope ratio mass spectrometry
3.2. VC: vein chert (IRMS). The carbon content of bulk rock samples was also deter-
mined, using an elemental analyzer. Detailed analytical procedures
Vein chert from the Warrawoona Group does not display lami- are given below.
nation or bedding. Very fine carbonaceous particles are distributed
homogeneously in some samples, whereas they comprise floccu-
4.3.1. Isolation of kerogen
lated grains in others (Fig. 3c). Relatively large quartz grains, lithic
Black chert samples were pulverized with a stainless steel mor-
fragments and mica are rare. This type of chert commonly contains
tar. Sample powders (150–350 g) were then treated with 6M-HCl.
abundant tabular crystals of secondary origin, which are assumed
A mixed acid (HF:HCl = 4:1) was added to sample powders for
to be a tourmaline-group mineral, based on XRD analyses.
digestion, followed by rinsing with distilled water. This mixed
acid treatment was repeated twice until silicates were decom-
3.3. CE1 and CE2: stratiform chert posed completely. Then, the residue was cleaned with hot HCl
(80 ◦ C) for 48 h, yielding residues composed of kerogen and pyrite.
Stratiform black chert from CE1 is characterized by parallel to Kerogen was separated from pyrite using a heavy liquid (CHBr3 ;
slightly undulating laminations and locally has abundant detrital 2.9 g/cm3 ). The separated kerogens were washed with CHCl2 in
carbonaceous grains (Fig. 3d). Stratiform black chert CE2, on the soxhlet extraction apparatus for 72 h, with the aim of removal of
other hand, is mostly massive, with local cross or parallel lamina- possible contamination by organic matter introduced during the
tion. It also contains a cavity-fill white chert layer with botryoidal experiment.
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 4.3.2. Stable carbon isotopic ratio (ı13 C)
the cavity-fill chert. The massive portion of this chert is composed The extracted kerogen (0.5–1.0 mg) was sealed in Vycor tubes
of a microcrystalline quartz matrix with disseminated carbona- that were preheated at 950 ◦ C. Atmospheric CO2 gas was evacuated
ceous material, unknown acicular crystals, and sulphide. Rare barite during sealing. Then, samples were converted into CO2 at 900 ◦ C for
and carbonate are also present. Carbonaceous particles in the mas- 4 h, with CuO as an oxidizer. The sample CO2 gas was first trapped in
sive matrix tend to be distributed heterogeneously, resulting in the Vycor tube in a liquid N2 bath (−196 ◦ C), and then released to the
the development of irregularly shaped pure chert masses that are second tube by replacing the liquid N2 bath with a liquid N2 -ethanol
morphologically similar to fenestrae (Fig. 3f). 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
4. Analytical methods the PDB scale. The precision of the IRMS analysis was ±0.05‰.

4.1. Major elements


5. Results
Concentrations of selected major elements (TiO2 , Al2 O3 , Fe2 O3
and P2 O5 ) were determined by X-ray fluorescence spectrometer The results of chemical analyses are shown in Table 1. Averages
(XRF) (PANalytical Axios), using fused-glass discs made from a mix- and ranges for some indices are listed in Table 2. Shale (PAAS)-
ture of sample powder and Li2 B4 O7 in the proportion of 1:8. 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 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-
All chert samples are characterized by low concentrations of ues. The samples show slight to moderate positive anomalies of La
TiO2 and Al2 O3 (TiO2 = 0.002–0.062%, Al2 O3 = 0.02–1.13%)(Table 1). and Eu (1.26–1.70 for La and 1.52–1.63 for Eu), but Ce-anomalies
Fe2 O3 (as total iron) concentrations range widely from 0.019 to are negligible (0.98–1.14).1 CE1 samples are characterized by
57.45%, reflecting the wide range of lithology. Total carbon content relative enrichment of LREE (Pr/YbPAAS = 1.10–4.00) and MREE
is from 0.023 to 0.073%, with an exception of SGH8 (0.12%) that (Sm/YbPAAS = 1.26–3.31), chondritic to super-chondritic Y/Ho ratios
probably is attributed to higher abundance of carbonate. (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).
5.2. Rare-earth elements

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 83

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- Ikeuchi, 1979; Masuda et al., 1987; Ohta and Kawabe, 2000). HREE-
nated to banded chert (LC) was deposited (Sugitani et al., 2003; also enrichment and positive La-anomalies have been reported from
see Fig. 2d). The geological context favours a marine origin for LC, Archean chemical sediments such as cherts, BIFs, stromatolites and
which can be tested by examination of their REE + Y characteristics. inter-pillow carbonates, and often taken as evidence for their sea-
water origin (Van Kranendonk et al., 2003; Yamamoto et al., 2004;
6.2.1. Description of REE + Y features Kamber et al., 2004; Bolhar et al., 2004, 2005).
The shale-normalized REE characteristics of most LC samples Y/Ho ratios range from 36.7 to 53.5 for Mount Grant LC sam-
are: (1) enrichment of HREE relative to LREE and MREE; (2) positive ples, and from 32.0 to 68.4 for Mount Goldsworthy samples. About
La-anomalies; (3) a wide range of Y/Ho, from chondritic to super- one-half of samples have markedly higher Y/Ho (>45). Such frac-
chondritic values (up to 70), positive Eu-anomalies (up to 2.56), and tionated Y/Ho ratios have been observed for modern seawater and
a wide range of Ce-anomalies (Table 1 and Figs. 4 and 6). Among is interpreted to reflect preferential scavenging of REE by particu-
these characteristics, HREE-enrichment, positive La-anomalies and late matter in the seawater column (Nozaki et al., 1997) and/or near
super-chondritic Y/Ho values characterize modern seawater, and hydrothermal vent settings (Bau and Dulski, 1999). On the other
chemical and biogenic sediments of seawater origin (Masuda et hand, no fractionations are expected between Y and Ho during high
al., 1987; Lee and Byrne, 1993; Bau and Dulski, 1996; Webb and temperature fluid–rock interaction (Bolhar et al., 2005), resulting
Kamber, 2000). HREE-enrichment is explained by preferential cou- in chondritic values of hydrothermal water (Y/Ho = 26–27; Pack et
pling of HREE with carbonate ions due to their smaller ionic al., 2007). Data of Y/Ho for river waters are scarce and variable,
radius compared to LREE and MREE, resulting in selective reten- with commonly lower values than for seawater and with some
tion of HREE in seawater and thus their relative enrichment (Lee equal to upper continental crust (28) (Nozaki et al., 1997; Lawrence
and Byrne, 1993). The positive La-anomaly, on the other hand, et al., 2006). Like HREE-enrichment and positive La-anomalies,
is explained by the W-type tetrad effect that is observed in sea- Y/Ho ratios have recently been used as a proxy for a marine or
water and chemical sediments of seawater origin (Masuda and non-marine origin of Archean chemical sedimentary rocks (e.g.,
84 H. Sugahara et al. / Precambrian Research 177 (2010) 73–87

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
Fig. 6. [La/{Pr(Pr/Nd)2 }]PAAS vs. [Ce/{Pr(Pr/Nd)}]PAAS plot, discriminating between mass with a negligible Eu-anomaly and chondritic Y/Ho, of proba-
La-anomaly and Ce-anomaly (after Lawrence et al., 2006). Panorama Formation BIF ble non-marine origin. This introduced water represents seawater,
samples of hydrothermal origin (Archean) (Bolhar et al., 2005), and Strelley Pool which is consistent with the HREE-enrichment of most LC samples.
Chert carbonates (Archean) (Van Kranendonk et al., 2003) and Holocene micro- Additionally, all LC samples have positive La-anomalies (1.28–3.16)
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
and samples from the upper horizons have higher values (1.92–2.23
with the majority of CE1 and 2 and VC samples, Panorama samples and Holocene for the uppermost four samples from Mount Grant and 2.36–3.16
microbialites. 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.
Bolhar and Van Kranendonk, 2007).

6.2.2. Interpretation 6.3. REE + Y systematics of cherts


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, Chert lithologies VC, CE1 and CE2 have somewhat different
Eu-anomalies of LC samples also show an increase upsection from REE + Y characteristics from LC samples, as summarized below.
1.3 to 2.5 (Fig. 7b). Positive Eu-anomalies often have been regarded
as the signature of a hydrothermal component in Archean chemical (1) VC samples do not show HREE-enrichment relative to LREE
sedimentary rocks (Danielson et al., 1992; Sugitani, 1992; Kato et and MREE, but rather tend to be enriched in MREE (Fig. 4a).
al., 1998; Bau and Dulski, 1999; Kato and Nakamura, 2003; Bolhar They show positive La-anomalies (1.26–1.70) and no distinct
et al., 2005), because modern high-T hydrothermal vent solutions negative Ce-anomalies (0.98–1.14). Y/Ho ratios are chondritic

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

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 carbonaceous cherts that contain morphologically diverse, abun-
On the Y/Ho–Eu-anomaly diagram, most VC, CE1 and CE2 sam- dant microfossils (Sugitani et al., 2007). The chert samples for this
ples plot within a relatively narrow area of slightly super-chondritic study include black vein chert (VC) in the Warrawona Group mafic
Y/Ho ratios and small positive Eu-anomalies (Fig. 9). This area is to ultramafic volcanic sequence, stratiform black chert associated
close to, or overlaps with some of LC samples from the lower part with evaporite (CE1 and CE2) in the Farrel Quartzite and varicolored
of the Cleaverville Formation. laminated to banded chert (LC) in the Cleaverville Formation. Lam-
CE1 and CE2 cherts are closely associated with evaporite beds inated to banded cherts (LC) of the Cleaverville Formation show
(Fig. 2d), which suggests that the cherts were formed in a closed to a clear stratigraphic trend of increasing Y/Ho and Eu-anomaly,
semi-closed basin most likely in a continental setting (Sugitani et with HREE-enrichment and a positive La-anomaly. On the pro-
al., 2003, 2006a). In this setting, water mass was likely influenced by posed Y/Ho–Eu-anomaly diagram, LC samples comprise an array
non-marine water. Slight LREE-enrichment, slight super-chondritic showing mixing of the two end-member components; one is the
Y/Ho ratios and negligible Eu-anomalies of CE1 samples all refute most likely Archean seawater with super-chondritic (∼100) Y/Ho
that they originated solely from seawater: rather, they are more ratio and a weak positive Eu-anomaly (∼3) and the other charac-
likely precipitated from a water mass whose REE + Y features were terized by chondritic Y/Ho and negligible Eu-anomaly is assumed
significantly controlled by non-marine sources such as continental to be non-marine water such as continental run-off, ground water,
run-off and ground water, and possibly geothermal water, con- or geothermal water, considering their supposed continental mar-
sidering it does not always have positive Eu-anomaly (e.g., Wood, gin depositional setting for the Farrel Quartzite (Sugitani et al.,
2006). CE2 samples except for two samples, on the other hand, have 2003, 2006a). Other chert samples including black cherts associ-
more seawater-like REE + Y features as described above, suggest- ated evaporite (CE1 and CE2) in the Farrel Quartzite, except two,
ing their precipitation from a water mass that was influenced by plot on the array defined by LC, clustering around the supposed
seawater components to a larger degree. non-marine end-member component. The result suggests that the
Although REE + Y characteristics of VC samples are difficult to water mass chemistry, from which CE1 and CE2 black cherts were
explain, the results of our study suggest that black vein chert would precipitated, was influenced significantly by non-marine water and
not be necessarily products of high-temperature deep hydrother- that formation of black vein chert (VC) is not necessarily attributed
mal activity (Van Kranendonk, 2006; Lindsay et al., 2007). Rather, to high-T hydrothermal activity. The microfossil-bearing black
the origin of black vein chert studied here could be interpreted as cherts of the ca. 3.0 Ga Farrel Quartzite in the Mount Goldswor-
low-T hydrothermal activity or in an analogy with the carbona- thy greenstone belt were formed in a moderate and habitable
ceous vein chert in Barberton greenstone belt, which were thought condition.
formed by hydraulic fracturing (Hofmann and Bolhar, 2007). In
either case, it can be emphasized that REE characteristics of VC are Acknowledgements
distinct from microfossil-bearing CE2.
This paper is a product of a grant-in-aid supported by the Japan
6.4. Implications of Archean non-marine ecosystem Society for the Promotion of Science (No. 19340150). We wish to
express our gratitude to Dr. K. Grey for her support to our fieldwork
Despite the similar occurrence with CE2 samples containing in the Pilbara Craton and to Dr. M.J. Van Kranendonk for his help-
abundant microfossils of diverse morphologies, CE1 black cherts do ful comments on interpretations of geology of Mount Goldsworthy
not contain microfossils. However, this may be merely attributed and Mount Grant area and for informal review and constructive
to their destruction during reworking and transportation, consid- comments. We also acknowledge to Mike Tice and an anonymous
ering that sedimentary textures of the CE1 cherts indicate their reviewer for their critical and constructive comments.
deposition under a higher energy environment compared with CE2
black chert (Sugitani et al., 2007). In either case, significantly light References
carbon isotopic values are consistent with a biogenic origin of car-
Alibert, C., McCulloch, M.T., 1993. Rare earth element and neodymium isotopic com-
bonaceous matter. Although light carbon isotopes cannot be “a
positions of the banded iron-formations and associated shales from Hamersley,
smoking-gun” for microbes (Brasier et al., 2005; McCollom and western Australia. Geochim. Cosmochim. Acta 57, 187–204.
Seewald, 2006; Lindsay et al., 2007), the presence of microfossils Allwood, A.C., Walter, M.R., Kamber, B.S., Marshall, C.P., Burch, I.W., 2006. Stroma-
in black chert of the similar occurrence (CE2) supports the biogenic tolite reef from the Early Archaean era of Australia. Nature 441, 714–718.
Bau, M., 1991. Rare-earth element mobility during hydrothermal and metamorphic
origin of CE1 carbonaceous matter. fluid–rock interaction and the significance of the oxidation state of europium.
CE2 black cherts are also believed deposited in the evapor- Chem. Geol. 93, 219–230.
itic basin to which both non-marine and marine waters could Bau, M., Dulski, P., 1996. Distribution of yttrium and rare-earth element in the Penge
and Kuruman iron-formations, Transvaal Supergroup, South Africa. Precambrian
have inflow as discussed above. Unfortunately, source of non- Res. 79, 37–55.
marine water cannot yet be specified. It is, however, inferred from Bau, M., Dulski, P., 1999. Comparing yttrium and rare earths in hydrothermal fluids
the present results that microorganisms had already flourished 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,
in shallow, evaporitic environment and even comprised complex 77–90.
ecosystem, probably in the continental margin setting by at least Bau, M., Möller, P., 1993. Rare earth element systematics of the chemically precipi-
3.0 Ga. This is consistent with or supports some previous studies tated component in Early Precambrian iron formations and the evolution of the
terrestrial atmosphere-hydrosphere-lithosphere system. Geochim. Cosmochim.
suggesting the early evolution of shallow to sub-aerial and/or non-
Acta 57, 2239–2249.
marine ecosystem (e.g., Watanabe et al., 2000; Allwood et al., 2006; Bolhar, R., Van Kranendonk, M.J., Kamber, B.S., 2005. A trace element study of
Tice and Lowe, 2006a,b; Bolhar and Van Kranendonk, 2007). 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
7. Conclusions
northern Fortescue Group, Pilbara Craton, inferred from trace element geochem-
istry of stromatolitic carbonates. Precambrian Res. 155, 229–250.
Systematic REE + Y analyses were conducted to understand the Bolhar, R., Kamber, B.S., Moorbath, S., Fedo, C.M., Whitehouse, M.J., 2004. Character-
origins and depositional environments of Archean (ca. 3.0 Ga) isation of early Archaean chemical sediments by trace element signatures. Earth
Planet. Sci. Lett. 222, 43–60.
cherts of various lithologies and occurrences from the Mount Brasier, M.D., Green, O.R., Lindsay, J.F., McLoughlin, N., Steele, A., Stoakes, C., 2005.
Goldsworthy greenstone belt in the Pilbara Craton, including black 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 87

chert, Chinaman Creek, Western Australia. Precambrian Res. 140, 55–102. REE(III)-carbonate complexation constants. Geochem. J. 34, 455–473.
Danielson, A., Möller, P., Dulski, P., 1992. The europium anomalies in banded iron Pack, A., Russell, S.S., Shelley, J.M.G., Van Zuilen, M., 2007. Geo- and cosmochem-
formations and the thermal history of the oceanic crust. Chem. Geol. 97, 89–100. istry of the twin elements yttrium and holmium. Geochim. Cosmochim. Acta
Derry, L.A., Jacobsen, S.B., 1990. The chemical evolution of Precambrian seawater: 71, 4592–4608.
evidence from REEs in banded iron formations. Geochim. Cosmochim. Acta 54, Rasmussen, B., 2000. Filamentous microfossils in a 3,235-million-year-old vol-
2965–2977. canogenic massive sulphide deposit. Nature 405, 676–679.
Douville, E., Bienvenu, P., Charlou, J.L., Donval, J.P., Fouquet, Y., Appriou, P., Gamo, Shimizu, H., Kunimaru, T., Yoneda, S., Adachi, M., 2001. Sources and depositional
T., 1999. Yttrium and rare earth elements in fluids from various deep-sea environments of some Permian and Triassic cherts: significance of Rb–Sr and
hydrothermal systems. Geochim. Cosmochim. Acta 63, 627–643. Sm–Nd isotopic and REE abundance data. J. Geol. 109, 105–125.
Dunlop, J.S.R., Milne, V.A., Groves, D.I., Muir, M.D., 1978. A new microfossil assem- Smithies, R.H., Van Kranendonk, M.J., Hickman, A.H., 2004. De Grey, W.A. Sheet 2757
blage from the Archaean of Western Australia. Nature 274, 676–678. (Version 2.0): Western Australia Geological Survey, 1:100000 Geological Series.
Farquhar, J., Bao, H., Thiemens, M., 2000. Atmospheric influence of earth’s earliest Sugitani, K., 1992. Geochemical characteristics of Archean cherts and other sedi-
sulfur cycle. Science 289, 756–758. mentary rocks in the Pilbara Block, Western Australia: evidence for Archean
Frei, R., Dahl, P.S., Duke, E.F., Frei, K.M., Hansen, T.R., Frandsson, M.M., Jensen, L.A., seawater enriched in hydrothermally-derived iron and silica. Precambrian Res.
2008. Trace element and isotopic characterization of Neoarchean and Paleopro- 57, 21–47.
terozoic iron formations in the Black Hills (South Dakota, USA): assessment of Sugitani, K., Grey, K., Nagaoka, T., Mimura, K., 2009a. Three-dimensional mor-
chemical change during 2.9–1.9 Ga deposition bracketing the 2.4–2.2 Ga first phological and textural complexity of Archean putative microfossils from
rise of atmospheric oxygen. Precambrian Res. 162, 441–474. the northeastern Pilbara Craton: indications of biogenicity of large (>15 ␮m)
Grey, K., Sugitani, K., 2009. Palynology of Archean microfossils (ca. 3.0 Ga) from spheroidal and spindle-like structures. Astrobiology 9, 603–615.
the Mount Grant area, Pilbara Craton, Western Australia: further evidence of Sugitani, K., Grey, K., Nagaoka, T., Mimura, K., Walter, M.R., 2009b. Taxonomy and
biogenicity. Precambrian Res. 173, 60–69. biogenicity of Archaean spheroidal microfossils (c. 3.0 Ga) from the Mount
Hickman, A.H., 2008. Regional review of the 3426-3350 Ma Strelley Pool Forma- Goldsworthy–Mount Grant area in the northeastern Pilbara Craton, Western
tion, Pilbara Craton, Western Australia. Geological Survey of Western Australia, Australia. Precambrian Res. 173, 50–59.
Record 2008/15. Sugitani, K., Mimura, K., Suzuki, K., Nagamine, K., Sugisaki, R., 2003. Stratigraphy and
Hickman, A.H., Van Kranendonk, M.J., 2008. Archean crustal evolution and min- sedimentary petrology of an Archean volcanic-sedimentary succession at Mt.
eralization of the northern Pilbara Craton—a field guide. Geological Survey of Goldsworthy in the Pilbara Block, Western Australia: implications of evaporite
Western Australia, Record 2008/13. (nahcolite) and barite deposition. Precambrian Res. 120, 55–79.
Hirata, T., Shimizu, H., Akagi, T., Sawatari, H., Masuda, A., 1988. Precise determina- Sugitani, K., Yamashita, F., Nagaoka, T., Yamamoto, K., Minami, M., Mimura, K.,
tion of rare earth elements in geological standard rocks by inductively coupled Suzuki, K., 2006a. Geochemistry and sedimentary petrology of Archean clastic
plasma source mass spectrometry. Anal. Sci. 4, 637–643. sedimentary rocks at Mt.Goldsworthy, Pilbara Craton, Western Australia: evi-
Hofmann, A., 2005. The geochemistry of sedimentary rocks from the Fig Tree Group, dence for the early evolution of continental crust and hydrothermal alteration.
Barberton greenstone belt: implications for tectonic, hydrothermal and surface Precambrian Res. 147, 124–147.
processes during mid-Archaean times. Precambrian Res. 143, 23–49. Sugitani, K., Yamashita, F., Nagaoka, T., Minami, M., Yamamoto, K., 2006b. Geo-
Hofmann, A., Bolhar, R., 2007. Carbonaceous cherts in the Barberton greenstone chemistry of heavily altered Archaean volcanic and volcaniclastic rocks of the
belt and their significance for the study of early life in the Archean record. Warrawoona Group, at Mt. Goldsworthy in the Pilbara Craton, Western Aus-
Astrobiology 7, 355–388. tralia: implications for alteration and origin. Geochem. J. 40, 523–535.
Holland, H.D., 1994. Early Proterozoic atmospheric change. In: Bengston, S. (Ed.), Sugitani, K., Grey, K., Allwood, A., Nagaoka, T., Mimura, K., Minami, M., Marshall,
Early Life on Earth. Columbia University Press, New York, pp. 237–244. C.P., Van Kranendonk, M.J., Walter, M.R., 2007. Diverse microstructures from
Kato, Y., Nakamura, K., 2003. Origin and global tectonic significance of Early Archean Archaean chert from the Mount Goldsworthy–Mount Grant area, Pilbara Craton,
cherts from the Marble Bar greenstone belt, Pilbara Craton, Western Australia. Western Australia: Microfossils, dubiofossils, or pseudofossils? Precambrian
Precambrian Res. 125, 191–243. Res. 158, 228–262.
Kato, Y., Ohta, I., Tsunematsu, T., Watanabe, Y., Isozaki, Y., Maruyama, S., Imai, Taylor, S.R., McLennan, S.M., 1985. The Continental Crust: Its Composition and Its
N., 1998. Rare earth element variations in mid-Archean banded iron forma- Evolution. Blackwell, Oxford, 312 pp.
tions: Implications for the chemistry of ocean and continent and plate tectonics. Tice, M.M., Lowe, D.R., 2006a. The origin of carbonaceous matter in pre-3.0 Ga green-
Geochim. Cosmochim. Acta 62, 3475–3497. stone terrains: a review and new evidence from the 3.42 Ga Buck Reef Chert.
Kamber, B.S., Bolhar, R., Webb, G.E., 2004. Geochemistry of late Archaean stroma- Earth Sci. Rev. 76, 259–300.
tolites from Zimbabwe: evidence for microbial life in restricted epicontinental Tice, M.M., Lowe, D.R., 2006b. Hydrogen-based carbon fixation in the earliest known
seas. Precambrian Res. 132, 379–399. photosynthetic organisms. Geology 34, 37–40.
Kamber, B.S., Webb, G.E., 2001. The geochemistry of late Archean microbial carbon- Van Kranendonk, M.J., 2006. Volcanic degassing, hydrothermal circulation and the
ate: implications for ocean chemistry and continental erosion history. Geochim. flourishing of early life on Earth: a review of the evidence from c. 3490–3240 Ma
Cosmochim. Acta 65, 2509–2525. rocks of the Pilbara Supergroup, Pilbara Craton, Western Australia. Earth Sci. Rev.
Knoll, A.H., Barghoorn, E.S., 1977. Archean microfossils showing cell division from 74, 197–240.
the Swaziland system of South Africa. Science 198, 396–398. Van Kranendonk, M.J., Webb, G.E., Kamber, B.S., 2003. Geological and trace element
Lee, J.H., Byrne, R.H., 1993. Complexation of trivalent rare earth elements (Ce, Eu, evidence for a marine sedimentary environment of deposition and biogenicity of
Gd, Tb, Yb) by carbonate ions. Geochim. Cosmochim. Acta 57, 295–302. 3.45 Ga stromatolitic carbonates in the Pilbara Craton, and support for a reducing
Lindsay, J.F., Brasier, M.D., McLoughlin, N., Green, O.R., Fogel, M., Steele, A., Mertz- Archaean ocean. Geobiology 1, 91–108.
man, S.A., 2007. The problem of deep carbon—an Archean paradox. Precambrian Van Kranendonk, M.J., Hickman, A.H., Smithies, R.H., Williams, I.R., Bagas, L., Farrell,
Res. 143, 1–22. T.R., 2006. Revised lithostratigraphy of Archean supracrustal and intrusive rocks
Lawrence, M.G., Greig, A., Collerson, K.D., Kamber, B.S., 2006. Rare earth element and in the northern Pilbara Craton, Western Australia. Geological Survey of Western
yttrium variability in South East Queensland waterways. Aquat. Geochem. 12, Australia, Record 2006/15.
39–72. Van Kranendonk, M.J., Smithies, R.H., Hickman, A.H., Champion, D.C., 2007. Review:
Masuda, A., Kawakami, O., Dohmoto, Y., Takenaka, T., 1987. Lanthanide tetrad effects secular tectonic evolution of Archaean continental crust: interplay between hor-
in nature: two mutually opposite types, W and M. Geochem. J. 21, 119–124. izontal and vertical processes in the formation of the Pilbara Craton, Australia.
Masuda, A., Ikeuchi, Y., 1979. Lanthanide tetrad effect observed in marine environ- Terra Nova 19, 1–38.
ment. Geochem. J. 13, 19–22. Watanabe, Y., Martini, J.E.J., Ohmoto, H., 2000. Geochemical evidence for terrestrial
McCollom, T.M., Seewald, J.S., 2006. Carbon isotope composition of organic com- ecosystems 2.6 billion years ago. Nature 408, 574–578.
pounds produced by abiotic synthesis under hydrothermal conditions. Earth Webb, G.E., Kamber, B.S., 2000. Rare earth elements in Holocene reefal microbialites:
Planet. Sci. Lett. 243, 74–84. a new shallow seawater proxy. Geochim. Cosmochim. Acta 64, 1557–1565.
Murray, R.W., Buchholtz ten Brink, M.R., Gerlach, D.C., Russ III, G.P., Jones, D.J., 1991. Westall, F., de Wit, M.J., Dann, J., van der Gaast, S., de Ronde, C.E.J., Gerneke, D.,
Rare earth, major, and trace elements in chert from the Franciscan Complex 2001. Early Archean fossil bacteria and biofilms in hydrothermally-influenced
and Monterey Gorup, California: assessing REE sources to fine-grained marine sediments from the Barberton Greenstone Belt, South Africa. Precambrian Res.
sediments. Geochim. Cosmochim. Acta 55, 1875–1895. 106, 93–116.
Nozaki, Y., Zhang, J., Amakawa, H., 1997. The fractionation between Y and Ho in the Wood, S.A., 2006. Rare earth element systematics of acidic geothermal waters from
marine environment. Earth Planet. Sci. Lett. 148, 329–340. Taupo Volcanic Zone, New Zealand. J. Geochem. Explor. 89, 424–427.
Oehler, D.Z., Robert, F., Walter, M.R., Sugitani, K., Allwood, A., Meibom, A., Mostefaoui, Yamamoto, K., Itoh, N., Matsumoto, T., Tanaka, T., Adachi, M., 2004. Geochemistry of
S., Selo, M., Thomen, A., Gibson, E.K., 2009. NanoSIMS: insights to biogenicity and Precambrian carbonate intercalated in pillows and its host basalt: implications
syngeneity of Archaean carbonaceous structures. Precambrian Res. 173, 70–78. for the REE composition of circa 3.4 Ga seawater. Precambrian Res. 135, 331–
Ohta, A., Kawabe, I., 2000. Theoretical study of tetrad effects observed in REE distri- 344.
bution coefficients between marine Fe–Mn deposit and deep seawater, and in