Geoscience Frontiers 12 (2021) 549–572

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Research Paper

Depositional age and tectonic environment of the Gouap banded iron

formations from the Nyong group, SW Cameroon: Insights from isotopic,
geochemical and geochronological studies of drillcore samples
Landry Soh Tamehe a, b, Chongtao Wei a, *, Sylvestre Ganno b, Carlos Alberto Rosi
ere c,
Jean Paul Nzenti b, Chesther Gatse Ebotehouna d, Guanwen Lu a
a
Key Laboratory of CBM Resources and Reservoir Formation Process, Chinese Ministry of Education, China University of Mining and Technology, Xuzhou, Jiangsu,
221116, China
b
Department of Earth Sciences, University of Yaounde I, P.O. Box 812, Yaounde, Cameroon
c
Department of Geology, Universidade Federal de Minas Gerais, 31270-901, Belo Horizonte, Minas Gerais, Brazil
d
School of Civil and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China

A R T I C L E I N F O A B S T R A C T

Handling Editor: Christopher Spencer The discovery of the Gouap banded iron formations (BIFs)-hosted iron mineralization in the northwestern of the
Nyong Group (Ntem Complex) in southwestern Cameroon provides unique insights into the geology of this region.
Keywords: In this contribution, we firstly report detailed study of geochemistry, isotopic and geochronology of well pre-
Gouap served samples of the Gouap BIFs collected from diamond drillcores. The Gouap BIFs consist mainly of amphibole
Banded iron formations
BIFs and amphibole–pyrite BIFs characterized by dominant Fe2O3 þ SiO2 contents and variable contents of CaO,
Isotope geochemistry
MgO and SO3, consistent with the presence of amphibole, chlorite, epidote and pyrite, formed during amphibolite
Zircon geochronology
Ryacian period facies metamorphism and overprinted hydrothermal event. The amphibole–pyrite BIFs are typically enriched in
Brasiliano–Congo orogeny trace and rare earth elements (REE) compared to the amphibole BIFs, suggesting the influence of detrital materials
as well as secondary hydrothermal alteration. The Post Archean Australian Shale (PAAS)-normalized REE–Y
profiles of the Gouap BIFs display positive La, Eu anomalies, weak negative Ce anomalies, indicating a mixture of
low-temperature hydrothermal fluids and relatively oxic conditions probably under relative shallow seawater.
We present here the first isotopic data of BIFs within the Ntem Complex. The δ30SiNBS28 values of the quartz
from the Gouap BIFs vary from 1.5‰ to 0.3‰ and from 0.8‰ to 0.9‰ for the amphibole BIFs and
amphibole–pyrite BIFs, respectively. The quartz has δ18OV-SMOW values of 6.8‰–9.5‰ (amphibole BIFs) and
9.2‰–10.6‰ (amphibole–pyrite BIFs). The magnetite from the Gouap BIFs shows δ18O values ranging from
3.5‰ to 1.8‰ and from 3‰ to 1.7‰ for the amphibole BIFs and amphibole–pyrite BIFs, respectively.
Moreover, the pyrite grains in the amphibole–pyrite BIFs display δ34S values of 1.1‰–1.8‰. All isotopic data of
the Gouap BIFs confirm that they might have precipitated from low-temperature hydrothermal fluids with detrital
input distant from the volcanic activity. According to their geochemical and isotopic characteristics, we propose
that the Gouap BIFs belong to the Superior type.
In situ U–Pb zircon dating of BIFs was conducted to assess the BIF depositional age based on strong evidence of
zircon in thin section. The Gouap BIFs were probably deposited at 2422  50 Ma in a region where sediments
extended from continental shelf to deep-water environments along craton margins like the Cau^e Formation of the
Minas Supergroup, Brazil. The studied BIFs have experienced regional hydrothermal activity and metamorphism
at 2089  8.3 Ma during the Eburnean–Transamazonian orogeny. These findings suggest a physical continuity
between the protocratonic masses of both S~ao Francisco and Congo continents in the Rhyacian Period.

* Corresponding author.
E-mail addresses: weighct@163.com (C. Wei), sganno2000@yahoo.fr (S. Ganno).
Peer-review under responsibility of China University of Geosciences (Beijing).

https://doi.org/10.1016/j.gsf.2020.07.009
Received 27 August 2019; Received in revised form 22 April 2020; Accepted 2 July 2020
Available online 25 August 2020
1674-9871/© 2020 China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
L. Soh Tamehe et al.
1. Introduction
The banded iron formations (BIFs) are one of the key rocks to get
insightful information of the Earth’s history. In fact, the BIFs occur in
Precambrian terrains throughout the world and therefore they play a
significant role for understanding the composition of the Earth’s hydro-
sphere and atmosphere as well as the evolution of the Earth’s crust
(Trendall, 2002; Huston and Logan, 2004; Bekker et al., 2010; Kato et al.,
2006; Soh Tamehe, 2020). These explain the several researches that have
been conducted worldwide on the BIFs during the past decades. Despite
the abundant literature on BIFs dealing with their mineralogy, petrology,
geochemistry and geochronology, the BIFs remain enigmatic rocks while
constituting an important source of iron ore for the steel industry
nowadays.
The Precambrian Ntem Complex corresponds to the northern edge
extension of the Congo craton in southern Cameroon (Maurizot et al.,
1986). The Ntem Complex has usually been subdivided into the Nyong
and Ntem Groups, where iron deposits are hosted by metamorphic BIFs
(e.g., Suh et al., 2009; Chombong and Suh, 2013; Ilouga et al., 2013;
Ganno et al., 2015, 2016). The BIFs of the Ntem Complex mainly consist
Fig. 1. Geological map of the SW Cameroon showing the location of the studied area (blue square) and major BIF-hosted iron deposits (red circle) (adapted from
Maurizot et al., 1986). Inset illustrating the position of the SW Cameroon (red rectangle) relative to the Congo craton in Africa.
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Geoscience Frontiers 12 (2021) 549–572
of oxide-facies, characterized by rhythmic and rarely irregular alterna-
tion of granular or recrystallized quartz-rich and iron-rich layers. These
BIFs exhibit strong deformational features and they are spatially associ-
ated with different country rocks (e.g., gneiss, quartzite, schist,
amphibolite, syenite, epidotite), which both have undergone a greens-
chist to granulite facies metamorphic grade (Ganno et al., 2015, 2016,
2017, 2018; Teutsong et al., 2017; Ndime et al., 2018, 2019; Soh Tamehe
et al., 2018, 2019). Previous studies have been attempted to characterize
the features and genesis of the metamorphic BIFs of the Ntem Complex
(e.g., Ganno et al., 2017; Teutsong et al., 2017; Soh Tamehe et al., 2018;
Ndime et al., 2018, and references therein). Nevertheless their deposi-
tional settings remain to be precisely constrained. Earlier authors have
classified these rocks as being deposited in a volcanic environment
(Algoma-type; Teutsong et al., 2017; Nzepang Tankwa et al., 2020) or on
a passive margin (Superior-type; Ganno et al., 2015, 2017; Soh Tamehe
et al., 2018) according to their petrographical and geochemical
characteristics.
Previous studies on metamorphic BIFs in the Nyong Group were
carried out mostly on surface weathered outcrops (Ganno et al., 2016,
2017; Soh Tamehe et al., 2018). Besides the reliable outcomes achieved
L. Soh Tamehe et al. Geoscience Frontiers 12 (2021) 549–572

for their studies, they cannot record the expected information for un-
derstanding their origin, whereas drillcore allow us to collect well pre-
served samples to better constrain the genesis as well as the depositional
environment of the BIFs. Drilling exploration programs have been con-
ducted by G-Stones Resources Ltd. at the Gouap prospect in the northwest
of the Nyong Group (Fig. 1), providing drillcore samples that displays the
interlayering of the iron formations with gneisses, schists, quartzites and
dolerite sills (Soh Tamehe et al., 2019). Limited geological investigations
have so far been accomplished on BIF core samples from the Nyong
Group (Soh Tamehe et al., 2019; Nzepang Tankwa et al., 2020) compared
to those from the Ntem Group (Teutsong et al., 2017; Ndime et al., 2018,
2019).
This paper presents the first detailed geochemical and geochrono-
logical studies of well preserved samples of the Gouap BIFs collected from
diamond drillcores in the Gouap iron deposit, which represents a pro-
spective area for iron ore in southwestern Cameroon. Furthermore, this
study provides the first isotopic data of quartz, magnetite and pyrite of
the BIFs within the Ntem Complex. Direct dating of zircon extracted from
the Gouap BIFs was achieved using laser ablation inductive coupled
plasma mass spectrometry (LA-ICP-MS). These new results aim to
constrain the genesis and depositional age of the Gouap BIFs as well as
the tectonic environment from which the BIFs were precipitated.
Thereby, this study is a substantial contribution towards the improved
understanding of the BIF genesis of the Nyong Group.

Fig. 2. (a) Detailed geological map of the Nyong Group showing the location of the Gouap prospect (black square) and BIF-hosted iron deposits (red circle) (modified
after Lerouge et al., 2006). (b) Sketch map of the Congo and S~ao Francisco cratons (greyed area) with limits of NE Brazil and Central West Africa illustrating location of
the studied area (red star).

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2. Geological background
2.1. The Nyong Group
The Gouap iron deposit belongs to the Nyong Group (Fig. 2), which
consists mainly of metasedimentary and metavolcanic rocks as well as
syn- to late-tectonic intrusive rocks. It includes various migmatitic rocks,
gneisses, mafic granulites, charnockites, pyroxenites, amphibolites,
schists, quartzites and BIFs (e.g., Toteu et al., 1994; Lerouge et al., 2006;
Ndema et al., 2014; Ganno et al., 2017). Intrusions of metadiorites,
granodiorites, and syenites cut rocks of the Nyong Group, along with
post-tectonic dolerites (Toteu et al., 1994; Lerouge et al., 2006). More
recently, well-preserved to variably retrogressed eclogite facies meta-
morphic rocks (eclogites and serpentinitized peridotites) have been re-
ported in the Nyong Group (Loose and Schenk, 2018; Bouyo
Houketchang et al., 2019; Nga Essomba et al., 2020).
The metasedimentary and metaplutonic rocks of the Nyong Group
have undergone a granulite facies metamorphism associated with the
intrusion of charnockitic rocks (Toteu et al., 1994; Lerouge et al., 2006).
Toteu et al. (1994) reported U–Pb zircon metamorphic ages (~2050 Ma)
from gneissic rocks at Kribi and Akom II (see Fig. 2). Subsequently, the
high-grade metamorphic event (2100–2000 Ma) associated with tecto-
nomagmatic activities (2055  5 Ma) were established using the Sensi-
tive High Resolution Ion-Microprobe (SHRIMP) U–Pb analyses on zircon
grains from metasedimentary and metaplutonic rocks collected at Lolo-
dorf (Lerouge et al., 2006). The emplacement of these plutonic rocks
within the Nyong Group is associated with Eburnean high-grade meta-
morphism which continued probably up to 1985  8 Ma (Lerouge et al.,
2006). In addition, these authors (Toteu et al., 1994; Lerouge et al., 2006)
identified other non-Archean events recorded by Eburnean zircon growth
and titanite ages in metagranitoids. Thus, the Nyong Group recorded
Paleoproterozoic and Pan-African reworking. More recently, Chombong
et al. (2017) obtained Neoarchean age (2699  7 Ma) and Neo-
proterozoic age (600–500 Ma) from zircon of magnetite gneisses. The
former age represents the maximum age of formation of the magnetite
gneisses, whereas the later age is interpreted as the Pan-African distur-
bance recorded by these gneisses (Chombong et al., 2017).
Additionally, Loose and Schenk (2018) demonstrated that the Nyong
Group underwent an eclogite facies metamorphism at 2093  45 Ma
based on SHRIMP U–Pb dating performed on zircon grains from eclogites
collected near the Bipindi area. This age is comparable to that of meta-
morphic events reported earlier by Toteu et al. (1994) and Lerouge et al.
(2006). This implies that the Nyong Group experienced similar meta-
morphism during the Paleoproterozoic between 2100 and 2000 Ma
(Bouyo Houketchang et al., 2019).
The Nyong Group displays flat-lying foliations with N–S to NNE–SSW
axial fold lineations and E–W to NW–SE stretching lineations that indi-
cate an eastward-directed movement (Maurizot et al., 1986).
2.2. The Gouap iron deposit
Detailed stratigraphical, petrographical and structural information of
the Gouap iron deposit are given by Soh Tamehe et al. (2019). The
geological sketch map of the deposit is presented in Fig. 3. The Gouap
iron deposit is comprised of amphibole BIFs and amphibole–pyrite BIFs,
well interlayered with amphibolite facies gneisses (garnet, amphib-
ole–magnetite and amphibole–garnet–pyrite gneiss), staurolite micas-
chists and quartzites displaying sharp to gradational contact. Younger
dolerite sills crosscut the gneisses and BIFs. The deposit has experienced
three principal deformations events that led to the development of foli-
ation, folding and faulting on a regional scale.
The Gouap iron deposit hosts both soft and hard iron ore types. The
soft iron ore type, which dominantly occurs in the western and northern
areas of the Gouap deposit, is comprised of hematite–martite and mag-
netite–hematite, whereas the hard type is magnetitic and mainly found in
the southern part of the deposit. The magnetite ore bodies are mostly
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Geoscience Frontiers 12 (2021) 549–572
concentrated on the hinge zones of the F2 folds, while the hema-
tite–martite and magnetite–hematite bodies developed on highly frac-
tures zones.
3. Samples description and analytical methods
3.1. Samples description
For this study, we focused on the two major BIF lithofacies (amphi-
bole BIFs and amphibole–pyrite BIFs) of the Gouap deposit. The BIF
samples were collected from different depths of three drillholes: DD036
(length ¼ 151.50 m, azimut ¼ 115 and dip ¼ 55 ), DD042 (length ¼
200.90 m, azimut ¼ 115 and dip ¼ 60 ), and DD043 (length ¼ 183.00
m, azimut ¼ 115 and dip ¼ 55 ). These drillholes are located in the
southern part of the Gouap iron deposit (Fig. 3), and they are represen-
tative drillholes in terms of the geology of the deposit (Soh Tamehe et al.,
2019). The studied BIF samples are all fresh and free from weathering.
The Gouap BIF samples collected are described below.
In hand specimen, samples of amphibole BIF from the Gouap deposit
are slightly dark gray to dark green in color (Fig. 5a and b). The rocks are
fine-grained and display a well-developed banding consisting of inter-
calated laminations of thinner silica-rich (1–3 mm thick) and oxide-rich
(0.5–2 mm thick) layers (Fig. 5a and b). On a microscopic scale, the
amphibole BIF exhibits granoblastic texture with abundant magnetite,
quartz and amphibole grains, and minor epidote and zircon (Fig. 5c–f).
The silica-rich layers are dominated by amphibole and quartz, whereas
the oxide-rich layers are made up of magnetite (Fig. 5c–f). Magnetite
forms coarse (2.3 mm  0.7 mm) euhedral to subhedral crystals with
preferred orientation and is typically surrounded by quartz and amphi-
bole (Fig. 5cd). Magnetite often contains quartz inclusions. Quartz
appears as fine to medium-grained subhedral to euhedral crystals (0.7
mm  0.3 mm), and generally contains inclusions of magnetite and
zircon (Fig. 5c–f). Amphibole mostly occurs as fine subhedral to euhedral
crystals (0.1–0.5 mm), and intergrowths with quartz. Zircon is scarce and
occurs as very fine-grained (<0.1 mm) euhedral crystals in samples such
as GB11–2 and GB9 (Fig. 5c–f).
At the Gouap deposit, samples of the amphibole–pyrite BIF display
dark gray to dark green color and banding structure in hand specimen
(Fig. 6a and b). The rocks are coarse-grained and their primary sedi-
mentary micro-banding is obliterated and tectonically transposed with
the development of metamorphic foliation characterized by alternating
light silica-rich (1–2.5 mm thick) and dark oxide-rich (0.5–1.5 mm thick)
bands (Fig. 6a and b). In thin section, the amphibole–pyrite BIF is char-
acterized by heterogranular granoblastic texture made mainly of quartz,
magnetite, amphibole, pyrite, and minor clinopyroxene, epidote, chlorite
and zircon. Quartz and amphibole composed the silica-rich laminae,
while magnetite and pyrite constitute the oxide-rich laminae (Fig. 6c–f).
Quartz occurs as fine- to medium-grained anhedral crystals (0.1–0.9
mm), and commonly contains inclusions of magnetite and zircon
(Fig. 6c–f). Amphibole forms subhedral to anhedral laths crystals
(0.3–0.5 mm) which is often altered to chlorite (Fig. 6c–f). Magnetite
grains (0.3–1.4 mm) appears as elongated subhedral to euhedral crystals
and contains quartz inclusions (Fig. 6c–f). Pyrite generally occurs as fine-
to medium-grained (0.06–0.3 mm) euhedral to subhedral crystals, and is
disseminated in the rock matrix or is aggregated with magnetite
(Fig. 6c–f). Secondary chlorite and epidote flakes (0.1–0.3 mm) occur as
an alteration product of biotite and amphibole, respectively (Fig. 6c and
d). Clinopyroxene appears as fine-grained (0.6–0.8 mm) subhedral to
anhedral crystals, and is often associated with magnetite (Fig. 6c–f).
Zircon grains (<0.1 mm) commonly appears as euhedral to subhedral
crystals in quartz grain (Fig. 6c–f).
3.2. Major and trace elements geochemistry
Sixteen BIF samples (eight amphibole BIFs and eight amphib-
ole–pyrite BIFs) were collected from different depths of drillholes
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Fig. 3. Geological map of the Gouap iron deposit (adapted after Soh Tamehe et al., 2019).

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Fig. 4. Stratigraphic columns showing the location of the BIF samples collected from the drillholes of the Gouap iron deposit (modified after Soh Tamehe et al., 2019).

DD036, DD042 and DD043 (see Fig. 3) and used for geochemical ana-
lyses. The locations of the BIF samples are shown in Fig. 4a–c. Major and
trace elements analyses were performed at the Australian Laboratory
Services (ALS) of Guangzhou, China. For major elements, a prepared
sample is fused with lithium metaborate-lithium tetraborate flux which
also includes an oxidizing agent (Lithium Nitrate), and then poured into a
platinum mould. The resultant disk is in turn analyzed by X–ray fluo-
rescence (XRF) spectrometry. The XRF analyses are determined in
conjunction with a loss-on-ignition at 1000  C. The resulting data from
both determinations are combined to produce a “total”.
For trace elements, a prepared sample is added to lithium metaborate-
lithium tetraborate flux, mixed well and fused in a furnace at 1025  C.

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Fig. 5. Drillcore samples and photomicrographs of the amphibole BIF from the Gouap iron deposit. (a, b) Typical hand specimen consisting of oxide-rich layer
alternating with silica-rich layer. (c, d) Granoblastic texture showing a crystallographic preferred orientation of magnetite and quartz coexisting with amphibole and
zircon inclusion (plane polarized light). (e, f) Magnetite megacryts surrounded by quartz megacrysts (reflected light). Abbreviations: Amp, amphibole; Mag, magnetite;
Qtz, quartz; Zr, zircon.

The resulting melt is then cooled and dissolved in an acid mixture con-
taining nitric, hydrochloric and hydrofluoric acids. This solution is then
analyzed by ICP-MS. Analytical uncertainties vary from 0.1% to 0.04%
for major elements; and 0.1%–0.5% for trace elements. Various standards
were used and data quality assurance was verified by running these
standards between samples as unknowns. The detection limits were 0.01
ppm for the REE and Y.
3.3. Isotopes geochemistry
Quartz and magnetite grains were separated from nine BIF samples.
One amphibole BIF (GB9) sample was collected from drillhole DD036,
whereas three amphibole–pyrite BIF (GB10–1, GB10–2 and GB10-3) and
five amphibole BIF (GB11-1 to GB11-5) samples were collected from
drillhole DD043 (see location in Fig. 4b and c). Quartz grains were
separated prior to silicon and oxygen isotope analyses, while magnetite
grains were separated only prior to oxygen isotope analyses. Prior to
sulfur isotope analyses, the pyrite grains were extracted from ten BIF
samples (GB10-1 to GB10-10, see location in Fig. 4c) collected from
drillhole DD043. Quartz, magnetite and pyrite grains were handpicked
from the 60–80 mesh mineral crush under a binocular (purity > 99%).
All the isotopic analyses were performed at the Analytical Laboratory
Beijing Research Institute of Uranium Geology (ALBRIUG), Beijing,
China.
For oxygen isotope analyses, quartz and magnetite grains were
crushed into 200 mesh and reacted with pure BrF5 during 14 h at
500–680  C under vacuum pressure of 103 Pa. The reaction generated
O2 and impurity components (SiF4 and BrF3), which was separated by
freezing method. Then pure O2 was reacted with a carbon rod at 700  C,
producing CO2 which was collected by freezing method and analyzed by
MAT–253 mass spectrometer for oxygen isotope compositions. The result
of the measurement is expressed as δ18OV-SMOW in parts per mil (‰)
based on the Vienna Standard Mean Ocean Water (V–SMOW). The ac-
curacy of the analyses was 0.2‰.
Silicon isotope analyses of quartz were preceded after quartz grains
were crushed into 200 mesh and reacted with pure BrF5 at 500–680  C
for 14 h under 103 Pa vacuum pressure. The reaction released SiF4
which was separated, collected, and purified using dry ice, liquid nitro-
gen and alcohol, respectively. The Si isotope composition was measured
by MAT–253 mass spectrometer. The measurement result is expressed as
δ30SiNBS-28 in parts per mil (‰) relative to the NBS–28 as standard. The
analytical uncertainties were better than 0.1‰.

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Fig. 6. Drillcore samples and photomicrographs of the amphibolepyrite BIF from the Gouap iron deposit. (a, b) Typical hand specimen showing pyrite grains within
oxide-rich layer. (c, d) Granoblastic texture displaying magnetite coexisting with pyrite in oxide-rich layer (plane polarized light). (e, f) Intergrown Py þ Mag þ Qtz
with minor Amp þ Cpx and Zr inclusion (reflected light). Abbreviations: Amp, amphibole; Bt, biotite; Cpx, clinopyroxene; Mag, magnetite; Qtz, quartz; Py, pyrite;
Zr, zircon.

For sulfur isotope analyses, pyrite grains were crushed into 200 mesh
and mixed uniformly with cuprous oxide. The reaction was heated at 980

C under 2  102 Pa vacuum pressure. The SO2 was generated and
collected by freezing method, then analyzed by a MAT–251 mass spec-
trometer for sulfur isotopes. The measurement result is reported as δ34SV-
CDT in parts per mil (‰) based on the Vienna Ca~ non Diablo Troilite
(V–CDT) standard. The accuracy of the analyses was better than 0.2‰.
3.4. Zircon U–Pb dating
Two representative BIF samples (GB10-1 and GBW3-1) collected from
drillholes DD042 and DD043 were used for dating (see location in
Fig. 4a–c). Zircon grains were extracted from each sample using con-
ventional gravimetric and magnetic techniques, following by hand-
picking under a binocular microscope at Langfang Rock Detection
Technology Services Ltd (Hebei, China). Then all subsequent zircon
treatment was conducted at the Beijing Kehui Testing International Co.
Ltd, China. Representative zircon grains were mounted in epoxy resin
and polished to mid-section to expose their cores for analyses. Cath-
odoluminescence (CL) images, transmitted and reflected light micro-
photographs of all zircon grains were taken to examine their internal
structures and select appropriate spots prior to U–Pb dating. Back-
scattered electron (BSE) images of zircon grains were further taken to
better interpret their internal fabrics. CL and BSE images were collected
using a JSM 6510 scanning electron microscope (SEM; JEOL) attached to
a Gatan CL detector with a voltage of 10 kV.
Zircon U–Pb analyses were performed using an ESI NWR 193 nm laser
ablation system and an AnalytikJena PQMS Elite ICP-MS instrument. The
zircon grains were analyzed using a 32 μm spot diameter. All analyses
were conducted with a 10 Hz repetition rate and energy of 2.5 J cm2.
For every set of 5–10 analyses, five reference standards were used: (1)
NIST610 glass (http://georem.mpch-mainz.gwdg.de/), (2) 91500 (Wie-
denbeck et al., 1995), (3) GJ1 (Jackson et al., 2004), (4) Plesovice (Slama
et al., 2008), and (5) Qinhu (Li et al., 2013). This was done to correct for
laser-induced elemental fractionation, instrumental mass fractionation
and drift, to calibrate the measured isotopic ratios, and to validate the
measurement procedure (Quinn et al., 2016). The ICPMSDataCal 8.4
software was used for fractionation correction and calculation of the
dating results (Liu et al., 2010). The 207Pb/206Pb, 206Pb/238U, 207U/235U
and 208Pb/232Th isotopic ratios were corrected using zircon 91500 as an
external standard for both instrumental bias and elemental and isotopic
fractionation. Common lead was corrected using the method of Anderson

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(2002). Uncertainties in the age analysis are quoted at 1σ, whereas errors

105.05
in the weighted mean ages are calculated at 2σ level (95% confidence).

53.65

32.31

85.96
Mean

0.23

3.93
0.23
3.15
2.43
0.20
0.39
0.17
8.42
2.59

4.17
Concordia diagrams, weighted average age calculation and probability
density plotting were processed using Isoplot/Ex 3.0 (Ludwig, 2003).

GB10-2
171.35
DD043
A detailed description for LA-ICP-MS instrument is presented in Ap-

47.21

36.80

99.74
84.01
0.25

5.86
0.07
3.01
3.51
0.21
0.95
0.37
1.50
0.42

6.11
pendix S1, whereas full analytical data for zircon grains (analyzed spots
and standards) is given in Appendix S2. This follows the recommenda-
tions outlined by Kosler et al. (2013) and Horstwood et al. (2016). To

GB10-1
171.30
DD043

44.79

39.94

99.55
84.73
0.29

5.16
0.07
3.27
3.07
0.24
0.96
0.44
1.32
0.95

5.45
calculate the most geologically appropriate age from our U–Pb zircon
geochronological data, we also follow the recommendations by Spencer
et al. (2016). However, the maximum depositional age (MDA) of the BIF

160.00
DD042

55.40

36.66

99.84
92.06
GB6*
samples was calculated as the weighted average of the youngest detrital

0.11

2.14
0.07
2.29
1.68
0.10
0.58
0.31
0.50
0.03

2.25
zircon population (minimum of n ¼ 3) that overlap within uncertainty at
the 2σ level (Dickinson and Gehrels, 2009). The MDA for sample GB10-1

GBW3-5
was further calculated after excluding data of overdispersed grain spots.

184.50

111.45
DD042

62.08

21.98

16.70

84.06
0.16

4.76
0.32
2.68
2.01
0.61
0.11
0.04

4.71

4.92
4. Results

GBW3-4
181.10
DD042

<0.01
67.03

24.25

99.32
91.28
4.1. Major elements

0.01

0.42
0.19
3.68
3.29
0.08

0.04
0.33
0.48

0.43
The major elements analyses of the Gouap BIFs are presented in

GBW3-3
Table 1. The amphibole BIFs are characterized by high Fe2O3

177.00

102.59
DD042

60.65

28.83

89.48
0.01

0.81
0.29
3.82
3.25
0.09
0.02
0.07
4.75
1.23

0.82
(44.57–60.83 wt.%, expressed as Fe total) and SiO2 (36.22–50.12 wt.%)
contents, which represent the major components (>91 wt.%) of the bulk
rock (Table 1). The Al2O3 and TiO2 have low concentrations ranging from

GBW3-2*
Amphibole–pyrite BIF
0.15 to 3.23 wt.% and <0.01 to 0.10 wt.%, respectively. Other oxides

151.54

107.74
DD042

58.22

26.27

10.75

84.49
0.43

6.71
0.44
3.28
1.47
0.12
0.04
0.01

2.81

7.14
such as MgO (2.19–3.85 wt.%) and CaO (0.71–2.28 wt.%) display sig-
nificant contents in the studied BIFs, which is consistent with the pres-
ence of amphibole. Very low concentrations of MnO (0.04–0.18 wt.%), GBW3-1*
144.55

120.18
DD042
Na2O (0.02–0.34 wt.%), P2O5 (0.17–0.26 wt.%), and SO3 (0.02–0.24

33.84

43.76

10.11

77.60
0.59

5.61
0.36
3.15
1.12
0.13
0.07
0.05
31.5

6.20
wt.%) characterize these amphibole BIFs. Most BIF samples except for
GB4-3 and GB11-2 show K2O contents below the detection limit (<0.001
wt.%). Loss on ignition (LOI) is very low for all the amphibole BIF

100.57
41.56

53.53

95.09
Mean

0.04

0.85
0.08
3.01
1.17
0.09
0.07
0.20
0.07
1.10

0.89
samples and ranges from 1.51 to 0.80 wt.%.
The amphibole–pyrite BIFs consist principally of high SiO2 content
(33.84–67.03 wt.%) and relatively low content of Fe2O3 (21.98–43.76
129.50

100.36
DD036

<0.01
50.12

44.57

94.69
0.01

0.20
0.18
2.71
2.28
0.04

0.19
0.06
0.80

0.21
GB9

wt.%, as Fe total), when compared to amphibole–BIFs. The TiO2 content

is generally low, ranging from 0.01 to 0.59 wt.%, while the Al2O3 content
Major elements compositions (wt.%) of the Gouap BIFs. *Data from Soh Tamehe et al. (2019).

(0.42–6.71 wt.%) is noticeably high in these BIFs. Concentrations of CaO

GB11-2
104.00

101.03
DD043

43.32

48.64

91.96
and MgO are also elevated within the amphibole–pyrite BIFs, ranging
0.10

3.23
0.13
3.85
1.14
0.34
0.08
0.18
0.02
0.85

3.33
from 1.12 to 3.51 wt.% and 2.29 to 3.82 wt.%, respectively. This cor-
roborates the occurrence of Mg-hornblende, tremolite and cumming-
GB11-1
103.00

100.29
DD043

tonite in these BIFs (Soh Tamehe et al., 2019). The studied BIFs also have
<0.01
37.81

58.45

96.26
0.03

0.71
0.05
2.19
0.71
0.05

0.26
0.03
1.13

0.74
significant SO3 contents (0.33–16.70 wt.%), which confirm the presence
of pyrite. All other oxides such as MnO (0.07–0.44 wt.%), Na2O
(0.08–0.24 wt.%), K2O (<0.01–0.96 wt.%), and P2O5 (0.01–0.44 wt.%)
154.05

100.96
DD042
GB4-5

<0.01

<0.01

<0.01
36.22

60.83

97.05
0.17
0.04
2.73
0.72
0.03

0.22

1.51

0.17

have very low contents. The amphibole–pyrite BIFs display low to high
LOI varying from 0.03 to 10.11 wt.%. The samples with high LOI also
show high SO3 contents, suggesting highly hydrothermal alteration of
147.00

100.41
DD042
GB4-4

<0.01

<0.01

<0.01
41.47

54.25

95.72
0.15
0.05
3.50
0.77
0.03

0.19

1.02

0.15

these rocks.

4.2. Trace and rare earth elements

GB4-3*
136.50

100.16
DD042

40.24

52.32

92.56
0.06

1.78
0.08
3.71
1.60
0.10
0.05
0.20
0.02
0.90

1.84

The trace and rare earth elements analyses of the Gouap BIFs are given
Note: Fe2OT3, total Fe expressed as Fe2O3.

in Table 2. The amphibole BIFs particularly have very low (<5 ppm) to
GB4-2*
133.10

100.55
DD042

moderate (<40 ppm) concentrations of trace elements when compared to

<0.01

<0.01
42.28

53.97

96.25
0.22
0.04
2.51
1.10
0.02

0.17
0.24
1.16

0.22

the average composition of the upper continental crust from Rudnick and
Amphibole BIF

Gao (2003) (Fig. 7a). Except Zn (15–67 ppm) and Cr (10–30 ppm) con-
tents, the amphibole BIFs are characterized by low concentrations (<20
GB4-1*
132.05

100.78
DD042

<0.01
41.04

55.18

96.22
0.01

0.30
0.05
2.88
1.01
0.08

0.20
0.03
1.44

0.31

ppm) of transition trace metals. In terms of large ion lithophile elements

(LILE), these BIFs have very low contents (<5 ppm) except for Sr and Ba
contents varying between 9.5–39.4 ppm and 1.0–24.8 ppm, respectively.
Fe2OT3 þ SiO2
Al2O3 þ TiO2

The high field strength elements (HFSE) display also very low concentra-
Rock code
Depth (m)
Drill hole
Lithology

tions (<5 ppm) in the amphibole BIFs, except for Zr which reaches values
Fe2O3T
Table 1

Al2O3

Na2O

Total
MnO

P2O5
MgO
TiO2
SiO2

CaO

K2O

SO3

up to 27 ppm. The contents of other trace elements (e.g., Li, Be and Ga) are
LOI

trivial in all these BIF samples (Table 2, Fig. 7a). Most amphibole BIF

557
 L. Soh Tamehe et al.
Table 2
Trace and rare earth elements (ppm) of the Gouap BIFs.
Lithology Amphibole BIF Amphibole–pyrite BIF

Rock code GB4-1 GB4-2 GB4-3 GB4-4 GB4-5 GB11-1 GB11-2 GB9 Mean GBW3-1 GBW3-2 GBW3-3 GBW3-4 GBW3-5 GB6 GB10-1 GB10-2 Mean
Depth (m) 132.05 133.10 136.50 147.00 154.05 103.00 104.00 129.50 144.55 151.54 177.00 181.10 184.50 160.00 171.30 171.35
Drill hole DD042 DD042 DD042 DD042 DD042 DD043 DD043 DD036 DD042 DD042 DD042 DD042 DD042 DD042 DD043 DD043

Li 1.7 1.6 4.1 2.0 1.4 2.7 4.1 0.2 2.23 8.6 9.0 1.5 1.0 8.6 6.9 8.4 7.8 6.48
Be 0.48 0.44 0.73 0.63 0.46 0.30 0.31 0.40 0.47 0.15 0.18 0.58 0.31 0.41 0.49 3.06 2.07 0.91
Sc 0.4 0.3 2.1 0.2 0.3 0.4 1.4 0.2 0.66 14.6 13.4 2 2.4 7.5 2.3 7.9 6.6 7.09
V 6 <5 15 <5 <5 7 18 2 6 80 59 13 11 33 23 39 41 37.38
Cr 20 20 30 20 10 10 23 17 18.75 110 100 40 40 90 40 26 21 58.38
Co 0.6 0.8 3.0 0.9 1.0 1.6 2.7 1.5 1.51 176 62.4 42.3 11.9 133 4.8 4.4 3.1 54.74
Ni 2.4 2.5 5.4 2.3 3.2 4.3 4.1 2.5 3.34 289 96.6 41.6 9.3 124.5 7.6 10.2 5.9 73.09
Cu 1.4 0.7 5.5 0.7 2.3 0.5 1.7 1.1 1.74 2460 390 319 30 1170 34.8 95.8 39.0 567.33
Zn 24 17 46 20 19 15 67 24 29.00 275 137 341 279 188 54 53 49 172.00
Ga 0.9 0.9 5.0 0.8 0.9 2.3 7.1 1.3 2.40 10.6 8.3 3.3 3.0 7.6 8.2 7.2 7.1 6.91
Rb 0.3 0.2 0.9 0.2 0.2 1.0 4.3 0.3 0.93 5.7 1.4 0.7 0.5 3.0 19.2 32.1 32.4 11.88
Sr 9.5 12.1 9.5 9.7 9.6 10.0 39.4 12.7 14.06 13.7 5 11.7 15.7 33.2 20.1 285 532 114.55
Zr 5 4 14 2 2 9 27 5 8.50 1210 231 17 34 79 32 219 215 254.63
Nb 0.4 0.3 1.5 0.2 0.3 0.6 1.2 0.3 0.60 6.1 4.4 2.0 0.8 1.4 2.9 5.1 4.7 3.43
Cs 0.03 0.02 0.04 0.04 0.02 0.05 0.21 0.01 0.05 0.89 0.21 0.05 0.09 0.31 1.12 0.74 0.76 0.52
Ba 2.5 2.6 7.3 1.0 0.8 7.9 24.8 1.8 6.09 163.5 40.3 3.7 6.2 22.1 101.5 459 453 156.16
La 2.1 1.9 11.0 1.8 1.8 4.7 5.4 2.9 3.95 164.0 10.7 5.9 4.4 9.4 9.0 58.7 51.2 39.16
Ce 4.6 3.7 20.6 3.9 4.0 9.1 10.9 5.3 7.76 322 22.0 14.9 9.9 17.4 18.9 122.5 103.5 78.89
Pr 0.56 0.44 2.30 0.46 0.51 1.02 1.22 0.60 0.89 34.2 2.58 2.06 1.28 1.87 2.25 14.15 11.70 8.76
Nd 2.4 1.9 8.7 2.1 2.2 3.8 5.2 2.3 3.58 120.0 10.7 9.2 5.4 6.5 8.9 53.4 44.3 32.30
Sm 0.52 0.44 1.69 0.49 0.54 0.72 1.03 0.46 0.74 17.50 3.42 2.25 1.34 1.28 1.75 9.26 7.64 5.56
Eu 0.25 0.20 0.59 0.26 0.28 0.36 0.33 0.18 0.31 1.88 0.82 0.39 0.26 0.38 0.58 2.43 2.82 1.20
558

Gd 0.66 0.60 1.73 0.64 0.68 0.80 0.96 0.62 0.84 12.90 5.69 2.24 1.54 1.40 1.95 6.65 5.57 4.74
Tb 0.10 0.10 0.26 0.10 0.12 0.14 0.15 0.11 0.14 1.76 1.00 0.39 0.25 0.26 0.30 0.81 0.65 0.68
Dy 0.69 0.64 1.71 0.74 0.84 0.89 0.93 0.71 0.89 9.84 6.13 2.41 1.64 1.94 1.83 4.05 3.18 3.88
Y 5.1 4.9 9.7 5.7 5.8 6.7 6.4 7.0 6.41 41.2 30.2 15.3 11.5 13.1 11.6 21.6 17.7 20.28
Ho 0.17 0.15 0.35 0.17 0.19 0.22 0.22 0.17 0.21 1.81 1.21 0.56 0.38 0.47 0.39 0.78 0.60 0.78
Er 0.49 0.48 1.00 0.52 0.54 0.68 0.62 0.52 0.61 4.71 3.22 1.62 1.21 1.56 1.07 1.88 1.54 2.10
Tm 0.08 0.07 0.14 0.08 0.08 0.10 0.09 0.08 0.09 0.66 0.46 0.25 0.19 0.28 0.16 0.25 0.22 0.31
Yb 0.52 0.55 0.93 0.54 0.55 0.66 0.66 0.53 0.62 4.41 3.02 1.52 1.27 2.00 1.05 1.59 1.38 2.03
Lu 0.08 0.08 0.13 0.09 0.09 0.11 0.10 0.09 0.10 0.66 0.45 0.24 0.19 0.32 0.17 0.26 0.23 0.32
Hf <0.2 <0.2 0.4 <0.2 <0.2 0.3 0.8 0.2 0.21 29.9 5.8 0.4 0.2 2.1 0.8 5.5 5.2 6.24
Ta <0.1 <0.1 0.1 <0.1 <0.1 0.08 0.09 <0.05 0.03 0.2 0.2 0.1 <0.1 0.1 0.1 0.35 0.28 0.17
Au 0.010 0.005 <0.005 <0.005 <0.005 <0.005 <0.005 0.006 0.01 0.006 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 0.007 0.00
Pb 0.6 0.7 0.9 0.5 2.1 <0.5 1.4 <0.5 0.78 3.2 1.4 0.9 <0.5 5.2 1.5 5.9 10.2 3.54
Th 0.28 0.28 1.70 0.19 0.26 0.79 0.47 0.34 0.54 31.9 1.52 0.76 0.29 2.50 0.43 16.60 12.80 8.35
U 0.07 0.08 0.24 0.10 0.12 0.20 0.21 0.18 0.15 0.94 0.25 0.27 0.10 0.28 0.07 1.13 1.10 0.52
Th/U 4.00 3.50 7.08 1.90 2.17 3.95 2.24 1.89 3.34 33.94 6.08 2.81 2.90 8.93 6.14 14.69 11.64 16.14
ΣREE-Y 18.3 16.2 60.8 17.6 18.2 30.0 34.2 21.6 27.11 737.5 101.6 59.2 40.8 58.2 59.9 298.3 252.2 200.96
Y/Ho 30.00 32.67 27.71 33.53 30.53 30.45 29.09 41.18 31.89 22.76 24.96 27.32 30.26 27.87 29.74 27.69 29.50 27.51

Geoscience Frontiers 12 (2021) 549–572

(La/Yb)PAAS 0.23 0.20 0.68 0.19 0.19 0.41 0.47 0.32 0.34 2.14 0.20 0.22 0.20 0.27 0.49 2.13 2.14 0.97
(Sm/Yb)PAAS 0.40 0.32 0.72 0.36 0.39 0.43 0.62 0.34 0.45 1.57 0.45 0.59 0.42 0.25 0.66 2.31 2.19 1.08
(Pr/Yb)PAAS 0.27 0.20 0.62 0.21 0.23 0.39 0.46 0.28 0.33 1.93 0.21 0.34 0.25 0.23 0.53 2.22 2.11 1.08
(Ce/Ce*)PAAS 0.98 0.93 0.94 0.99 0.96 0.96 0.98 0.93 0.96 0.99 0.97 0.97 0.96 0.95 0.97 0.98 0.98 0.98
(Eu/Eu*)PAAS 2.02 1.77 1.62 2.17 2.04 2.10 1.52 1.48 1.84 0.58 0.82 0.76 0.83 1.22 1.47 1.47 2.08 1.08
(La/La*)PAAS 1.13 1.33 1.07 1.45 1.08 1.01 1.31 1.11 1.19 0.95 1.14 0.98 0.99 0.98 0.98 0.93 0.98 0.96
(Pr/Pr*)PAAS 0.99 0.97 1.01 0.94 1.00 1.02 0.95 1.01 0.99 1.02 0.99 1.02 1.02 1.03 1.02 1.03 1.02 1.02
(Y/Y*)PAAS 0.12 0.10 0.16 0.19 0.18 0.18 0.32 0.25 0.19 0.11 0.07 0.20 0.15 0.05 0.16 0.26 0.31 0.16

Note: post-Archean Australian shale (PAAS, McLennan, 1989). The REE-Y ratios are calculated as follow: (Ce/Ce*)PAAS ¼ CePAAS/(2PrPAAS  NdPAAS) (Bolhar et al., 2004), (Eu/Eu*)PAAS ¼ EuPAAS/(0.67SmPAAS þ 0.33TbPAAS)
(Bau and Dulski, 1996), (La/La*)PAAS ¼ LaPAAS/(3PrPAAS  2NdPAAS), (Pr/Pr*)PAAS ¼ 2PrPAAS/(CePAAS þ NdPAAS), (Y/Y*)PAAS ¼ 2YPAAS/(DyPAAS þ HoPAAS).
L. Soh Tamehe et al.
Fig. 7. Spider diagrams of the amphibole BIFs (straight line) and the amphibole–pyrite BIFs (dash line) from the Gouap deposit displaying (a) the trace element
composition normalized to the Upper Continental Crust (Rudnick and Gao, 2003) and (b) the REE–Y data normalized to the Post Archean Australian Shale (PAAS;
Taylor and McLennan, 1985).
samples have Au content less than 0.005 ppm excepting three samples
GB4-1 (0.01 ppm), GB4-2 (0.005 ppm) and GB9 (0.006 ppm).
The rare earth elements (ΣREE–Y) abundances in the amphibole BIFs
is distinctly moderate ranging from 16.2 to 60.8 ppm (average: 27.11
ppm). The Post Archean Australian Shale (PAAS)-normalized REE–Y
patterns of these BIF samples exhibit relative enrichment of HREE (Pr/
YbPAAS ¼ 0.20–0.62) with respect to LREE (La/YbPAAS ¼ 0.19–0.68) and
enrichment of MREE (Sm/YbPAAS ¼ 0.32–0.72) with respect to HREE
(Fig. 7b). The REE–Y patterns of all amphibole BIFs are also characterized
by: (i) slight positive La anomalies (La/La*PAAS ¼ 1.01–1.45), (ii) slight
negative to no Ce (Ce/Ce*PAAS ¼ 0.93–0.99) and Y anomalies (Y/Y*PAAS
¼ 0.94–1.02) anomalies, and (iii) pronounced positive Eu anomalies
((Eu/Eu*)PAAS ¼ 1.48–2.17). The amphibole BIFs show super-chondritic
Y/Ho ratios varying between 27.71 and 41.18 (average: 31.89).
The amphibole–pyrite BIFs typically have high and variable trace
elements contents compared to the amphibole BIFs with notable
559
Geoscience Frontiers 12 (2021) 549–572
enrichment of transition metals such as Cu (30–2460 ppm), Zn (49–341
ppm), Ni (5.9–289 ppm), Co (3.1–176.0 ppm), Cr (21–110 ppm), V
(11–80 ppm), and Sc (2–14.6 pppm) (Table 2, Fig. 7a). These BIFs also
contain high and variable LILE contents including Sr (5–532 ppm) and Ba
(3.7–453 ppm), except Rb and Cs which show much lower contents (<35
ppm). Zr has the highest contents (17–1210 ppm) for the HFSE in the
amphibole–pyrite BIFs, reflecting the presence of zircon as observed in
thin section (Fig. 5c–f). The other HFSE contents range from very low to
moderate abundances (0.07–29.9 ppm), whereas the remainder trace
elements (Li, Be and Ga) have insignificant contents in these BIFs
(Table 2, Fig. 7a). Most of these BIFs displays very low Au contents
(<0.005 ppm) except for two samples GBW3-3 and GB10-2 with 0.006
ppm and 0.007 ppm, respectively.
When normalized to the PAAS (Taylor and McLennan, 1985), the
amphibole–pyrite BIFs are obviously enriched in REE–Y (Fig. 7b). The
PAAS-normalized REE–Y patterns for these BIFs (except samples
L. Soh Tamehe et al. Geoscience Frontiers 12 (2021) 549–572

Table 3
Silicon and oxygen isotopic compositions of the Gouap BIFs.
Drillhole Depth (m) Lithology Sample Mineral δ30SiNBS28 (‰) δ18OV-SMOW (‰) Δ18Omt-qtz (‰)

DD036 129.50 Amphibole BIF GB9 quartz 0.3 9.5 13

magnetite 3.5
DD043 103.00 Amphibole BIF GB11-1 quartz 1.3 7.5 9.6
magnetite 2.1
DD043 104.00 Amphibole BIF GB11-2 quartz 1.3 6.8 8.6
magnetite 1.8
DD043 105.00 Amphibole BIF GB11-3 quartz 1.3 7 9.2
magnetite 2.2
DD043 106.00 Amphibole BIF GB11-4 quartz 1 7.8
DD043 107.00 Amphibole BIF GB11-5 quartz 0.5 8.2
DD043 171.30 Amphibole–pyrite BIF GB10-1 quartz 0.8 10.6 12.9
magnetite 2.3
DD043 171.35 Amphibole–pyrite BIF GB10-2 quartz 0.9 9.2 12.2
magnetite 3
DD043 174.50 Amphibole–pyrite BIF GB10-3 magnetite 1.7

GBW3-1, GB6, GB10–1 and GB10-2) show depletion of LREE and MREE
relative to HREE, with (La/Yb)PAAS of 0.20–2.14 and (Sm/Yb)PAAS of
0.25–2.31 (Fig. 7b). Their REE–Y patterns also display slight positive La
anomalies and slight negative Ce anomalies with (La/La*)PAAS and
(Ce/Ce*)PAAS ratios 0.93–1.14 and 0.95–0.99, respectively. Negative to
positive Eu anomalies ((Eu/Eu*)PAAS ¼ 0.58–2.08 and pronounced
negative Y anomalies (Y/Y*)PAAS ¼ 0.05–0.31) is notable for most sam-
ples. The amphibole–pyrite BIFs exhibit chondritic Y/Ho ratios ranging
from 22.76 to 30.26 (av: 27.51).
4.3. Isotopes composition
The isotopes data of the Gouap BIFs is presented in Tables 3 and 4.
The δ30SiNBS28 values of the quartz range from 1.5‰ to 0.3‰
(average: 0.95‰) and from 0.8‰ to 0.9‰ (average: 0.85‰) for
the amphibole BIFs and amphibole–pyrite BIFs, respectively (Table 3).
The quartz is characterized by δ18OV-SMOW of 6.8‰–9.5‰ (mean: 7.8‰)
for the amphibole BIFs and of 9.2‰–10.6‰ (mean: 9.9‰) for the
amphibole–pyrite BIFs (Table 3). The magnetite δ18OV-SMOW varies from
3.5‰ to 1.8‰ (average: 2.4‰) and from 3‰ to 1.7‰ (average:
2.3‰) for the amphibole BIFs and amphibole–pyrite BIFs, respectively
(Table 3). The Δ18Omt-qtz values of the Gouap BIFs range from 8.6‰ to
13‰ (Table 3). The δ34SV-CDT values of the pyrite from the amphib-
ole–pyrite BIFs vary between 1.1‰ and 1.8‰ with an average value of
1.37‰ (Table 4).
4.4. LA-ICP-MS zircon U–Pb dating
Zircon U–Pb age data for the two Gouap BIF samples (GB10-1 and
GBW3-1) is reported in Appendix S2 and shown in Figs. 8 and 9.
Detrital zircon grains recovered from the sample GB10-1 are gener-
ally euhedral to subhedral with size of 75–200 μm. CL images reveal that
most zircon grains are short to long prismatic with low to high lumi-
nescence and distinct oscillatory zoning (Fig. 8a). These zircon grains
display variable Th and U contents ranging from 33.4 to 433.4 ppm and
from 149.9 to 949.2 ppm, respectively. Their distinct oscillatory zoning
and relatively high Th/U (0.12–0.77, average: 0.43, Table 3) indicate a
magmatic origin (e.g., Koschek, 1993; Belousova et al., 2002; Hoskin and
Schaltegger, 2003; Corfu et al., 2003; Li et al., 2019, 2020). This is
confirmed on the BSE images by the absence of alteration haloes or zircon
overgrowths due to the overprint of hydrothermal events (Fig. 8a). The
obtained ages from the most twenty-eight concordant (>95%) grain
spots range from 2377  24 Ma to 2929  22 Ma (Appendix S2), sug-
gesting Mesoarchean to Paleoproterozoic source provenance. The age’s
distribution shows evidence of two main zircon populations. The first
population is composed of older detrital zircon grains, whose obtained
ages are concordant and plot near or on the concordia line and yield a
weighted mean 207Pb/206Pb age of 2619  34 Ma (MSWD ¼ 6.3, n ¼ 11;
Fig. 8b and c). The second and younger detrital zircon population (four
grain spots) yielded a weighted average 207Pb/206Pb age of 2422  50
Ma (MSWD ¼ 1.9, n ¼ 4; Fig. 8b), suggesting early Paleoproterozoic
maximum depositional age (MDA) for the Gouap BIFs.
Based on the CL images, most zircon grains in sample GBW3-1 are
euhedral short angular (56–84 μm) to rounded, whereas a few are short
to long prismatic (up to 130 μm) (Fig. 9a). Most zircon grains largely
preserve magmatic oscillatory zoning at the core, with U-rich hydro-
thermal replacement rims. On the BSE images, all the zircon grains of this
sample do not show any particular internal structure and appear homo-
geneous (Fig. 9a). These zircon grains commonly show low Th and
moderate U contents varying between 35.2–64.1 ppm and 64.9–670.8
ppm, respectively. Most zircon grains display low Th/U ratio ranging
between 0.06 and 0.77 (Appendix S2) as well as high Nb, Hf and Ti
contents, low LREE, and large positive Ce anomalies (not shown). This
suggests that these zircon grains are late-magmatic to hydrothermal
zircon (e.g., Pettke et al., 2005; Schaltegger, 2007; Ayers and Peters,
2018; Jiang et al., 2019). Thirty-four analyzed spots yield apparent
207
Pb/206Pb ages varying between 2031 and 2194 Ma, with a weighted
average age of 2089  8.3 Ma (MSWD ¼ 0.80; Fig. 9b and c).

5. Discussion
Table 4
The δ34SV-CDT values (‰) of pyrite from the Gouap amphibole–pyrite BIFs from
drillhole DD043. 5.1. Contamination in BIFs and influence on REE patterns
34
Depth (m) Sample Mineral δ SV-CDT (‰)
5.1.1. Detrital input
171.30 GB10-1 pyrite 1.1 In most cases, iron formations are detritus-free (e.g., Dymek and
171.35 GB10-2 pyrite 1.5
Klein, 1988; Beukes and Klein, 1990; Bau and Dulski, 1996; Mloszewska
174.50 GB10-3 pyrite 1.4
174.75 GB10-4 pyrite 1.5 et al., 2012; Liu et al., 2014; Peng et al., 2018), but terrigenous
175.15 GB10-5 pyrite 1.1 contamination have been reported worldwide (e.g., Pecoits et al., 2009;
175.45 GB10-6 pyrite 1.8 Mloszewska et al., 2012; Gourcerol et al., 2016; Ghosh and Baidya, 2017;
175.90 GB10-7 pyrite 1.3
Aoki et al., 2018; Ganno et al., 2017; Soh Tamehe et al., 2018; Sun et al.,
177.10 GB10-8 pyrite 1.4
178.00 GB10-9 pyrite 1.3 2018; Hou et al., 2019). Some authors also report the association of
178.70 GB10-10 pyrite 1.3 chemically pure and impure BIFs within the same depositional

560
L. Soh Tamehe et al.
Fig. 8. (a) Representative CL and BSE images with corresponding apparent U–Pb ages (Ma) of zircon from the sample GB10-1 (spot number in red and U–Pb age in
yellow). (b) Concordia plot of zircon U–Pb ages from the sample GB10-1. (c) LA-ICP-MS 207Pb/206Pb weighted mean age of zircon analyses from the sample GB10-1.
environment (Haugaard et al., 2013; Viehmann et al., 2015; Wang et al.,
2015; Barrote et al., 2017; Ndime et al., 2019). Overall, oxides (Al2O3
and TiO2), HFSE, LILE and transition metals are excellent monitor to
identify terrigenous contamination (e.g., Manikyamba et al., 1993; Arora
et al., 1995; Rao and Naqvi, 1995; Haugaard et al., 2013; Viehmann et al.,
2015; Wang et al., 2015). Zr, Rb, Sr, U and Th abundances in BIFs are
indicative of contamination from felsic crustal rocks, whereas the higher
contents of Cr, Ni, Co, Sc and V reflect input from mafic rocks (e.g.,
Manikyamba et al., 1993; Arora et al., 1995; Rao and Naqvi, 1995).
The content of Al2O3þTiO2 in the Gouap amphibole BIFs is low (<0.8
wt.%) except for samples GB4-3 and GB11-2 that show elevated con-
centration of these elements (Table 1). Most of the Gouap amphib-
ole–pyrite BIFs (except samples GBW3-3 and GBW3-4) display high
Al2O3þTiO2 content ranging from 2.25 to 7.14 wt.% (Table 1). Addi-
tionally, the Gouap BIFs show weak to strong positive correlation be-
tween Al2O3 and TiO2 (Fig. 10a), which may imply incorporation of
terrigenous components (Barrote et al., 2017, and references therein).
This is also corroborated by slight to strong positive correlations between
Al2O3þTiO2, Zr and other trace elements (Figs. 10b–h and 11a–d). The
higher contents of Zr, Sr, Th, Cr, Ni, Co and Cu in the amphibole-pyrite
BIFs compared to those of the amphibole BIFs are consistent with pres-
ence of felsic and mafic clastic components during the deposition of the
Gouap BIFs (e.g., Manikyamba et al., 1993; Arora et al., 1995, and ref-
erences therein).
Since Zr contents are low (ca. 2.2–10.2 ppm) in BIFs, previous studies
considered that the influence of contribution of clastic and volcanic
components on REE contents is trivial (e.g., Bolhar et al., 2004; Frei and
Polat, 2007; Friend et al., 2008). However, elevated ΣREE contents in
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Geoscience Frontiers 12 (2021) 549–572
BIFs are generally ascribed to admixture of clastic and volcanic material
during BIF deposition (e.g., Lan et al., 2019), albeit the interaction be-
tween later magmatic fluids and the BIFs may probably caused such REE
abundance (Barrote et al., 2017). The Gouap BIFs display variable high
ΣREE contents of 11.25–51.13 ppm (mean: 20.70 ppm) for the amphi-
bole BIFs and 29.25–696.33 ppm (mean: 180.69 ppm) for the amphib-
ole–pyrite BIFs. Fig. 11e–g shows that La, Sm and Yb contents are
positively correlated with Zr contents, suggesting that the REE contents
of the Gouap BIFs were influenced by detrital material.
Terrestrial materials such as felsic and basaltic rocks have a constant
chondritic Y/Ho ratio of ~27, whereas seawater and associated chemical
sediments have superchondritic Y/Ho values (e.g., Bau and Dulski, 1999;
Bolhar et al., 2005). Little admixtures of clastic and volcanic components
would depress seawater-like Y/Ho ratios of >44 (Bau and Dulski, 1996;
Bolhar et al., 2004). Most of the Gouap BIFs have higher Y/Ho ratio
(>27) and display a positive correlation between Zr content and Y/Ho
ratios (Fig. 11h). These features suggest the involvement of detrital
materials during the deposition of the Gouap BIFs.
5.1.2. Hydrothermal and metasomatic alteration
Post-depositional processes such as hydrothermal and metasomatic
alteration generally affect the trace metals and REE patterns in BIFs
particularly under high fluid/rock ratios (e.g., Hensler et al., 2015; Sil-
veira Braga et al., 2015; Peng et al., 2018). At the Gouap area, the
occurrence of minerals such as epidote, chlorite and specially dissemi-
nated pyrite in the amphibole-pyrite iron formations suggests secondary
hydrothermal alteration. The chondrite-like signature (24 < Y/Ho < 34)
of this rock also indicate the resetting of HREE content through the
L. Soh Tamehe et al.
Fig. 9. (a) Representative CL and BSE images with corresponding apparent U–Pb ages (Ma) of zircon from the sample GBW3-1 (spot number in red and U–Pb age in
yellow). (b) Concordia plot of zircon U–Pb ages from the sample GBW3-1. (c) U–Pb age histogram displaying the results of zircon analyses from the sample GBW3-1.
interaction with hydrothermal fluids as already discussed by Hensler
et al. (2015) and Sampaio et al. (2018). Further evidence of hydrother-
mal alteration is provided through the positive co-variation of the
redox-sensitive elements such as Ce and Eu with ΣREE (Fig. 12a and b).
5.2. Source of the Gouap BIFs
The REE–Y signature of iron formations have been used as a proxy to
identify the source of silica and iron (e.g., Bau and Dulski, 1996; Bolhar
et al., 2004; Alexander et al., 2008; Planavsky et al., 2010; Silveira Braga
et al., 2015; Ganno et al., 2017; Soh Tamehe et al., 2018; Ndime et al.,
2019). The conspicuous positive Eu anomalies in Archean and Paleo-
proterozoic BIFs indicates the involvement of hydrothermal fluids from
deep-sea spreading centers to sub-oceanic waters (e.g., Bau and Dulski,
1996; Bolhar et al., 2004; Kato et al., 2006; Planavsky et al., 2010, and
references therein). Strong positive anomalies characterize hydrothermal
fluids of high-temperature (>250  C), while weak to no Eu anomaly are
typical of low-temperature (<200  C) fluids (Basta et al., 2011). The
(Eu/Eu*)PAAS values of the Gouap amphibole BIFs vary from 1.48 to 2.17
and amphibole–pyrite BIFs from 0.58 to 2.08 that inversely correlates with
ΣREE (Fig. 12c), indicating that a secondary enrichment of these elements
was responsible for the decreased anomaly. The positive correlation of Ni
vs. Cr, Co vs. Cr and Ni vs. Co (Fig. 10e–g), suggests a primary hydrothermal
source for these elements (Dymek and Klein, 1988), though the influence of
detrital contaminant as well as hydrothermal and metasomatic alteration
should not be neglected as discussed in the previous section.
The Gouap BIFs exhibit distinctive (but less pronounced) seawater
signatures such as LREE-depletion, HREE-enrichment, and slight positive
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Geoscience Frontiers 12 (2021) 549–572
La and Eu anomalies (Bolhar et al., 2004) as depicted in their PAAS
normalized REE–Y patterns (Fig. 13). Similar features have been
observed in other least contaminated BIFs (Fig. 13; Wang et al., 2015;
Brando Soares et al., 2017; Soh Tamehe et al., 2018). However, the
studied BIFs show slight negative Y anomaly, which may be attributed to
slow rates of precipitation (Bau and Dulski, 1996). In Fig. 13, it is note-
worthy that the Gouap BIFs plot near the average compositions
low-temperature (<250  C) hydrothermal fluids (amphibole–pyrite BIFs)
or lie between the average composition of Low-T hydrothermal fluids and
South Pacific seawater (amphibole BIFs). On the other hand, the pro-
portion of seawater versus hydrothermal fluids is further emphasized in
Y/Ho vs. Eu/Sm and Sm/Yb vs. Eu/Sm diagram of Alexander et al.
(2008). Plotted on both diagrams (Fig. 14a and b), most of the Gouap
BIFs cluster near seawater and low-temperature hydrothermal fluids
(0.1%) fields, and far away from high-temperature hydrothermal fluids
(5%). Therefore, we suggest that the REE–Y signatures of the Gouap BIFs
were inherited from low-temperature (<200  C) hydrothermal fluids.
Using a combination of the above geochemical signatures, it can be
summarized that the Gouap BIFs were precipitated from a mixture of
low-temperature hydrothermal fluids and seawater with relatively high
detrital contamination.
5.3. Depositional environment and ocean redox chemistry
The Gross (1980) scheme has been widely used to classify the BIFs
into Algoma-type and Lake Superior-type based on their depositional
environment. Algoma-type BIFs are often interlayered with or strati-
graphically associated with volcanic rocks in greenstone belts, whereas
L. Soh Tamehe et al. Geoscience Frontiers 12 (2021) 549–572

Fig. 10. Binary diagrams of elemental contents for the Gouap BIFs: (a) TiO2 vs. Al2O3, (b) Zr vs. (Al2O3 þ TiO2), (c) Rb vs. Sr, (d) Th vs. U, (e) Ni vs. Cr, (f) Co vs. Cr,
(g) Ni vs. Co, (h) Sc vs. V.

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Fig. 11. Zr variation diagrams of (a) Co, (b) Cr, (c) Ni, (d) (Sc), (e) La, (f) Sm, (g) Yb and (h) Y/Ho ratio for the Gouap BIFs.

564
L. Soh Tamehe et al.
Fig. 12. ΣREE variation plots of (a) Ce, (b) Eu and (c) (Eu/Eu*)PAAS for the
Gouap BIFs.
the Lake Superior-type BIFs are typically deposited on stable continental
shelves and commonly in no association with volcanic rocks (Bekker
et al., 2010).
The Gouap BIFs, for instance, are mainly interbedded with meta-
sedimentary rocks including garnet gneisses, quartzites and staurolite
micaschists (Soh Tamehe et al., 2019). Although these BIFs display some
geochemical similarity with volcanic rocks in terms of transition metals
such as Cr, Co, Ni and Cu, no metavolcanics or volcaniclastic sediments
have been reported in the Gouap deposit. This suggests that the deposi-
tion of the Gouap BIFs is not linked to hydrothermal volcanic activity in
an island arc environment (e.g., Liu et al., 2014). Previous studies on BIFs
from the Nyong Group suggest that these BIFs were probably deposited in
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Geoscience Frontiers 12 (2021) 549–572
a back-arc basin or continental marginal ocean environment, similar to
Superior-type BIFs (Ganno et al., 2017; Soh Tamehe et al., 2018). All the
Gouap BIFs (except five samples, see Table 2) are largely characterized by
low (Eu/Eu*)PAAS ratio < 1.8, that are typical of Superior-type BIFs
(Huston and Logan, 2004). Hence, we infer that the Gouap BIFs were
deposited in a region where sediments extended from continental shelf to
deep-water settings along craton margins as proposed for the Krivoy Rog
BIFs (Viehmann et al., 2015).
Most of the Gouap BIFs lack negative Ce anomalies in the (Pr/
Pr*)PAAS vs. (Ce/Ce*)PAAS diagram (Fig. 15; Bau and Dulski, 1996). This
suggests that the Gouap BIFs were precipitated in suboxic to relatively
anoxic seawater, albeit LREE-depletion relative to HREE of these BIFs in
PAAS-normalized diagram (Fig. 13) indicates deposition under oxidized
shallow seawater. The above interpretations imply that the Gouap basin
may have varied redox conditions and a strong redoxcline separating an
upper oxic water column from deeper waters that were suboxic to anoxic
(Planavsky et al., 2010).
5.4. Isotopic constrains of the Gouap BIFs
Although contaminated BIFs are poor seawater archive, their isotopes
compositions are particularly useful as proxies of paleo-environmental
conditions from where the BIFs were precipitated (e.g., Becker and
Clayton, 1976; Perry, 1983; and references therein). Si isotope compo-
sitions of quartz in BIFs have been applied on discriminating weathering
and hydrothermal sources of silica (e.g., Steinhoefel et al., 2010; Heck
et al., 2011), whereas O isotope studies of BIFs have been focused to
constrain paleo-temperatures as well as fluid-mineral interactions and
temperatures of equilibration or isotopic exchange (e.g., Gregory and
Criss, 1986; Valley, 2001; Hyslop et al., 2008). On the other hand, S
isotopic signatures of BIFs commonly distinguish biogenic and volcanic
sources of pyrite (e.g., Cameron, 1983; Bowins and Crocket, 1994).
Although our BIF samples were collected from an iron mineralized zone,
the minerals from the iron ore were not analyzed in this study.
In general, quartz with negative δ30SiNBS28 (<0‰) is thought to have
been derived from hydrothermal fluids (e.g., Ding et al., 1996; Andre
et al., 2006; Li et al., 2014), whereas quartz with positive δ30SiNBS28
(>0‰) point out the influence of a continental source or precipitation
from isotopically heavy seawater (Robert and Chaussidon, 2006; Van den
Boorn et al., 2007). The quartz in the Gouap BIFs is highly depleted in
30
Si with δ30SiNBS28 values ranging from 1.5‰ to 0.3‰ (mean:
0.95‰) and from 0.8‰ to 0.9‰ (mean: 0.85‰) for the amphibole
BIFs and amphibole–pyrite BIFs, respectively (Table 3). This implies that
the quartz of the Gouap BIFs was probably formed by precipitation from
hydrothermal fluids. Similar δ30SiNBS28 values are documented for the
quartz of the Huoqiu BIFs (Hou et al., 2017, 2019) and the Yuanjiacun
BIFs (Hou et al., 2014; Men et al., 2019) in the North China Craton.
Nonetheless, a terrigenous input of silica cannot be ruled out as a source
of the depleted silicon isotopes (δ30Si < 0) of quartz within the Gouap
BIFs (Wang et al., 2016).
The quartz within the Gouap BIFs have δ18OV-SMOW values of 6.8‰–
9.5‰ (mean: 7.8‰) and 9.2‰–10.6‰ (mean: 9.9‰) for the amphibole
BIFs and the amphibole–pyrite BIFs, respectively (Table 3). These
δ18OV-SMOW values falls between those for quartz within igneous rocks
and values for marine siliceous rocks, similar to siliceous rocks that
formed by high-temperature hydrothermal sedimentation (Li and Jiang,
1995; Hou et al., 2014, 2019; Li et al., 2014). Although the Gouap BIFs
have been metamorphosed up to amphibolite facies conditions (Soh
Tamehe et al., 2019), this metamorphism and hydrothermal fluid ex-
change are likely to have decreased rather than increased quartz
δ18OV-SMOW values (Knauth and Lowe, 2003; Knauth, 2005; Robert and
Chaussidon, 2006). This suggests that the real δ18OV-SMOW values of
quartz within the Gouap BIFs are expected to have been higher than the
obtained values of this study as proposed for the quartz from the Huoqiu
BIFs (Hou et al., 2019) and the Yuanjiacun BIFs (Hou et al., 2014) in the
North China Craton.
L. Soh Tamehe et al.
Fig. 13. Average PAAS-normalized REE–Y patterns of the Gouap BIFs compared with the average of seawater and hydrothermal fluids are from Bolhar et al. (2004)
and Bau and Dulski (1999), respectively. Data of Yuanjiacun BIFs (Wang et al., 2015), Biquinho BIFs (Brando Soares et al., 2017) and Kpwa-Atog Boga BIFs (Soh
Tamehe et al., 2018) are also shown for comparison.
Magnetite with δ18O values <þ0.9‰ indicates a precipitation from
low-temperature (400  C) hydrothermal processes, whereas magnetite
with δ18O values >þ0.9‰ is interpreted to have originated from a
magma or high-temperature magmatic fluids (~800–1000  C) (Jonsson
et al., 2013). The δ18O values of the magnetite from the Gouap BIFs
(3.5‰ to 1.8‰ for the amphibole BIFs and 3‰ to 1.7‰ for the
amphibole–pyrite BIFs) fall within the range (4‰ to þ5‰) of weakly
metamorphosed Archean to Paleoproterozoic BIFs (Gutzmer et al.,
2006). However, our data also overlap the overall δ18O isotope values
(9.5‰ to þ3.2‰) of some iron oxides formed during iron mineraliza-
tion in the Thabazimbi, Noamundi, Pic de Fon, Carajas, Hamersley, and
Gorumahishani-Badampahar high-grade iron ore deposits (Gutzmer
et al., 2006; Cope et al., 2008; E Silva et al., 2008, E Silva et al., 2013;
Thorne et al., 2009; Ghosh and Baidya, 2017). Because the Gouap BIFs
have undergone secondary alteration, we suggest that the observed δ18O
isotope signature of the magnetite from the Gouap BIFs might be
inherited from secondary hydrothermal alteration processes but without
significant iron enrichment.
Additionally, previous O isotope studies of BIFs have demonstrated
that quartz-magnetite oxygen isotope can be a useful geothermometer to
constrain the thermal gradients from which the BIFs have been meta-
morphosed (e.g., Becker and Clayton, 1976; Perry, 1983; Hyslop et al.,
2008; Hoefs, 2009; Li et al., 2013). It is noticeable that the Δ18Omt-qtz
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Geoscience Frontiers 12 (2021) 549–572
values of the Gouap BIFs are ranging from 8.6‰ to 13‰ (see Table 3).
Because the Gouap BIFs have been metamorphosed, it is useful to plot
δ18O values of quartz and magnetite, which often record discordant
temperatures in slowly cooled metamorphic rocks since these minerals
are resistant to post-metamorphic exchange (Perry, 1983; Hoefs, 2009).
In this plot which gives calculated temperature ranges for pair minerals,
the quartz–magnetite of amphibole BIFs fall between 450 and 600  C;
while the temperature indicated for this pair mineral of amphib-
ole–pyrite BIFs is  450  C (Fig. 16a). Conformable results were obtained
while using the plot of fractionation of Perry (1983) which also provides
temperature of metamorphism for pair minerals (Fig. 16b). Since the
quartz and magnetite are the major components of the BIFs, we can es-
timate that the Gouap BIFs were metamorphosed at 350–600  C, which
corresponds well with their low- to medium-grade metamorphic
conditions.
Given that the presence of pyrite in the Gouap BIFs rather indicates
secondary hydrothermal alteration, their δ34S isotope signature may
reveal an influence from hydrothermal fluids (E Silva et al., 2008, E Silva
et al., 2013). The δ34S values of the amphibole–pyrite BIFs ranging from
1.1‰ to 1.8‰ seem compatible with a chemical precipitation by hy-
drothermal fluids related to magmatic processes (Shanks, 2001). How-
ever, the range of δ34S data for the Gouap BIFs is closed to the δ34S values
(between 2.84‰ and þ4.38‰, Table 4) obtained for twelve pyrite
L. Soh Tamehe et al.
Fig. 14. Composition of the Gouap BIFs plotted in diagram of (a) Y/Ho vs. Eu/
Sm and (b) Sm/Yb vs. Eu/Sm (after Alexander et al., 2008) displaying the
deposition of the studied BIFs in seawater with contribution of <0.1% hydro-
thermal fluids.
grains in the ~2.5 Ga Huoqiu BIFs from the North China Craton (Hou
et al., 2019). This suggests that the δ34S compositions of the Gouap BIFs
are akin to those of Superior-type BIF (Hou et al., 2019).
In summary, the different isotope data of the Gouap BIFs confirms the
influence of seawater as well as secondary hydrothermal alteration.
5.5. Depositional age of the Gouap BIFs
Wallrocks interlayered with the BIFs have been generally used to
constrain the depositional age (e.g., Zhang et al., 2011; Cabral et al.,
2012; Chombong et al., 2013; Wang et al., 2015; Barrote et al., 2017;
Brando Soares et al., 2017; Lan et al., 2019; Tong et al., 2019; Silveira
Braga et al., 2019). However, some authors (e.g., Lai and Yang, 2012; Cen
et al., 2012; Lan et al., 2014; Liu and Yang, 2015; Zhu et al., 2015; Kim
et al., 2018; Liu et al., 2018; Nzepang Tankwa et al., 2020) have delivered
direct dating of detrital zircon grains separated from the iron formations,
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Geoscience Frontiers 12 (2021) 549–572
providing a potentially precise depositional age for these rocks. We
conducted in-situ zircon dating of two amphibole–pyrite BIFs samples
(GB10-1 and GBW3-1) due to the petrographical evidence of this mineral
in thin section (see Fig. 6c, e) as well as to the detrital contamination as
interpreted from geochemical composition.
Our studies show that detrital zircon from sample GB10-1 have
oscillatory zoning (Fig. 8a) and high Th/U ratios (mean: 0.43, Appendix
S2), which are typical features of a magmatic origin. Thus, the
207
Pb/206Pb age of these zircon grains range from 2929 to 2378 Ma
indicating a Mesoarchean to Paleoproterozoic source. The youngest age
of detrital zircon defines the maximum depositional age (MDA) of the
Gouap BIFs at ca. 2422 Ma, thus during the early Paleoproterozoic time.
This age is similar to the previous SHRIMP U–Pb age of ~2423 Ma ob-
tained by Lerouge et al. (2006) on detrital zircon from metasediments in
the Nyong Group. The early Paleoproterozoic MDA is also consistent with
some geochemical characteristics of many Archean–Paleoproterozoic
transition BIFs (e.g., general trend of LREE depletion relative to HREE, a
weak positive Eu anomaly and no Ce anomalies) observed in the Gouap
BIFs (Planavsky et al., 2010; Fig. 15).
It is noteworthy that detrital zircons from sample GBW3-1 have no
oscillatory zoning and display multifaceted shapes with compositionally
homogenous texture on BSE images (Fig. 9a). Corfu et al. (2003) have
suggested that the development of homogenous texture in magmatic
zircon could be attributed to the modifications during late and
post-magmatic cooling. Additionally, the studied zircon grains display
magmatic cores surrounded by high-U light domains, probably formed by
metasomatism or recrystallization. Sample GBW3-1 is strongly hydro-
thermally altered as shown in the previous sections. This suggests that
the light regions surrounding the dark core may have formed by meta-
somatism. The analyzed zircon grains yield a 207Pb/206Pb age varying
between 2032 and 2194 Ma, with a weighted average age of 2089  8.3
Ma (MSWD ¼ 0.80). More recently, Loose and Schenk (2018) have
performed U–Pb SHRIMP dating of eclogite samples from the Nyong
Group and constrained the high-pressure metamorphic event at 2093 
45 Ma. This age, which is quite similar to that obtained in the Gouap
amphibole–pyrite BIFs, implies that the Nyong Group suffered a regional
metamorphism accompanied with hydrothermal activity during the
Paleoproterozoic, precisely at ca. 2.09 Ga.
Based on the above data, we propose that the Gouap BIFs were
deposited at ca. 2422 Ma and metamorphosed some ca. 330 Ma later,
during the Eburnean–Transamazonian orogeny.
5.6. Implication for the age of the Ntem complex BIFs and correlation with
the Brazilian IFs
In Cameroon, the BIF depositional age in the Ntem Group is relatively
constrained through the pioneering studies made by Chombong and Suh
(2013) and Ndime et al. (2019). Chombong and Suh (2013) have per-
formed SHRIMP U–Pb analyses on zircon from metavolcanics inter-
bedded with the Mbalam BIFs within the Ntem Group and reported an
age of 2883  20 Ma interpreted as the onset of BIF deposition. More
recently, Ndime et al. (2019) proposed a Neoarchean age of 2679 Ma as
the minimum depositional age of the Nkout West BIFs based on the
whole-rock Pb–Pb applied on magnetite BIF. These results indicate a
regional period of BIF deposition from Mesoarchean to Neoarchean
within the Ntem Group.
Although the ages of the BIF associated wallrocks in the Nyong Group
have not been precisely constrained yet, the detrital zircon ages of the
present study shed a new light on the geologic history of this region. The
LA-ICP-MS zircon U–Pb dating results of sample GB10-1 range from 2929
to 2378 Ma. The occurrence of the 2.9–2.3 Ga detrital zircon in the Gouap
BIFs suggests the existence of Mesoarchean (~2.9 Ga) crust in the Nyong
Group. This result is in good agreement with the ca. 2.92 Ga SIMS zircon
U–Pb crystallization age of charnockites from the Ntem Complex (Li
et al., 2016), while Tchameni et al. (2000) have reported Pb–Pb zircon
evaporation age of 2666  2 Ma and 2687  3 Ma on high-K granitic
L. Soh Tamehe et al.
Fig. 15. Composition of the Gouap BIFs plotted in a (Ce/Ce*)PAAS vs. (Pr/Pr*)PAAS diagram after Bau and Dulski (1996). Fields of late Paleoproterozoic BIFs (<2.0 Ga)
and Archean and early Paleoproterozoic BIFs (>2.4 Ga) are from Planavsky et al. (2010).
rocks from the same complex. The weighted mean 207Pb/206Pb detrital
age of 2619  34 Ma obtained in this study suggests an important Neo-
archean detrital component, probably of felsic composition (high-K
granitoid), during the Gouap BIF deposition.
Our direct LA-ICP-MS U–Pb zircon detrital ages has constrained the
MDA of the Gouap BIFs within the Nyong Group at ca. 2422 Ma, implying
an early Paleoproterozoic age. This age is much younger than the Neo-
archean age (2699  7 Ma; Chombong et al., 2017) reported in the
magnetite gneisses from the Ngovayang iron ore deposit (see Fig. 2),
suggesting at least two different BIF units within the Nyong Group. The
Gouap BIFs have also undergone regional hydrothermal activity and
metamorphism during 2194–2032 Ma, which overlaps the age of the
metamorphism (2100–2000 Ma) in the Nyong Group as reported by
previous authors (Toteu et al., 1994; Lerouge et al., 2006; Loose and
Schenk, 2018; Nzepang Tankwa et al., 2020).
Comparable ages have been documented by previous geochronolog-
ical studies for IF deposition in the Itabira Group (Cau^e and Gandarela
Formations) from the Quadrilatero Ferrífero Mining District of the S~ao
Francisco craton (Brazil). The age of the Cau^e IF is bracketed by the U–Pb
dates of ca. 2.6 Ga for the youngest detrital zircon from the underlying
Moeda Formation (Machado et al., 1992, 1996; Hartmann et al., 2006;
Martinez Dopico et al., 2017) and the Pb–Pb isochron date of 2419  19
Ma for carbonates of the overlying Gandarela Formation (Babinski et al.,
1995). These ages are comparable to the MDA (~2422 Ma) of the Gouap
BIFs. The ages of metamorphic monazite and titanite constrain the peak
of metamorphism at the late stage of the Transamazonian orogeny to ca.
2.03–2.06 Ga (Machado et al., 1992; Noce et al., 1998; Aguilar et al.,
2017). This latter age can be correlated with the metamorphic event of
the Gouap BIFs. Thus, the Nyong Group is part of the Palaeoproterozoic
Transamazonian belt, which once extended from west-central Africa to
northeastern Brazil, a consequence of the Eburnean–Transamazonian
collision ca. 2100 Ma of the Congo and the S~ao Francisco cratons (Toteu
et al., 1994; Feybesse et al., 1998; Penaye et al., 2004; Lerouge et al.,
2006; Nzepang Tankwa et al., 2020).
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Geoscience Frontiers 12 (2021) 549–572
6. Conclusion
The Gouap deposit is a recently discovered iron deposit located in the
Nyong Group of the Ntem Complex (southern Cameroon). This iron de-
posit is characterized by amphibole and amphibole–pyrite BIFs inter-
bedded with gneisses, micaschists and quartzites. Combining isotopic,
geochemical and geochronological studies of the Gouap BIFs, we came to
the following conclusions:
(1) The Gouap BIFs show variable high Fe2O3þSiO2 contents and
trace elements (e.g., Zr, Co, Cu, Ni and Sc), which suggests that
their chemical precipitation was influenced by variable terrige-
nous input and secondary hydrothermal alteration. Their REE–Y
patterns display LREE depletion and positive La anomalies, which
are inherited from seawater. Positive Eu anomalies further indi-
cate the contribution of hydrothermal fluids.
(2) The isotopic data (δ30Si, δ18O and δ34S) suggest that the Gouap
BIFs were formed by mixing of seawater and low-temperature
hydrothermal fluids.
(3) The Gouap BIFs were probably deposited in an extensive basin
between an oceanic volcanic center and a continental margin
setting, similar to paleogeographic settings proposed by Beukes
and Gutzmer (2008) for a combined Hamersley-Transvaal Basin.
(4) Detrital zircon grains extracted from two BIF samples reveal that
the Gouap BIFs were deposited at ca. 2422 Ma and experienced
medium-grade metamorphism and metasomatism at ca. 2089 Ma
during the Eburnean–Transamazonian orogeny, like the Cau^e
Formation at the SW-border of the S~ao Francisco protocraton.
(5) The Cau^e and the Gouap IFs were probably deposited at the border
of an adjoining Archean continental mass (protocratons) that were
amalgamated in the Rhyacian period (Transamazonian Orogeny)
and finally consolidated in the Brasiliano–Congo orogeny as the
S~ao Francisco-Congo craton.
L. Soh Tamehe et al.
Fig. 16. Diagrams depicting the metamorphic conditions for the Gouap BIFs: (a)
δ18O of quartz vs. δ18O of magnetite for metamorphic rocks (modified after
Kohn, 1999; Hoefs, 2009). (b) Plot of fractionation (Δ ¼ 1000 lnα) vs. Tem-
perature ( C) for different pair minerals including quartz-water (ΔQW),
siderite-water (ΔSW), calcite-water (ΔCW), magnetite-water (ΔMW), and
quartz-magnetite (ΔQM) (modified after Perry, 1983). ΔQW, ΔMW, and ΔSW data
are from Becker and Clayton (1976).
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
569
Geoscience Frontiers 12 (2021) 549–572
Acknowledgements
This work forms part of the first author’s PhD dissertation at China
University of Mining and Technology (Xuzhou, China). The authors
thank the mineral exploration company G-Stones Resources Ltd., espe-
cially Mr. Bougne Dieudonne, for the permission to access unpublished
data and collect drillcore samples of the Gouap iron deposit. We also
thank all geologists and technicians of the mineral company for assis-
tance during fieldwork. Associate Editor Christopher Spencer and one
anonymous reviewer are gratefully acknowledged for their constructive
reviews and comments. This work was supported by the “Fundamental
Research Funds for the Chinese Central Universities” (Grant No.
2017CXNL03) and the Chinese Scholarship Council(Grant No.
2015120T19). Prof. Hou Kejun, Prof. Li Huan, Lu Yang, Quan Ruiping
and Jiang Weicheng are thanked for their help with LA-ICP-MS zircon
U–Pb analyses and suggestions for data processing. We are grateful to
L.C. Zhang, C.L. Wang, Z.D. Peng, X.X. Tong and A.P. Djoukouo Soh for
constructive discussion and helpful advice during an early presentation
of this study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.gsf.2020.07.009.
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