GJ

Article
Vol. 28, No. 1, p. 27−49, February 2024
https://doi.org/10.1007/s12303-023-0037-2
pISSN 1226-4806 eISSN 1598-7477 Geosciences Journal

The Nkonko Ni-Cr bearing regolith in DRC: a study of

petrography and geochemistry to understand serpentini-
zation and weathering processes of mantle rock
Douxdoux Kumakele Makutu1 and Jung Hun Seo2*
1
Department of Energy Resource Engineering, Inha University, Incheon 22212, Republic of Korea
2
School of Earth and Environmental Sciences, Seoul National University, Seoul 08826, Republic of Korea

ABSTRACT: Regolith-hosted Ni-Cr prospects in the Nkonko serpentinized massif are located near Kananga city in the Democratic
Republic of Congo (DRC). This serpentinized massif displays an underground regolith profile divided into three main layers: (1)
unweathered serpentinite bedrock, (2) saprolite serpentinites, and (3) the pedozone top layer. The bedrock serpentinites consist of ser-
pentine (including lizardite and antigorite “garnierite”) as a major phase, with Cr-spinel and magnetite as a subsidiary phase. The rock
contains rare pseudo-olivine relicts. Saprolite serpentinites contain serpentines (e.g., lizardite, chrysotile, antigorite “garnierite”) and
subordinate ferrochromite and Cr-magnetite. These saprolite serpentinites are crosscut by veins of “garnierite” phase, talc, brucite,
magnetite, magnesite, and chlorite. The pedozone primarily consists of lateritic soils with red and yellow limonite. Saprolite ser-
pentinites exhibit relatively higher Al2O3, FeO, Fe2O3, and volatiles (LOI: loss on ignition) compared to bedrock serpentinites, while
maintaining similar SiO2 contents. For trace elements, saprolite serpentinites contain elevated Cr (up to 5.4 wt%) and Ni (up to 2.0 wt%) com-
pared to bedrock samples (Cr up to 0.9 and Ni up to 0.3 wt%). The REE concentrations are low (total REE of about 2.0 ppm) and remain
unchanged between the saprolites and bedrocks. Spinel is identified as the main host mineral for Cr, while secondary serpentine “gar-
nierite” is the primary host phase for Ni. Plots of Al2O3/SiO2 versus MgO/SiO2 for bedrock and saprolite serpentinites, along with the
REE patterns, suggest that the serpentine regolith originated from the alteration and weathering of harzburgite.
Key words: Nkonko serpentinite, Ni-Cr in regolith, EPMA, LA-ICP-MS, serpentinization and weathering

Manuscript received May 14, 2023; Manuscript accepted November 9, 2023

1. INTRODUCTION champs et al., 2013; Villanova-de-Benavent et al., 2013, 2014;

Mizukami et al., 2014) margins of subduction zones, oceanic
Serpentinites are derived from the alteration (or weathering) and continental rifts (Boschi et al., 2013; Nozaka et al., 2017),
of mafic and ultramafic rocks or any Mg-rich formations (Klein, and even inside shielded cratonic areas (Pasteris, 1981; Treloar,
2009; Deschamps et al., 2013; Nozaka et al., 2017). They are 1987; Mohanty et al., 2019) (Fig. 1).
associated with various geodynamic contexts, such as active In the Democratic Republic of Congo (DRC), serpentinites
(Reynard, 2013) and passive (Bonatti, 1976; Nozaka, 2003; Des- occur inside the Congo-Kasai Archean (> 3.3 Ga) craton (Fig. 2)
(Herman and Raucq, 1962; De Waele et al., 2008; Yang et al.,
Editorial responsibility: Jinwook Kim 2012; Debruyne et al., 2019) and this last one extends over
*Corresponding author:
countries such as Angola, Cameroon, Congo Brazzaville, Gabon,
Jung Hun Seo and Central Africa Republic (Cahen et al., 1984; Cahen et al.,
School of Earth and Environmental Sciences, Seoul National Univer- 1987; Hanson, 2003; Debruyne et al., 2019). Most serpentinites
sity, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea
originate from Mg-rich lithologies, such as peridotite, amphibolite,
Tel: +82-2-880-6738, Fax: +82-2-871-3269, E-mail: [email protected]
pyroxenites, dolomites, and, to a lesser extent, basaltic lavas. They
Electronic supplementary material
The online version of this article (https://doi.org/10.1007/s12303-023-
are often sources of nickel (Ni) and chromium (Cr) (Nozaka,
0037-2) contains supplementary material, which is available to autho- 2005; Frost and Beard, 2007; González-Mancera et al., 2009;
rized users. Frost et al., 2013; Huang et al., 2017; Nozaka et al., 2017). The
©The Association of Korean Geoscience Societies and Springer 2024 serpentinites in the Congo-Kasai craton originate from low-
28 Douxdoux K. Makutu and Jung Hun Seo

Fig. 1. A summarized global map of serpentinite rock and soil distributions: 1. Siberia (Southern Ural), 2. Philippines, 3. Japan, 4. Western Aus-
tralia, 5. New Zealand, 6. Newfoundland, USA, 7. Maryland, USA, 8. Cuba (Escambray), 9. Puerto Rico, 10. Brazil, 11. Norway (Leka ophiolite),
12. Finland, 13. Scotland, 14. Spain (Cerro del Almirez and Cabo Ortega), 15. Italy, 16. Greece, 17. Turkey (NW Anatolia), 18. Oman, 19. Burma,
20. South Africa, 21. France (Alps), 22. Poland, 23. Albania, 24. Czech Republic, 25. Taiwan, 26. England, 27. Mexico, 28. Zimbabwe, 29. Cam-
eroon, 30. Sri Lanka, 31. Nickel mountain, USA , 32.Atlantis Massif, 33.Mark and Vema seamount zone, 34. Hess Deep, 35. Sandwich arc, 36.
New Caledonia, 37. Mariana though, 38. Zagros, 39. Tso Morari, 40. Nkonko (and Lutshatsha) Massif (This study).

temperature (approximately 50–80 ℃) alteration of primarily Delhal et al., 1986; Hanson, 2003; Debruyne et al., 2019) covered
ultramafic rocks, including peridotites and pyroxenites (Raucq, the entire craton complex by focusing mainly on the petrography
1961; Herman and Raucq, 1962; Cahen et al., 1987; Debruyne et and geochemistry as well as age dating of igneous and metamorphic
al., 2019). In the Congo-Kasai craton, three main serpentinized rocks (e.g., granulite, gneiss, migmatite, and granites). Without
bodies including Lutshatsha, Fwamba, Nkonko (this study), providing detailed petro-geochemical information, they barely
and tens of minor dykes have been reported (Raucq, 1961; Her- mentioned the Nkonko massif as a dyke intrusion of the Congo
man and Raucq, 1962). craton. No updated and published studies specifically on the
The Nkonko serpentinized massif was first discovered in Nkonko serpentinized body have been carried out since then,
1958 during exploration missions supervised by King Leopold which led us to investigate the serpentinized body in detail.
II and conducted by Legrand and Raucq in collaboration with In this study, we report field data of the Nkonko serpentinite
the Africa Royal Museum of Tervuren (Belgium), The Forminière, body, which is approximately 20–24 km in length and 250–500 m
and The Bécéka Mining Company (Raucq, 1961; Herman and wide, and located about 20 km southwest of Kananga city in
Raucq, 1962). Despite the fact that the mission was initiated for DRC. We examine the rock (and mineral) petrography and
kimberlite dyke, the discovery of serpentinites in the Nkonko, geochemistry in the regolith zone, such as the saprolite and
Lutshatsha, and Mfwamba sites raised interests in precious pedozone, in comparison to the relatively unaltered bedrock in
metals, such as platinum group elements (PGE) and Ni-Cr. The order to understand serpentinization and weathering processes.
first well-documented report that described the Nkonko body This study offers updated petrologic-geochemical analyses of
was established and published in 1961 and 1962 (Raucq, 1961; the Nkonko serpentinite, using techniques such as petrographic
Herman and Raucq, 1962). This report contained field and observations, SEM (Scanning Electron Microscope), Raman
petrographic descriptions as well as results of chemical analyses. spectroscopy, XRD (X-ray Diffraction), EPMA (Electron Probe
Several decades later, a few studies (Cahen et al., 1984, 1987; Microanalyses), and XRF (X-ray Fluorescence), for a better

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 29

understanding of the enrichment processes of serpentinite-hosted Tanzanian block in Tanzania, the West-Nile complexes in the
Ni-Cr laterite, associated by-products (Al, V, Co, Zn), and industrial East African regions, and the Kasai-Lomami complex (the focus
minerals (talc, serpentine, and magnesite) in the regolith. of this study) in the DRC (Hanson, 2003; Kröner and Stern,
2005; Kadima et al., 2011; Li et al., 2016; Debruyne et al., 2019;
2. GEOLOGICAL SETTINGS Bruno et al., 2021). The Kasai-Lomami complex has yielded
Archean ages of 2.3–3.5 Ga (age dating by Sm-Nd, U-Pb and
2.1. Regional and Local Geology Rb-Sr) and hosts high-grade metamorphic rocks and igneous
rocks, including granulites, migmatites, amphibolites, gneiss,
The Nkonko serpentinized massif is part of the Archean gneiss-migmatites, migmatite-granites, granites, peridotite, and
Congo-Kasai shield, which is exposed in the central parts of serpentinite (Cahen et al., 1984, 1987; Delhal et al., 1986; Han-
Africa and covers about 50% of the DRC. The shield extends to son, 2003; Batumike et al., 2009; Fernandez-Alonso et al., 2012,
the neighboring coastal Atlantic of Angola and the northern 2016). The Kasai-Lomami complex, as a supergroup, consists of
Cameroon sides (Cahen et al., 1984, 1987; Delhal et al., 1986; five main groups or sub-complexes (Fig. 2), including (1) the
Cailteux et al., 1994; Carvalho et al., 2000; Li et al., 2016; Debruyne Luanyi charnockite-enderbite and granulite complex, (2) the
et al., 2019). The Congo-Kasai craton was formed by the Sandoa-Kapanga gneissic-granite complex, (3) the Kanda-Kanda
accretion of sparse blocks, including numerous small complex tonalite complex, (4) the Lueta gabbro-norites and charnockites
entities such as the Ntem-Chailu complex in Cameroon, the complex, and (5) the Dibaya granite and migmatite complex

Fig. 2. A simplified geological map of the Congo-Kasai craton as of the Archean Dibaya granitic and migmatitic complex yielding ages of
2680–2625 Ma. The red rectangle is used for the study area, the radiometric U-Pb ages are in bold texts, and Rb-Sr and/or Sm-Nd ages are
in regular texts (Cahen et al., 1984; Batumike et al., 2009; Fernandez-Alonso et al., 2012; Li et al., 2016; Debruyne et al., 2019).

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
30 Douxdoux K. Makutu and Jung Hun Seo

(this study) (Hanson, 2003; Debruyne et al., 2019). The Luanyi regional NW-SE foliations. The complex includes the Mufesu
complex (3.3–3.5 Ga, Sm-Nd) consists mainly of gneiss and granulites oriented NW-SE, and subsidiary foliated hypersthene
granulite crosscut by pegmatites. The Sandoa-Kapanga Complex gneisses (charnockites) and garnet ± sillimanite-bearing quartzo-
(3.0–3.1 Ga, U-Pb) consists mostly of granitic and granulite feldspathic rocks (Herman and Raucq, 1962; Cahen et al., 1987;
gneissic rocks, displaying NE-SE foliation trends overprinted by Debruyne et al., 2019). The Kanda-Kanda complex (2.8–3.1 Ga,
regional NW-SE foliations. The most representative bodies in U-Pb) is dominated by igneous rocks that display a zoned structure,
this complex are the Tshambogo biotite-gneiss and the Kakonda with a tonalite core that evolves into granodioritic and monzogranitic
granodiorite (De Waele et al., 2008; Debruyne et al., 2019). This in the outer rims. The Lueta gabbronoritic complex (2.3–2.4 Ga,
complex comprises also rejuvenated Neoarchean (2.5–2.6 Ga, Rb-Sr) consists mainly of igneous to meta-igneous rocks, including
U-Pb) gneisses and granites (Fernandez-Alonso et al., 2012, gabbro, gabbronorites, amphibolites, subordinate anorthosites,
2016; Debruyne et al., 2019). The Sandoa-Kapanga Complex and meta-dolerites. The Dibaya complex (2.6–2.7 Ga, Rb-Sr and
(3.0–3.1 Ga, U-Pb) is composed mainly of granitic and granulite U-Pb) consist of migmatite-granite series, and rare serpentinite
gneissic rocks displaying NE-SE foliation trends overprinted by and peridotite (Figs. 2 and 3) (Hanson, 2003; Fernandez-Alonso

Fig. 3. (a) The regional geological map showing main chronostratigraphic and tectonic units of the central sub-Saharan Africa zones. Num-
bers 1–3 refer to regionally main discovered serpentinite bodies including Nkonko, Lutshatsha, and Mfwamba respectively. (b) Local geo-
logical map unit showing the location, orientation and petrofacies of the Nkonko massif. White star is used for fully observed, described, and
sampled stations, while white circles are used for fully samples with additional chemical analyses.

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 31

et al., 2012, 2016; Debruyne et al., 2019). temperatures that involves an enrichment in lime and water,
The Dibaya complex covers mainly the eastern and western and a loss of silica and alkalis (Honnorez and Kirst, 1975; Klein,
Kasai provinces, between 20–23° East longitude and 5–7° South 2009), or a metamorphism at relatively elevated temperature at
latitude, with extensions into the Bandundu province and subduction zones with a loss of carbon and sulfur (Alt et al.,
neighboring Angola. This complex consists of cataclazed or 2013). Serpentinization and rodingitization processes are
mylonitized granites-tonalites, gneisses, calc-alkaline granites- described as low-temperature (< 200 ℃) alterations (weathering)
migmatites, subsidiary mantellic enclaves, stock-like bodies of that involve significant amounts of water (Nozaka, 2003, 2005;
amphibolites and pyroxene-amphibolites, and peridotite- Frost and Beard, 2007; Klein, 2009; Frost et al., 2013).
serpentinite dykes (Figs. 2 and 3a) (Herman and Raucq, 1962; The serpentine group minerals are part of inosilicates and
Cahen et al., 1984; Carvalho et al., 2000; Debruyne et al., 2019). include several related minerals on the basis of the chemical
The peridotite-serpentinite bodies within the Kasai-Lomami variation (Faust and Fahey, 1962; Frost, 1985; Lafay et al., 2012;
complex are oriented E-W and may be associated with deep- Frost et al., 2013). The formula that encompasses all members is
seated lineaments within the craton. These bodies consist of written as X2-3Si2O5(OH)4, and where X = Mg, Fe2+, Fe3+, Ni, Al,
three main massifs, namely Lutshatsha, Fwamba, and Nkonko Zn, or Mn. In rare cases, one of the two Si atoms may also be
(this study), as well as several smaller, unnamed bodies (Figs. 2 replaced by an Al3+ or Fe3+. Therefore, the complete formula can
and 3b) (Herman and Raucq, 1962; Debruyne et al., 2019). be rewritten as (Mg, Fe, Ni, Al, Zn, Mn)2-3(Si, Al, Fe)2O5(OH)4
The Nkonko serpentinized dyke is located 20–25 km from (González-Mancera et al., 2009; Gervilla et al., 2012; Frost et al.,
the Kananga city, and extends 19–24 km of length with ENE- 2013; Syverson et al., 2017). The serpentine group minerals
WSW trends and width of 250–500 m, while the nearby Lutshatsha contain several polymorphic minerals on the basis of their
body with E-W trends, is 24–26 km of its length (western 12 km chemical composition and crystallographic structures, including
covered by pyroxenolites and eastern 11 km by serpentinite) Antigorite serpentine-like ((Mg, Fe)3Si2O5(OH)4) with dominantly
and width of 1–2 km (Raucq, 1961; Herman and Raucq, 1962; green-blue colors, Amesite serpentine-like (Mg2Al(SiAl)O5(OH)4),
Kröner and Stern, 2005; Debruyne et al., 2019). The Fwamba Cronstedite serpentine-like (Fe2+Fe3+2(SiFe3+)O5(OH)4), Fraipontite
body consists of serpentinite, and shows similar E-W trends as serpentine-like ((Zn, Al)3(Si, Al)2O5(OH)4), Nepouite serpentine-
the above ones. These aforementioned serpentinite dykes are like (Ni3Si2O5(OH)4), and Chrysotile serpentine-like (Mg3Si2O5(OH)4)
known for their Ni-Cr prospects (Raucq, 1961; Herman and as a yellow asbestiform type (Faust and Fahey, 1962; Stalder and
Raucq, 1962). In this study, we have investigated the Ni-Cr Ulmer, 2001; Galí et al., 2012; Debret et al., 2013; Petriglieri et al.,
bearing regolith zone of the Nkonko serpentinite massif located 2015; Hamdy et al., 2018). Serpentine asbestiform are known to
near Kananga city (Fig. 3b). be carcinogenic (Richter et al., 1995; Smith and Wright, 1996;
Smith and Huyck, 1999) and caused human health problems in
2.2. Rock and Ore Mineralogy, Serpentinization and the world (Nicholson and Raffn, 1995; Nicholson, 2001). A group
Weathering Processes of mineralogists considers chrysotile as a sub-group of polymorphic
minerals with the same chemical composition but different
The term “serpentinite” is used to describe a rock that contains crystal lattices. Its polytypes include clinochrysotile (monoclinic),
abundant serpentine minerals, formed by the alteration process orthochrysotile (orthorhombic), parachrysotile (orthorhombic),
known as serpentinization of mafic, ultramafic, and Mg-rich and lizardite (hexagonal) (Page, 1968; Petriglieri et al., 2015;
derived igneous rocks (Klein, 2009; Klein and Garrido, 2011; Bayliss, 2018).
Klein et al., 2013; Nozaka et al., 2017; Luolavirta et al., 2018). The Ni-rich serpentine known as “Garnierite ((Mg, Ni)3Si2O5
The minerals in serpentinite include serpentines, spinel, magnetite, (OH)4)” is a green mineral or rock that contains high amounts
as well as relicts of the protolith such as olivine, pyroxene, of Ni, up to 5 wt%, and is often found in association with other
garnet, and amphibole, along with secondary or reprecipitated soft minerals like talc and chlorite (Poncelet et al., 1979; Galí et
minerals such as brucite (Hostetler et al., 1966), magnetite, al., 2012; Villanova-de-Benavent et al., 2014; Roqué-Rosell et al.,
calcite, magnesite, dolomite, chlorite(Bonney, 1877; Klein, 2009; 2017). It is possible that this Ni-rich serpentine (garnierite-like)
Deschamps et al., 2013; Hamdy et al., 2018), and even sulfides is the main Ni-bearing (Galí et al., 2012; Kumarathilaka et al.,
(Frost, 1985). Other related terms often used include “Verde 2014; Roqué-Rosell et al., 2017) ore mineral of the Nkonko
Antique”, a decorative stone with dark green colors composed massif (Raucq, 1961; Herman and Raucq, 1962).
mainly of serpentine, which often displays calcite veins running Serpentinized rocks are the result of alteration processes
through it, and “Rodingite”, which refers to metamorphosed known as “serpentinization” that involve the contribution of fluid
basalts and gabbro altered by a metasomatic process at low phases such as water (and sometimes carbon dioxide) to destabilize

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
32 Douxdoux K. Makutu and Jung Hun Seo

pre-existing minerals in a highly hydrated environment (Faust exploration trench and wells (Fig. 4a, j). The Nkonko serpentinized
and Fahey, 1962; Hostetler et al., 1966; Duffin, 2006; Brigatti et bodies can be subdivided into the 3 layers that are (I) the
al., 2011; Peters et al., 2017). This alteration is often followed by bedrock zone, (II) the saprolite zone, and (III) the pedozone.
weathering processes, such as cracking, fracturing, and transportation The saprolite and the pedozone constitute the regolith situated
of materials, which can lead to the formation of lateritic soils above the bedrock.
above the saprolite and bedrock, particularly in tropical areas.
During this process, immobile elements like Cr, Fe3+, and Al can 3. MATERIALS AND METHODS
become enriched and may result in residual deposits, while
mobile elements such as Mg and Ca are leached out (Hermann 3.1. Sample Preparations and Selection, Microscopic
et al., 2000; Guillot et al., 2009, 2015; Deschamps et al., 2013; Observations
Frost et al., 2013; Kumarathilaka et al., 2014; Rollinson and Ade-
tunji, 2016; Torres-Sánchez et al., 2017). A total of 12 rock samples were chosen based on their facies
(including color, texture, and existing fractures) and depth. Over
2.3. The Nkonko Massif Field Relationships 9 thin sections and 5 polished sections were observed using a
polarizing microscope at Inha University (Incheon, Republic of
The Nkonko massif contains (1) a Precambrian basement Korea) to identify and describe the mineral phases in the rock.
made of metamorphic and igneous rocks, (2) a phanerozoic Representative photos were taken using both plane polarizing
sedimentary coverage, and (3) ultramafic dyke intrusions. The light (PPL) and cross polarizing (XPL). Bulk rock powders were
basement is part of the Congo-Kasai Archean craton, and hosts prepared at the resource geology laboratory (Seoul National
old crystalline and foliated rocks, and subsequently covered by University, Seoul, Republic of Korea), and XRD analysis was
phanerozoic siliclastic series (Fig. 2) (Debruyne et al., 2019). performed at standard analytical laboratories (Inha University,
The Nkonko massif basement includes abundant (a) migmatites Incheon, Republic of Korea), and the XRF analysis was carried
and (b) granites, that consist of essentially quartz, K-felspar out at Activation Laboratories (Actlabs, Ontario, Canada).
(orthoclase and rare microcline), and micas (biotite and rarely
muscovite). Migmatites showed often alternating features of 3.2. Laser Raman, XRD, Cathodoluminescence (CL),
linear dark band as “melanosome” made of essentially biotite and SEM-EDS
and linear bright band as “leucosome” made of essentially quartz
and feldspar (Figs. 2 and S1 (electronic supplementary material)). Raman spectra were acquired using a HORIBA HR Evolution
The basement contains also (c) amphibolite that is composed of Raman spectrometer at Inha University, with a 532 nm laser
abundant amphiboles (hornblende ± tremolite) and rare plagioclase and an excitation source of 0.8 mW. Acquisition time varied
and biotite. This amphibolite was in contact with the serpentinized between 20 to 50 seconds, and Opus and Sigma Plot were used
dyke in the northern parts (Figs. 3b and S1). for processing the results.
The Phanerozoic coverage of the Nkonko area is characterized X-ray diffractometry (XRD) was conducted using the Empyrean
by superimposed siliciclastic series of sedimentary rocks, including range from Malvern Panalytical Products, United Kingdom.
conglomerate, which are located in the SW part of the massif 15–30 g of bulk rock powder was used for the analysis, which
(Fig. 3b). This conglomerate exhibits a yellowish color and is was performed at Inha University.
subdivided into two sub-facies. The lower part consists Scanning electron microscopy (SEM) cathodoluminescence
predominantly of sub-rounded quartz pebbles and lithic fragments (CL) and energy dispersive spectroscopy (EDS) were performed
cemented by a silico-argillaceous matrix (pebbles > matrix), at the Korea Polar Research Institute (KOPRI) and Inha
referred to as “orthoconglomerate” (Fig. S1). In contrast, the University, respectively, using a JSM-6610 model SEM with an
upper part comprises rare sub-rounded quartz pebbles and accelerating voltage of 15 kV and a working distance of 10 mm
lithic fragments dispersed within a primarily argillaceous matrix for the CL, and an accelerating voltage of 13 kV and a working
(pebbles < matrix), referred to as “paraconglomerate”. Detailed distance of 10–13 mm for the EDS.
data regarding the Nkonko massif rocks, structural measurements,
and field descriptions is provided in the Figure S3 and Table S1 3.3. EPMA, XRF, and LA-ICP-MS
of the electronic supplementary material.
The Nkonko ultramafic dyke intrusion consists of essentially Compositions of Cr-spinels from serpentinite were analyzed
serpentinized peridotite. This serpentinite is exposed along using a field emission electron microscope, the JEOL JXA-
rivers, streams, small valley, escarpment zones, and inside drilled 8530F PLUS model, at Busan National University. The analysis

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 33

Table 1. Electron probe microscope analysis (EPMA) results of spinel concentrates (chromite) of the Nkonko and Lutshatsha serpentinites
Cr2O3 Al2O3 FeOt MgO MnO ZnO NiO CoO SiO2 TiO2 CaO Total
Ore mineral
wt% wt% wt% wt% wt% wt% wt% wt% wt% wt% wt% wt%
(1) Lutshatsha chromite 51.2 17.2 19.8 9.2 1.0 0.3 0.1 0.1 0.5 0.6 0.0 100.0
(2) Lutshatsha chromite (in placer) 45.3 19.3 21.9 7.1 1.1 0.2 0.2 0.1 3.7 0.9 0.2 100.0
(3) Lutshatsha chromite 34.9 20.3 31.0 8.0 0.6 0.2 1.1 0.2 3.1 0.6 nd 100.0
(4) Lutshatsha chromite 46.2 17.1 21.9 8.1 0.4 0.2 0.3 0.1 4.3 1.2 0.2 100.0
(5) Lutshatsha chromite 35.2 22.2 26.1 8.1 1.0 0.2 0.4 0.2 6.2 0.4 nd 100.0
(6) Nkonko soil (III) 0.2 5.5 71.0 1.0 0.5 nd nd nd 12.7 7.1 2.0 100.0
(7) Nkonko chromite (II) 43.4 16.3 25.6 6.8 0.5 0.3 0.3 0.3 5.5 1.0 nd 100.0
(8) Nkonko chromite (I)/DMC-5 (bedrock) 46.5 19.0 20.0 8.5 0.4 0.1 0.2 0.1 4.0 1.1 0.1 100.0
(9) Nkonko chromite (II)/DMCP-3 (saprolite) 43.0 15.9 24.5 7.2 0.7 0.3 0.1 0.1 5.2 2.0 1.0 100.0
The analytical Data (1) to (7) are from Herman and Raucq (1962); (8) to (9) from this study.
The roman notations refer to the profile layers of Nkonko serpentinized rock as shown in Figure 10: I = Unaltered serpentinite (bedrock), II =
saprolite zone, and III = pedozone (lateritic soil), nd refers to no data.
A value of 0.0 means the number is above the detection limit but beyond 2 decimals.

conditions included an acceleration voltage of 15 kV, an acceleration ppm), Cu (10 ppm), Zn (30 ppm), Ga (1 ppm), Ge (1 ppm), As
current of 10 nA, and an electron beam of 3 mm. The analysis (5 ppm), Rb (2 ppm), Sr (2 ppm), Y (1 ppm), 90Zr, Nb (1 ppm),
involved a peak duration of 10 s and a background time of 5 s, Mo (2 ppm), Ag (0.5 ppm), Cd (excluded), In (0.2 ppm), Sn (1
examining elements such as Fe, Mn, Si, Al, Ti, Cr, Mg, Zn, Co, ppm), Sb (0.5 ppm), Cs (0.5 ppm), Ba (2 ppm), La (0.1 ppm), Ce
and Ni (Table 1). (0.1 ppm), Pr (0.05 ppm), Nd (0.1 ppm), Sm (0.1 ppm), Eu (0.05
For the EPMA, the detection limits of analyzed elements are ppm), Gd (0.1 ppm), Tb (0.1 ppm), Dy (0.1 ppm), Ho (0.1 ppm), Er
listed; Fe (0.01 wt%), Mn (0.01 wt%), Si (0.007 wt%), Al (0.01 (0.1 ppm), Tm (0.05 ppm), Yb (0.1 ppm), Lu (0.01 ppm), Hf (0.2
wt%), Ti (0.01 wt%), Cr (0.02 wt%), Mg (0.007 wt%), Zn (0.005 ppm), Ta (0.1 ppm), W (1 ppm), Re (1 ppm), Au (10 ppb), Tl
wt%), Co (0.005 wt%), and Ni (0.007 wt%). (0.1 ppm), Pb (5 ppm), Bi (0.4 ppm), Th (0.1 ppm), and U (0.1
X-ray fluorescence (XRF, Zetium, Malvern Panalytical, United ppm).
Kingdom) of the bedrock and saprolite serpentinites in Nkonko
was performed at Activation Laboratories (Actlabs, Canada). 4. RESULTS
The LA-ICP-MS analyses were conducted at both Activation
Laboratories (Actlabs) in Canada and the Korea Institute of 4.1. The Petrography of the Nkonko Serpentinites
Ocean Science & Technology (KIOST) (Tables 2 and 3). We
analyzed a total of 60 isotopes (7Li, 9Be, 23Na, 25Mg, 27Al, 29Si, 39K, The serpentinite bedrock consists of relatively unaltered
42
Ca, 45Sc, 49Ti, 51V, 53Cr, 55Mn, 57Fe, 59Co, 61Ni, 65Cu, 66Zn, 71Ga, peridotite located at deeper parts (approximately > 50 m of depths),
73
Ge, 75As, 85Rb, 88Sr, 89Y, 90Zr, 93Nb, 95Mo, 107Ag, 111Cd, 113In, 118Sn, which could not be accessed and sampled; and the unweathered
121
Sb, 133Cs, 137Ba, 139La, 140Ce, 141Pr, 146Nd, 147Sm, 151Eu, 157Gd, 159Tb, serpentinites that were sampled in the wells and escarped zones.
163
Dy, 165Ho, 167Er, 169Tm, 173Yb, 175Lu, 178Hf, 181Ta, 182W, 185Re, 197Au, The unweathered serpentinites (DMC-5 and DMC25; Fig. 3b)
205
Tl, 208Pb, 209Bi, 232Th, 238U). A 193 nm Argon-Excimer laser (LA- exhibit greenish colors (Fig. 4j) and coarse mesh-like textures
NWR 193) was coupled with a quadrupole mass spectrometer (Fig. 4h, i). They are primarily composed of serpentines (platy-
Agilent 7700X. We used a repetition rate of 5 Hz and a laser shaped lizardite, fibrous chrysotile, and primary massive to
energy density of 3.5–6.0 J/cm2. The laser beam diameter of the columnar antigorite) with disseminated Cr-spinel, magnetite,
ablated zone was 50μm for serpentine, spinel, talc, and magnetite. and rare pseudo-olivine relicts. The serpentinite bedrocks show
The mounted samples were loaded with reference glasses thin veins or veinlets of talc (Fig. 4i, j).
(NIST-612, BCR-2) as external standards, and Mg, Al, Si were The saprolites (DMC-65 and DMCP-3; Fig. 3b) exhibit red to
used as internal standards for signal processing under the SILLS red-grayish colors (Fig. 4d, g) and coarse to fine mesh-like textures
software (Guillong et al., 2008; Yang et al., 2020). For the LA- (Fig. 4b, c, e, f). They contain (1) slightly weathered and fractured
ICP-MS, the detection limits are listed; Li (5 ppm), Be (1 ppm), serpentinite with a thickness of less than 2 cm (lower saprolite;
Na (100 ppm), Mg (100 ppm), Al (100 ppm), Si (100 ppm), K Fig. 4g), and (2) strongly weathered, fractured, and drained
(100 ppm), Ca (100 ppm), Sc (1 ppm), Ti (10 ppm), V (5 ppm), serpentinite with a thickness greater than 2 cm (upper saprolite;
Cr (20 ppm), Mn (10 ppm), Fe (100 ppm), Co (1 ppm), Ni (20 Fig. 4d). The minerals in the saprolites primarily consist of

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
34 Douxdoux K. Makutu and Jung Hun Seo

Fig. 4. Representative field macrophotographs and microphotographs of the Nkonko serpentinite body: (a, b) Valley and escarpment show-
ing yellow and red lateric soils of the pedozone; (c–f) Weathered red to brown serpentinite (DMC-65, DMCP-3) of the saprolite zone dis-
playing abundant fracture sets, cracks and veins filled with talc, garnierite-like, magnetite, magnesite and brucite; The unweathered green
oily serpentinite (DMC-5, DMC-25) of the bedrock zone displaying rare veins and sampled deeper inside drilled wells; (i, j) Upper saprolite
serpentinite displaying relatively fine-mesh texture; (k, l) Lower saprolite serpentinite displaying relatively coarse-mesh texture; and (m, n)
Bedrock serpentinite displaying a coarse-mesh texture and pseudo-olivine relicts.

serpentine (lizardite, primary and secondary antigorite “garnierite”), and granite, which have gray-colored top soils. Serpentine phases
along with disseminated ferrochromite and magnetite. The in the bedrock and saprolite were identified by XRD (DMC-5;
saprolite is extensively crosscut by veins of various orientations Fig. 5a) and Raman spectroscopy (DMC-5, DMC-65, and
(Fig. S2a, b of the electronic supplementary material). The DMCP-3; Fig. 5b). The serpentine phases consist of abundant
thickness of these veins is relatively smaller (< 2 cm) in the lower antigorite and lizardite, with rare chrysotile (Fig. 5a, b). A Ni-
saprolite (Fig. 4g) and larger (2–10 cm or even more) in the rich variety of serpentine, secondary antigorite “garnierite”, was
upper saprolite (Fig. 4d). The veins are composed of talc (steatite), also identified by Raman spectroscopy (Fig. 5b), EPMA, and
secondary antigorite “garnierite”, magnesite, brucite, magnetite, SEM-EDS analyses (Table 2). This garnierite exhibits Raman
and rare chlorite and opal (Figs. 4d and 5a, b). (Haskin et al., 1997) peak positions of 232, 350, 390, 460, 620,
The pedozone, situated in subsurface zones at approximately 690, 3669, and 3708 cm−1, resembling antigorite (DMC-65; Fig.
2–4 meters, includes the top lateritic soil, which primarily consists 5b), making it difficult to clearly distinguish them. However,
of red limonite at the top and yellow limonite at the bottom (Fig. lizardite (DMC-5, DMCP-3) displays unambiguously different
4a). The topsoil above the serpentinite is red-colored, and this Raman peak positions of 230, 351, 394, 460, 622, 692, 3687, and
color has been used to differentiate serpentinite from migmatite 3706 cm−1. Identifying the serpentine phases becomes even

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 35

Fig. 5. (a) X-ray diffraction (XRD) result

of the Nkonko saprolite serpentinite
(DMC-65) showing the presence several
minerals including antigorite/lizardite
(Atg/Lz)-like, chromite (Ch), chrysotile -
like, talc (Tc)-like, magnesite (Ms), mag-
netite (Mt), brucite (Br), and rare smec-
tite (St), chlorite (Ch) and opal (Op); (b)
Raman spectra of the Nkonko saprolite
serpentinite (DMC-65, DMCP-3) and
bedrock serpentinite (DMC-5) showing
the presence of antigorite (garnierite)-
like and lizardite-like.

more challenging using microscopic polarizing images (DMC- spinels exhibit rims or magnetite inclusions (DMC-5; Fig. 6a, b),
5; Fig. 6c) and electron-induced images, where they appear and we observed that this rim texture is present in most spinels
grey-dark under SEM-BSE (DMC-5; Fig. 6a) and bright under in the saprolite.
SEM-CL (DMC-5; Fig. 6b). Talc, magnesite, and brucite from veins in the bedrock and
Spinel and magnetite crystals in the bedrock and saprolite saprolite were identified by XRD (Fig. 5a), and the talc composition
were clearly identified using a polarizing microscope (Fig. 4), was determined by LA-ICP-MS (Table 2). Talc in veins can be
XRD (Fig. 5a), SEM-BSE (Fig. 6a), and SEM-CL (Fig. 6b). Their distinguished using a polarizing microscope (DMC-5; Fig. 6c)
chemical compositions were determined by EPMA (Table 1) and SEM-BSE images (DMC-5; Fig. 6a). A few veins are filled
and LA-ICP-MS (Table 2). Magnetite appears relatively brighter, with early green serpentine “garnierite” at the vein walls, followed
and Cr-spinel appears darker under SEM-BSE, while Cr-spinel by white-yellowish talc (± magnetite), and finally magnesite (±
is brighter and magnetite is darker under SEM-CL. A few Cr- brucite) at the vein center (DMC-5; Fig. 6a, c, d).

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
36 Douxdoux K. Makutu and Jung Hun Seo

Fig. 6. A combination of photomicrographs of polarizing microscope and electronic images of the Nkonko saprolite serpentinite (DMC-65):
(a) SEM-BSE images showing abundant serpentines (gray color) and the dissemination of spinel (dark gray color) and magnetite (light color)
crystals, and veins filled with the serpentine (garnierite)-like in borders, and talc-magnetite in central parts of the vein; (b) Cathodolumi-
nescence (CL) image displaying dominant serpentine-like minerals (slight bright CL), and disseminated magnetite (dark CL) and Cr-spinel
(fully bright CL). Few Cr-spinel crystals show a texturally dark rim of magnetite in replacement of spinel or inclusions of magnetite inside Cr-
spinel; (c) A plane polarizing light (PPL) view of the saprolite serpentinite and its hosting vein constituents; (d, e) Corresponding macro-
photographs.

4.2. Major and Trace Element Compositions of Rocks SiO2 = 0.02–0.04, FeOt/SiO2 = 0.24–0.26, and LOI/SiO2 = 0.42–
0.44). On the other hand, the ratio MgO/SiO2 (1.06–1.07) is
The bedrock serpentinites of the Nkonko (DMC-5, DMC-25; higher in the bedrock serpentinites compared to the saprolite
Table 3) have SiO2 content of 35–36 wt%, Al2O3 of about 0.8 serpentinites (MgO/SiO2 = 0.86–0.96).
wt%, FeO of about 2.0 wt%, Fe2O3 of 7.2–7.8 wt%, MgO of The bedrock serpentinites contain significant amounts of Cr
37.3–38.1 wt%, CaO of about 0.6 wt%, MnO of 0.1–0.2 wt%, (4,500–9,300 ppm) and Ni (2,500–2,700 ppm), as well as non-
Na2O of 0.3–0.4 wt%, K2O of about 0.1 wt%, and LOIs (loss on negligible amounts of Zn (60–65 ppm), Co (140 ppm), V (460–
ignition) of 14.9–15.3 wt%. The saprolite serpentinites (DMC- 480 ppm), and As (15–16 ppm). The rocks are poor in REE
65, DMCP-3; Table 3) contain low silica and alkalis, similar to contents (ΣREEs of 2.2–2.3 ppm). The saprolite serpentinites
the bedrocks. Compared to the bedrocks, the saprolites have are enriched Cr (25,000–54,000 ppm) and Ni (3,300–20,000
similar SiO2 (35.1–35.6 wt%), CaO (0.5–0.6 wt%), Na2O (0.3 ppm), and which elements could be considered as part of majors
wt%), and K2O (0.1 wt%), but are relatively depleted in MgO in this layer. Except for Cr and Ni, the saprolite serpentinites
(30.2–34.0 wt%) and FeO (1.9–2.0 wt%), and enriched in Al2O3 also contain amounts of trace elements including Zn (52–54
(1.0–1.1 wt%), Fe2O3 (7.8–11.2 wt%), MnO (0.1–0.9 wt%), and ppm), Co (110–130 ppm), V (490–503 ppm), and As (11–20
volatiles (LOIs of 15.3–15.4 wt%). ppm), are also observed compared to the bedrocks. The REE
The ratios such as Cr2O3/SiO2 (0.10–0.23), FeOt/SiO2 (0.25– concentrations of the saprolite serpentinites (ΣREE of about 2.2
0.34), and LOI/SiO2 (0.43–0.44) are relatively higher in the saprolite ppm) remain relatively unchanged compared to the bedrock
serpentinites compared to the bedrock serpentinites (Cr2O3/ serpentinites. Trace elements behaviors are relatively different

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 37

Table 2. LA-ICP-MS results of minerals hosted in the bedrock and saprolite of serpentinite in the Nkonko massif (DRC)
LA-ICP-MS results of serpentinite minerals
Orogen/Age: Dibaya complex /Archean
Locality: Nkonko
Rock type: Serpentinite
Mineral : SP SP SP SP SERP SERP SERP SERP TLC TLC TLC
Layer : BR SAP BR SAP SAP SAP BR BR SAP BR SAP
DMC-5 DMC-65 DMC-25 DMCP-3 DMC-65 DMCP-3 DMC-5 DMC-25 DMC-65 DMC-5 DMCP-3
Samples
SP-1 SP-2 SP-3 SP-4 SERP-1 SERP-2 SERP-3 SERP-4 TLC-1 TLC-2 TLC-3
Major elements (wt%)
SiO2 0.8 2.9 7.8 3.4 30.1 39.1 40.8 42.1 41.5 42.7 37.8
TiO2 0.6 0.6 0.0 0.5 0.1 0.0 0.0 0.0 0.0 0.0 0.0
Al2O3 21.1 19.6 18.7 19.2 0.2 0.1 0.2 0.0 0.4 0.2 0.2
FeOt 15.5 17.5 16.4 19.0 27.9 4.1 4.3 1.8 2.3 2.5 2.8
MgO 11.4 10.3 10.3 10.4 37.8 54.9 51.4 48.8 51.3 53.2 48.1
MnO 0.6 0.8 0.2 2.0 0.3 0.2 0.1 0.4 2.6 0.0 0.0
K2O bdl bdl 0.0 bdl 0.0 0.0 0.0 bdl 0.0 0.0 0.0
Na2O 0.0 0.0 0.0 0.0 0.1 0.1 0.0 0.1 0.3 0.1 0.0
CaO bdl bdl 0.5 bdl bdl bdl 0.2 5.8 0.1 0.1 0.1
Cr2O3 49.9 48.3 46.2 45.4 3.5 1.5 3.1 1.0 1.5 1.1 10.9
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Minor elements (ppm)
V 1735 1942 275 2063 3134 766 1000 2000 663 642 507
Co 1237 1677 365 3628 265 180 132 65 98 56 120
Ni 1586 2441 3527 5229 8166 4435 3258 1748 2248 1852 2412
Cu 5 7 6 43 30 9 12 5 32 12 8
Zn 4066 4726 253 6034 53 48 28 68 29 19 28
Pb 15 4 1 25 11 16 7 22 68 5 6
Ratios
Cr# 70.3 71.2 71.2 70.3 95.3 91.6 94.6 98.0 79.0 85.4 98.4
Mg# 42.3 36.9 38.6 35.4 57.6 93.1 92.3 96.5 95.7 95.6 94.4
Fe# 57.7 63.1 61.4 64.6 42.4 6.9 7.7 3.5 4.3 4.4 5.6
V/Cu 342.9 264.2 43.3 48.4 105.3 87.8 81.2 410.7 20.9 52.2 62.9
V/Co 1.4 1.2 0.8 0.6 11.8 4.3 7.6 30.8 6.8 11.5 4.2
Al/Ti 34.8 35.4 862.6 36.3 2.7 14.2 16.2 6.4 28.4 18.6 21.3
Mn/Ti 1.1 1.4 7.3 3.7 5.4 18.7 6.6 135.0 188.1 4.5 5.6
Cr# = Cr/Cr + Al, Mg# = Mg/Mg + Fe, Fe# = Fe/Fe + Mg; bdl = below detection limit, SERP = serpentine, SP = spinel, TLC = talc, BR = Bed-
rock, SAP = Saprolite.
A value of 0.0 means the number is above the detection limit but beyond 2 decimals.

during alteration and weathering processes (Debret et al., 2013). serpentinites are similar and they contain La of 0.24–0.25 ppm,
Elements such as Cr and V as immobile prefer to accumulate in Ce of 0.78–0.87 ppm, Pr of 0.08–0.09 ppm, Nd of 0.41–0.42
situ while Co could be relatively mobile and leached-out (Galí et ppm, Sm of 0.10–0.11 ppm, Eu of 0.03 ppm, Gd of 0.11 ppm, Tb
al., 2012; Li and Audétat, 2012; Debret et al., 2013; Deschamps of 0.02 ppm, Dy of 0.14–0.15 ppm, Ho of 0.03 ppm, Er of 0.09
et al., 2013; Mohanty et al., 2019).This selective behavior can be ppm, Tm of 0.01 ppm, Yb of 0.09–0.10 ppm, and Lu of 0.01–
used to characterize possibly the occurred weathering in the 0.02 ppm.
regolith zone. Thus, the saprolite serpentinites display relatively
higher ratios of Cr/V (50.5–107.8), Cr/Co (198.0–516.5), and 4.3. Major and Trace Element Compositions of Minerals
V/Co (3.9–4.8) compared to the bedrock serpentinites (Cr/V =
10.0–19.3, Cr/Co = 31.5–68.7, and V/Co = 3.2–3.6). The Cr-spinels in the bedrock and saprolite serpentinites host
The REE concentrations in the Nkonko bedrock and saprolite major elements, including Cr2O3 of 42.1–48.5 wt%, SiO2 of 3.9–

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
38 Douxdoux K. Makutu and Jung Hun Seo

Table 3. Bulk-rock XRF and mineral LA-ICP-MS of the Nkonko ser- 5.1 wt%, Al2O3 of 15.6–18.9 wt%, FeOt of 19.9–24.0 wt%, MgO
pentinite (concentrations of major oxides are expressed in wt%, and
trace elements are expressed in ppm) of 7.0–8.5 wt%, MnO of 0.4–0.7 wt%, CaO of 0.1–0.4 wt%, and
TiO2 of 0.5–1.9 wt%. Based on the major element compositions,
LA-ICP-MS results of serpentinite rocks
Orogen/Age: Dibaya complex /Archean the spinel formula can be written as (Fe2+0.6 Mg0.4)O(Cr0.9 Al0.6
Locality: Nkonko Fe3+0.5)O3. Spinels in the saprolites is relatively enriched in FeOt
Rock type: Serpentinite (24.0 wt%) but depleted in Cr2O3 (42.1 wt%) and Al2O3 (15.6
Layer: Saprolite (II) Saprolite (II) Bedrock (I) Bedrock (I) wt%) compared to spinel in the bedrocks (FeOt = 19.9 wt%,
Estimated fracture/m² 30 8 4 1 Cr2O3 = 46.2 wt%, and Al2O3 = 18.9 wt%). The spinel is likely a
Samples DMCP-3 DMC-65 DMC-5 DMC-25 Cr-spinel in the bedrock serpentinites, whereas it is a ferrochromite
Major elements (wt%) in the saprolite serpentinites. The Cr-spinels showed amounts
SiO2 34.6 36.0 35.1 35.8 of trace elements including Zn of 250–6,000 ppm, Co of 360–
TiO2 0.4 0.3 0.3 0.4 3,600 ppm, Ni of 1,600–5,200 ppm, V of 280–2,100 ppm, Cu of
Al2O3 1.1 1.0 0.8 0.8
5–42 ppm, and Pb of 1–24 ppm (Tables 1 and 2).
FeO 1.9 2.0 2.0 2.0
The stability of minerals and trace element replacements and
Fe2O3 11.0 7.9 7.8 7.2
enrichments depend on the environment conditions. Processes
FeOt 11.9 9.1 9.0 8.5
MnO 0.9 0.1 0.1 0.1
such as alteration (serpentinization), fluid-rock interactions and
MgO 29.7 34.5 37.3 38.0 weathering may contribute in the mobility and enrichment of
CaO 0.5 0.6 0.6 0.6 V4+, Al3+, and Ti4+ because they tend to replace Cr3+ while depletion
Na2O 0.3 0.3 0.4 0.3 of Cu2+, Co2+, and Mn2+ because they are slightly replaced by
K2O 0.1 0.1 0.1 0.1 Fe2+ (Garrido et al., 2005; Gervilla et al., 2012; Deschamps et al.,
Cr2O3 5.3 2.5 0.9 0.5 2013; Mohanty et al., 2019). Spinels in both bedrock and
P2O5 0.0 0.0 0.1 0.0 saprolite serpentinites show values of 100Cr# (Cr/Cr + Al),
LOI 15.2 15.5 15.3 14.9 100Mg# (Mg/Mg + Fe), and 100Fe# (Fe/Fe + Mg) of 70–98, 35–
Total 100.0 100.0 100.0 100.0 42, and 57–64, respectively (Table 2). Ti and V are sensitive to
Minor elements redox state and they can be used to track the evolution of alteration
Co 105 125 136 144
of spinels. The ratios V/Cu, V/Co, Al/Ti, and Mn/Ti in spinels
Ni 3284 20377 2660 2505
are 43–343, 0.8–1.4, 35–863, and 1.1–7.3 in the bedrock serpentinites,
Zn 54 52 60 65
whereas they are 48–264, 0.6–1.2, 35–36, and 1.4–3.7 in the
As 20 11 16 15
V 503 490 483 455 saprolite serpentinites (Table 2).
La 0.25 0.24 0.25 0.25 The serpentines and talc-like hosted in both bedrock and
Ce 0.81 0.85 0.87 0.78 saprolite serpentinites showed relatively similar chemical compositions
Pr 0.08 0.09 0.08 0.09 (Table 2). The values of 100Mg# and 100Fe# for serpentine in
Nd 0.41 0.41 0.42 0.41 both bedrocks and saprolites range from 92–96 and 3–6, respectively.
Sm 0.10 0.10 0.10 0.10 A glimpse on trace elements, the ratios of V/Cu, V/Co, Al/Ti,
Eu 0.03 0.03 0.03 0.03 and Mn/Ti for serpentines hosted in the bedrock serpentinites
Gd 0.11 0.12 0.11 0.11 are respectively 81–411, 8–31, 6–16, and 7–135, whereas they are
Tb 0.02 0.02 0.02 0.02 respectively 85–105, 4–12, 3–14, and 5–19 for serpentine in the
Dy 0.15 0.14 0.15 0.14
saprolite serpentinites (Table 2). The same ratios of V/Cu (52–
Ho 0.03 0.03 0.03 0.03
100), V/Co (12–21), Al/Ti (19–40), and Mn/Ti (5–174) for talc-
Er 0.09 0.09 0.09 0.09
like in the bedrock serpentinites are relatively high and differ
Tm 0.01 0.01 0.01 0.01
Yb 0.10 0.09 0.09 0.10
from those of talc-like in the saprolite serpentinites as of V/Cu
Lu 0.02 0.01 0.02 0.02 (21–63), V/Co (4–7), Al/Ti (21–28), and Mn/Ti (6–188).
∑ REE 2.20 2.24 2.27 2.18
Ratios 4.4. Tectonic Features and Structural Measurements
Mg# 100 71.5 79.1 80.6 81.8
Fe# 100 28.5 20.9 19.4 18.2 In the Nkonko massif, various tectonic features such as fractures,
Cr# 100 82.6 72.3 52.9 35.9 veins, and, rarely, micro faults were observed (Fig. 4e–g). A
Cr# = Cr2O3/Cr2O3 + Al2O3, Mg# = MgO/MgO + FeO, Fe# = FeOt/FeOt + geostatistical analysis using stereographic projections in upper
MgO. A value of 0.0 means the number is above the detection limit but
Wulff canvases (Dips software) of one hundred measured veins
beyond 2 decimals.

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 39

and fractures (Fig. S2a, b) revealed three main prevailing direction increase of 4 wt% in FeOt, when comparing spinels in the
trends: 40–60° (NE-SW), 0–10° (N-S), and 135–160° (NW-SE), bedrock (DMC-5, Table 1) to those in the saprolite serpentinites
which can be interpreted as trends of local orogen overprints. (DMCP-3, Table 1). This correlates with the observed spinel
The prevailing dip-angle values in the Nkonko massif were found textures, where a dark rim (or inclusions) of magnetite borders
to range between 45–80°. Veins and fractures exhibited variable the crystal, as shown by SEM-BSE and SEM-CL images (Fig. 6a,
thicknesses, with the dominant thickness range being 1 to 5 cm b). This suggests a progressive replacement of the Cr-spinel in
(Fig. S2a, b). Some veins could reach greater than 10 cm (Fig. 4d, bedrock serpentinites by ferrochromite and, eventually, magnetite
e). The proportions of vein thickness are 77% for 1–5 cm, 16% for in the saprolite serpentinites, since ferrochromite and magnetite
6–10 cm, and 7% for 11–15 cm. The estimated distributions of veins require a higher amount of Fe compared to Cr-spinel in the
by layers are 1–4 veins/m2 in the bedrock serpentinites and 8–30 bedrock (Herman and Raucq, 1962). The initial Cr-spinel can
veins/m2 in saprolite serpentinites (Table 3). be gradually altered to ferrochromite, then to Cr-magnetite, and
finally to magnetite; this explains the contrasting chemistry of
5. DISCUSSIONS spinels hosted in bedrock and saprolite serpentinites (Mohanty
et al., 2019).
5.1. The Rock-Mineral Textures and Element Enrich- Ni is primarily hosted in secondary antigorite serpentines
ments “garnierite” and, to a lesser extent, in Cr-spinel and talc. The LA-
ICP-MS results show that Ni is enriched in garnierite (4,400–
Microscopic descriptions of the Nkonko bedrock serpentinites 8,200 ppm) hosted in the saprolite serpentinites (DMC-65,
reveal coarse mesh textures, while the saprolite serpentinites DMCP-3, Table 2), whereas it is somewhat depleted in garnierite
display coarse to fine mesh textures (Fig. 4). This suggests that (1,700–3,300 ppm) in the bedrock serpentinites (DMC-5, DMC-
rocks in the regolith zone were affected by intense fracturing 25, Table 2). Although Ni is a geochemically mobile element
and destruction caused by fluxes of percolating water. Prolonged during weathering processes and is expected to be depleted in
exposure to water amplifies serpentinization (hydration) and the regolith zone, this study shows that Ni is also enriched in the
weathering (Klein, 2009; Klein and Garrido, 2011; Debret et al., regolith’s limonite-rich zone. This Ni enrichment can be explained
2013; Deschamps et al., 2013; Klein et al., 2013; Harvey et al., as a result of the leaching of primary serpentine (Ulrich et al.,
2014). The observed quasi-mesh texture, especially in the 2019), which induces Ni loss that is quickly absorbed by the
saprolite serpentinites, is consistent with the intensive alteration possible subsequent reprecipitation of secondary garnierite
and weathering of the rock. inside veins (Roqué-Rosell et al., 2017). The enrichment of Ni in
The secondary “garnierite” antigorite, a Ni-enriched (Hamdy the regolith zone is thus interpreted as a result of dissolution-
et al., 2018) serpentine group mineral abundant in the regolith reprecipitation of garnierite (Galí et al., 2012; Roqué-Rosell et
zone, has possibly re-precipitated during fluid-rock interactions al., 2017; Hamdy et al., 2018; Delina et al., 2020). Ni in the Cr-
of serpentinization-weathering processes at the nearby paleo- spinel and talc can be explained by the possible substitution of
water table fluctuation zones. Ni was leached out from preexisting divalent cations Mg2+ (Fe2+) with Ni2+, and in rare cases, the
pseudo-olivine or primary antigorite serpentine and possibly replacement of trivalent cations Cr3+ (Al3+, Fe3+) with Ni3+ (Des-
incorporated into the incipiently reprecipitated garnierite in champs et al., 2013; Rollinson and Adetunji, 2016; Mohanty et
fractures (Roqué-Rosell et al., 2017). In the Nkonko regolith, al., 2019).
this secondary garnierite often occurs as a greenish, massive, The enrichment of Ni and Cr in the regolith zone compared
and platy mineral bordering both sides of veins, while the inner to the bedrock can be interpreted as a result of dissolution-
parts of the veins are filled with talc magnesite, magnetite, and, reprecipitation by dominantly meteoric water, whereas REE
rarely, brucite. This intense green coloration of the secondary remained unchanged in both regolith zone and bedrock, probably
garnierite can be explained by the replacement of Mg by Fe (or due to its lower salinities, neutral pH, and fewer ligand such as
Ni) in octahedral sites during dissolution-reprecipitation reactions F−, Cl−, CO32−, and SO42−, etc. in the water involved in the
(Kodolányi et al., 2012; Lafay et al., 2012; Deschamps et al., serpentinization and weathering processes (Galí et al., 2012;
2013; Villanova-de-Benavent et al., 2014). Roqué-Rosell et al., 2017; Hamdy et al., 2018; Delina et al., 2020).
The possible replacement of Cr3+ and Al3+ by Fe3+, and Mg2+
by Fe2+ (Fe enrichment) can be explained by the compositions 5.2. Geochemical Proxies for Serpentinite Weathering
of spinels and serpentines hosted in the saprolite serpentinites
(Tables 1 and 2) (Ulrich et al., 2019). We observed a decrease of The Nkonko bedrocks and saprolite serpentinites reveal that
approximately 4 wt% in Cr2O3 and 3 wt% in Al2O3, as well as an elements such as Fe3+, Al, Cr, and Ni are relatively enriched,

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
40 Douxdoux K. Makutu and Jung Hun Seo

whereas Mg and Fe2+ are depleted in the saprolites compared to bedrock to saprolite serpentinites, caused by episodes of leaching
the bedrock. The amount of water (e.g., LOI) also slightly increased and drainage in the regolith zone above the bedrock (Figs. 7c, d
in the saprolite serpentinites by about 0.2–0.6% compared to the and S3a, d (electronic supplementary material)) (Boschi et al.,
bedrock serpentinites, which is consistent with the alteration 2013; Deschamps et al., 2013; Mohanty et al., 2019).
and weathering processes of the serpentinites. The sums (ΣREEs) The bedrock serpentinite shows higher ratios of MgO/SiO2
of the bedrock and saprolite serpentinites remain relatively (> 1) and lower ratios of Cr2O3/SiO2 (0.02–0.05), FeOt/SiO2
unchanged, suggesting that the REEs in the serpentinite are less (0.23–0.26), and LOI/SiO2 (0.42–0.44) compared to the saprolite
affected by alteration and weathering. serpentinites (MgO/SiO2 < 1, Cr2O3/SiO2 = 0.09–0.24, FeOt/
Major and trace elements can be used to characterize the SiO2 = 0.25–0.34, and LOI/SiO2 = 0.43–0.45). Noticeable enrichments
alteration and weathering processes that affect serpentinized of immobile elements such as Cr, Fe3+, Al, and mobile elements
rocks (González-Mancera et al., 2009; Boschi et al., 2013; Debret such as Ni by reprecipitation in the Nkonko regolith zone are
et al., 2013). This rock chemistry helps to estimate the intensity thus results of the alteration-weathering-reprecipitation processes
and scope of the coupling alteration-weathering processes, such above the unweathered bedrock serpentinite (Boschi et al.,
as the increase of the FeOt/MgO ratio from the unweathered 2013; Rouméjon et al., 2018).
bedrock serpentinite to the saprolite serpentinite (Boschi et al., The distribution of Ni during laterization is strongly influenced
2013; Malvoisin, 2015; Malvoisin et al., 2017). Plots including by the stability of the host minerals during weathering and the
Cr2O3/SiO2 versus MgO/SiO2, FeOt/SiO2 versus MgO/SiO2, reprecipitation of secondary Ni-rich phases such as garnierite
and LOI/SiO2 versus MgO/SiO2 provide proxies that better near the paleo water table (Galí et al., 2012; Villanova-de-Benavent
characterize the evolution of the invoked processes from the et al., 2013, 2014). High V concentrations in weathered soils

Fig. 7. The Nkonko serpentinite (bedrock and saprolite) bulk-rock chemistry: (a) Plots of MgO/SiO2 versus Al2O3/SiO2 diagram for the recon-
stitution of the protolith. The large grey line represents the bulk silicate earth evolution so-called “terrestrial array” (Boschi et al., 2013; Des-
champs et al., 2013); (b) The ternary diagram of (Na2O + K2O) versus FeOt versus MgO, used to distinguish igneous-derived source of
serpentinite as of arc-related gabbro (gray filled), arc-related mafic cumulates (blue light filled) and arc-related ultramafic cumulates (yellow
green filled); the Nkonko serpentinite corresponds to the field of ultramafic related cumulates (Boschi et al., 2013); (c, d) Plots of Cr2O3/SiO2
versus MgO/SiO2, and FeOt/SiO2 versus MgO/SiO2 used as proxies showing the serpentinite weathering evolution from the bedrock to the
saprolite zones. The gray arrow shows the weathering and drainage evolution trend and relative serpentinization maturity.

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 41

(Garrido et al., 2005; Ulrich et al., 2019) are indicative of oxidized The REE including Ce and Eu anomalies can be used for
environments (Oyarzún et al., 2016, 2017; Peters et al., 2017; redox-sensitive status (Dai et al., 2016). REE concentrations
Cheng et al., 2019; Chen et al., 2023). Cr is relatively mobile in were normalized to chondrite values (McDonough and Sun,
hydrothermal systems, while immobile under high P-T metamorphic 1995; McLennan et al., 1995). The Nkonko bedrock and saprolite
conditions (Treloar, 1987; Alt et al., 2013; Deschamps et al., serpentinites show relatively slight Ce positive and Eu negative
2013; Delina et al., 2020). Zn2+, Mg2+, Ni2+, and Fe2+ are mobile anomalies (Fig. 8). The estimated values of Ce (Ce/Ce* = CeN/
cations that can be leached from the bedrocks, resulting in lower (LaN*PrN)0.5) and Eu (Eu/Eu* = EuN/(SmN*GdN)0.5) anomaly
concentrations in altered rocks, while Fe3+, Al3+, Cr3+, V3+/4+, and values (Taylor and and McLennan, 1981; Braun et al., 1990;
Si4+ are considered immobile cations that are preferentially enriched Rudnick, 1992; McDonough and Sun, 1995; McLennan et al.,
in the remaining phase of the weathered rock, potentially leading 1995) in the Nkonko bedrock and saprolite serpentinites are
to a residual enrichment of some economic metals (Coleman, respectively 1.09–1.57 and 0.68–0.74, that barely fluctuate between
1971; Galí et al., 2012; Gervilla et al., 2012; Daval et al., 2013; slightly oxidized and reduced environment. The Nkonko bedrock
Frost et al., 2013; Kumarathilaka et al., 2014; Delina et al., 2020). and saprolite serpentinites show ratios of (La/Sm)N, (La/Yb)N,
Higher ratios of Cr/V, Cr/Co, and V/Co in saprolite serpentinite, and (Gd/Yb)N of respectively 1.51–1.57, 1.73–1.82, and 0.96–
compared to bedrock serpentinite, can therefore be interpreted 0.99, and typical of ultramafic rocks (Fig. 8).
as a result of intensive weathering of the serpentinites in the Serpentinites primarily originate from mafic and ultramafic
regolith zone. Ratios of V/Cu, V/Co, Al/Ti, and Mn/Ti are higher rocks, and in rare cases, alteration (e.g., skarn) of dolomites
in spinel, serpentine, and talc hosted in bedrock serpentinite (Bonatti, 1976; Klein, 2009; Boschi et al., 2013; Deschamps et al.,
than in the same minerals hosted in saprolite serpentinite. This 2013; Reynard, 2013). Rock chemistry and mineralogy can help
can also be interpreted as the contribution of oxidizing water trace the protolith. In the Nkonko serpentinite, we utilized
(and carbon dioxide) during the alteration and weathering of petrographic features (such as the presence of pseudo-olivine
these minerals in the serpentinite regolith. relicts, Fig. 4h, i) and chemical proxies (Figs. 7a and 8) such as
MgO/Al2O3 ratios and REE patterns in both bedrock and
5.3. Protolith of the Serpentinite Regolith in the Nkonko saprolite serpentinites to determine the protolith. REEs are trace
Massif elements that are relatively less affected by alteration and tectono-
metamorphic processes (Garrido et al., 2005; Boschi et al., 2013;
The MgO/SiO2 and Al2O3/SiO2 ratios are useful for distinguishing Debret et al., 2013; Deschamps et al., 2013), except for their
between different types of terrestrial rocks. Mafic gabbroic rocks redox-sensitivity with Eu and Ce (Braun et al., 1990; Tang et al.,
typically have Al2O3/SiO2 ratios ranging from 0.06 to 0.10. Ultramafic 2015; Dai et al., 2016). In the case of the Nkonko (bedrock and
lherzolitic rocks have Al2O3/SiO2 ratios between 0.04 and 0.06, saprolite) serpentinites, the REE patterns (Fig. 8) better match
whereas ultramafic harzburgitic rocks have Al2O3/SiO2 ratios the harzburgite-dunite field. Additionally, plots of MgO/SiO2
lower than 0.04 (Boschi et al., 2013; Deschamps et al., 2013) versus Al2O3/SiO2 rely on the nearby terrestrial array line, and
(Fig. 7a). Plots of MgO/SiO2 versus Al2O3/SiO2 ratios for the are consistent with the ultramafic harzburgitic-peridotite (Fig.
Nkonko saprolite and bedrock serpentinites are displayed on 7a) (Boschi et al., 2013; Deschamps et al., 2013).
the terrestrial array of ultramafic harzburgite-derived rocks.
(Fig. 7a). The ternary plot of (Na2O + K2O) versus FeOt versus 5.4. Geochemistry of Serpentinization Processes in
MgO geochemically distinguish (1) arc-related gabbro, (2) arc- the Nkonko
related mafic cumulates, and (3) arc-related ultramafic cumulates
(Mohanty et al., 2019). The plot indicates that both the Nkonko Serpentinization is a process that requires fluids, such as
saprolite and bedrock serpentinites fall within the field of meteoric water and potentially dissolved CO2, when combined
ultramafic-related cumulates (Fig. 7b), and consistent with the with carbonation (Klein, 2009; Boschi et al., 2013; Daval et al.,
geologic context in the Nkonko massif serpentinized rock that it 2013; Klein et al., 2013; Delina et al., 2020). The Nkonko massif
is derived from peridotitic dyke. Binary plots of Cr# versus Mg#, is located in tropical areas, and these meteoric waters would be
Fe# versus Cr#, and ternary plots of Mg# versus Cr# versus Fe# originated from the tropical rain (average rain intensity of
are useful for characterizing the geodynamic contexts of peridotite 1,000–1,200 mm/year), streams and underground waters above
complex types (Mohanty et al., 2019). The results of these plots unweathered peridotitic dyke (Inogwabini et al., 2006; Kierczak
for spinels in both bedrock and saprolite serpentinites in the et al., 2007).
Nkonko massif indicate that it belongs to the field of intracratonic The hydration of Mg-rich parental-minerals (e.g., olivine)
peridotite complexes (Fig. 9a–c). leads to the formation of serpentine-like minerals [2Mg2SiO4 +

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
42 Douxdoux K. Makutu and Jung Hun Seo

3H2O → Mg3Si4O10(OH)2 + Mg(OH)2: olivine + aqueous fluids and magnesite primarily occur in veins that crosscut the massive
→ serpentine + brucite] (Reaction 1) (Rudge et al., 2010; Ger- saprolite serpentine, confirming the suggested carbonation
villa et al., 2012; Kelemen and Hirth, 2012; Okamoto et al., 2013; reactions.
Kawahara et al., 2016). As shown above, these hydration reactions
generate other minerals such as the brucite that occurred in 5.5. Distribution of Rock Fractures and Its Role on
most of veins in the regolith zone. Serpentinization and Weathering
In a CO2-rich environment, carbonation of olivine may easily
occur [2Mg2SiO4 + 2CO2 → 2MgCO3 + SiO2: olivine + CO2 The serpentinization-weathering process can be significantly
fluids → magnesite + quartz] (Reaction 2) (Kelemen and Hirth, promoted by geological structures, such as cracks and fractures
2012; Rouméjon et al., 2018). In rare veins that crosscut the in the rock, which allow substantial amounts of water to be
Nkonko serpentinized bedrock and massive veins in the saprolite retained and enable circulation within the rock mass during its
serpentinite, we noticed the occurrence of magnesite and destabilization (Guillot et al., 2009, 2015; Kelemen and Hirth,
garnierite-magnetite-brucite (Figs. 4d and 5a). The presence of 2012; Lafay et al., 2012; Malvoisin et al., 2017). The greater the
magnesite in the Nkonko serpentinite can be interpreted as circulation of water, the more intense the serpentinization-
carbonation during serpentinization, potentially due to meteoric weathering processes. These fractures also serve as “receptacles”
water enriched in dissolved carbon dioxide [2Mg2SiO4 + CO2 + for water refill and reprecipitation of minerals in veins, such as
2H2O → Mg3Si2O5 (OH)4 + MgCO3: olivine + dissolved carbon secondary antigorite “garnierite”, talc, magnesite, magnetite, and
dioxide + water → serpentine + magnesite] (Reaction 3) (Klein, brucite (Hostetler et al., 1966; Honnorez and Kirst, 1975; Her-
2009; Rudge et al., 2010; Mohanty et al., 2019). The origin of mann et al., 2000; Malvoisin et al., 2017). In the Nkonko massif,
dissolved CO2 in water can stem from organic-rich soil (humus, fractures may be a tectonic overprint of orogenic processes. A
dead plants) or carbon-rich rocks (limestone, dolomite), which geostatistical analysis (using DIPS software) of hundreds of
may promote carbonation reactions in the Nkonko serpentinized measured veins and fractures in the Nkonko massif revealed
rocks [4Mg2SiO4 + 5CO2 + H2O → Mg3Si4O10 (OH)2 + 5MgCO3: ENE-WSW dominant trend directions. These trend directions
olivine + aqueous fluid + dissolved CO2 → serpentine + magnesite] align with those of the regional Archean Dibaya migmatite
(Reaction 4) (Klein, 2009; Rudge et al., 2010; Kelemen and complex. We also observed additional trend directions of N-S,
Hirth, 2012). The co-occurrence of talc and magnesite in veins NE-SW, and NW-SE, which can be interpreted as post-Dibaya
may result from the carbonation processes of the preexisting orogen overprints. These correspond to the Paleoproterozoic,
serpentines [2Mg3Si2O5 (OH)4 + 3CO2 → Mg3Si4O10 (OH)2 + Mesoproterozoic, and Neoproterozoic orogens, respectively (De
3MgCO3 + 3H2O: serpentine + carbon dioxide → talc + magnesite Waele et al., 2008; Debruyne et al., 2019), and these ultramafic
+ water] (Reaction 5) (Rudge et al., 2010; Kelemen and Hirth, dyke intrusions are embedded along deep lineaments that
2012; Boschi et al., 2013; Malvoisin et al., 2017). Magnesite can crosscut the African continent (Delhal et al., 1986; Cahen et al.,
be formed by carbonation of both olivine (pseudo-olivine relicts) 1987; Hanson, 2003; Debruyne et al., 2019). The presence of
and serpentine-group minerals. In the Nkonko massif, both talc fractures provides a favorable framework for the widespread

Fig. 8. The chondrite-normalized REE patterns of the Nkonko bedrock and saprolite serpentinites showing globally a decreasing trend and
slight Ce positive anomaly. Numbers 1, 2, and 3 are used to show peridotite derived-type fields, and the Nkonko serpentinite as a harzbur-
gite-derived rock, showed results that matches and can be extended beyond the delimited dunite-harzburgite field (zone 3, orange filled)
(Boschi et al., 2013).

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 43

Fig. 9. The mineral chemistry of Cr-spinel hosted in Nkonko serpentinite (bedrock and saprolite): (a) Plots of Mg# versus Cr# versus Fe# show-
ing spinel end-member compositions and the geodynamic context of peridotite-derived complex; and (b, c) Plots of 100Cr# versus 100Mg#
and 100Fe# versus 100Cr# used to determine the dynamic context of peridotite-derived complex. Numbers 1, 2, and 3 are used to show per-
idotite complex type fields. The Nkonko serpentinite as a peridotite-derived rock is plotted in the field of intracratonic peridotite complex
(zone 2, orange filled). Background compiled spinel data for comparison are from many studies (Proenza et al., 2004; Gervilla et al., 2012; Tor-
res-Sánchez et al., 2017; Mohanty et al., 2019; Ulrich et al., 2019).

occurrence of serpentinization-weathering processes, which are deep lineaments crosscut the entire Congo-Kasai craton and
essential for the development of the regolith zone above the allowed an intrusion of the Nkonko peridotitic dyke (Delhal et
unweathered bedrock serpentinite. al., 1986; Cahen et al., 1987; Hanson, 2003; Debruyne et al., 2019).
Over millions of years (2.6 Ga) ago (Hanson, 2003; Debruyne
5.6. A Genetic Model for the Nkonko Ni-Cr Regolith et al., 2019), this peridotitic intrusion has been altered and
weathered in the presence of percolating water enriched in
Ni-Cr bearing serpentinite in the regolith zone of the Nkonko dissolved CO2, forming serpentines and associated minerals
massif was initially a peridotitic dyke in connection with deep found in the bedrock and regolith zones (consisting of lower
lineaments-oriented ENE-WSW, covering 22°26' to 22°28' of and upper saprolites, and the pedozone) (Kierczak et al., 2007;
East-longitude and 6°06' to 6°07' of South-latitude (Table S1), Malvoisin et al., 2017; Delina et al., 2020). This alteration is
approximately long of 20–24 km and large of 250–500 m. These generally depicted as serpentinization (and carbonation) that

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
44 Douxdoux K. Makutu and Jung Hun Seo

includes hydration, dissolution, and reprecipitation; it was followed wt% of Fe-oxide and can eventually be considered as an Fe-
by stages of weathering and drainage of serpentinized rocks bauxite deposit (Raucq, 1961; Herman and Raucq, 1962). Although
(González-Mancera et al., 2009; Klein, 2009; Klein and Gar- the Nkonko serpentinized massif is known for its Ni and Cr
rido, 2011; Hamdy et al., 2018; Mohanty et al., 2019). These prospects (Raucq, 1961; Herman and Raucq, 1962), it may also
serpentinization and weathering processes are associated with encompass significant amounts of industrial minerals such as talc,
Ni-Cr enrichments that constitute valuable deposits in the regolith magnesite, brucite, and serpentines (Carmignano et al., 2020).
zone of the Nkonko massif. In some cases, this serpentinization Here we suggest a reconstructed genetic processes (Fig. 10) of
of rocks culminates in the formation of bauxite deposits and Ni- the Nkonko serpentinized massif including (1) the peridotitic
rich lateritic soils, especially in “tropical” climates (Kierczak et dyke intrusion, (2) the serpentinization of the peridotite to form
al., 2007; Delina et al., 2020). Laterites and lateritic soils may be the bedrock, (3) the early alteration and weathering of the bedrock
considered as important deposits of Ni, Fe, and Al (Kierczak et serpentinite to form the saprolite serpentinite, and (4) finally the
al., 2007; Villanova-de-Benavent et al., 2013, 2014; Roqué-Rosell et advanced alteration and weathering of the saprolite serpentinite
al., 2017; Iseppi et al., 2018; Delina et al., 2020) and even platinum led to a formation of cap lateritic soils. These geologic processes
group elements (PtGE) (Proenza et al., 2004). Some laterites are we proposed lead us to conclude that the Nkonko Ni-Cr deposit
exceptional Ni sources when they host a Ni-rich limonite (e.g., is of the laterite-type formed within ultramafic intrusions.
(Fe, Ni)O(OH)n.H2O), which may contain up to 1 wt% of NiO A cross-section of the Nkonko serpentinized massif can be
and even more (Herman and Raucq, 1962; Villanova-de-Benavent subdivided into the following layers based on their petrographic
et al., 2013, 2014; Roqué-Rosell et al., 2017; Delina et al., 2020). and chemical characteristics: (1) The unaltered peridotite and
Lateritic soils of the Nkonko regolith zone contained up to 71 unweathered serpentinite constitute the underlying “bedrock

Fig. 10. A suggested genetic model of the Ni-Cr bearing Nkonko serpentinized body showing petrographic and geochemical evolution of
the serpentinization and weathering stages from the bedrock to the regolith zone.

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 45

(I)”. (2) The weathered serpentinite forms the “saprolite or and the Kroëner Foundation for their assistance with sample
saprorock (II)”, which is in contact with the bedrock. This layer transportation costs. We also thank Sangki Kwon, Ongendangenda
is subdivided into: a. Lower saprolite (IIa), which is slightly fractured Tienge Albert, Hyundon Shin, Yonggil Lee Dominic, Cheongu
and weathered. b. Upper saprolite (IIb), which is strongly fractured, Kang, Makutu Ma-Ngwayaya Adalbert, Kanika Mayena Thomas,
weathered, and drained. This sub-layer is in contact with the Makoka Mwanza Frederic, and Kabonwa Janvier for their
“pedozone (III)”. (3) The pedozone (III) is made of top lateritic soils constructive discussions, advice, and valuable comments on
and hosts sub-layers, including: a. Lower pedozone, composed this study’s achievements.
mainly of “yellow-limonite”. b. Upper pedozone, composed of Special thanks go to Musomo Mfumu Krys, Junhee Lee,
“red-limonite”. The saprolite zone and the pedozone together TongHa Lee, Yevgeniya Kim, Yuri Choi, Hahyeon Park, Yechan
form the regolith zone, which hosts the majority of the Nkonko Jeon, and Ivan Bongwe for their help with material and sample
Ni-Cr prospects. preparations. We also appreciate Mamanongo Mapeto Dorothe,
Julie Idiamashi, Alexis Ingungu, Lele Marcelin, Yvan Ndala,
6. CONCLUSIONS Ivan Bongwe, and Milikwini Mpia Dedel for their subsidiary
support during field trips and sample transportation.
This study provides updated data on the Nkonko serpentinites, This study received financial support from the National
encompassing the petrography and geochemistry of both the Institute for International Education and Development (NIIED-
bedrock and the regolith zone. We established geochemical proxies 2020, grant number NIIED-200807-0012) in the Republic of
that better characterize the evolution of the serpentinization and Korea (D.K.M.) and the National Research Foundation (NRF)
weathering processes. The following are important conclusions of Korea, funded by the Korean government (MSIT, grant No.
drawn from this work: 2022R1A2C4001512) (J.H.S.). This work was supported by the
1. Comprehensive petrographic and geochemical studies, including New Faculty Startup Fund from Seoul National University. This
mineral and whole-rock analyses using Raman spectroscopy, work was also supported by Korea Polar Research Institute
XRD, LA-ICP-MS, and EPMA, suggest that the Nkonko serpentinite (KOPRI), under grant numbers PE24050.
protolith is peridotite-harzburgite. We determined the geodynamic
context of the Nkonko peridotite complex to be intraplate or REFERENCES
intracratonic. The overall results show that the Nkonko Ni-Cr
deposit is can be considered as a laterite-type. Alt, J.C., Schwarzenbach, E.M., Früh-Green, G.L., Shanks, W.C., Berna-
2. The ore mineral geochemistry show that the Cr is mainly sconi, S.M., Garrido, C.J., Crispini, L., Gaggero, L., Padrón-Navarta,
hosted in spinels of the bedrock and saprolite, whereas Ni is J.A., and Marchesi, C., 2013, The role of serpentinites in cycling of
carbon and sulfur: seafloor serpentinization and subduction meta-
mainly hosted in serpentine a secondary “garnierite” of the
morphism. Lithos, 178, 40–54. https://doi.org/10.1016/j.lithos.2012.12.006
saprolite. Olivines and pyroxenes of the initially peridotite dyke
Batumike, J.M., Griffin, W.L., O’Reilly, S.Y., Belousova, E.A., and
were replaced by serpentine-like such as lizardite (rarely chrysotile) Pawlitschek, M., 2009, Crustal evolution in the central Congo-
and antigorite (primary “garnierite”) in the unweathered bedrock Kasai Craton, Luebo, D.R. Congo: insights from zircon U-Pb ages,
serpentinite, which minerals were also lately replaced by antigorite Hf-isotope and trace-element data. Precambrian Research, 170,
(secondary “garnierite”) in the regolith during reprecipitation 107–115. https://doi.org/10.1016/j.precamres.2008.12.001
within fractures. Cr-spinel in the initial peridotite and bedrock Bayliss, P., 2018, Unit cell data of serpentine group minerals. Miner-
serpentinite was progressively replaced by ferrochromite and alogical Magazine, 44, 153–156. https://doi.org/10.1180/minmag.
1981.044.334.06
Cr-magnetite in the saprolite serpentinite. Subsequently, Cr-
Bonatti, E., 1976, Serpentinite protrusions in the oceanic crust. Earth
magnetite was replaced by hematite-limonite during advanced
and Planetary Science Letters, 32, 107–113. https://doi.org/10.1016/
alteration (hydrolysis) in the pedozone (top lateritic soil). 0012-821X(76)90048-0
3. The Nkonko massif regolith zone can also be valuable for Bonney, T.G., 1877, On the serpentine and associated rocks of the Liz-
industrial minerals such as talc, serpentine, magnesite, and brucite. ard district. Journal of the Geological Society, 33, 884–924. https://
The presence of magnesite suggests a possible contribution from doi.org/10.1144/GSL.JGS.1877.033.01-04.51
oxidized meteoric water containing dissolved CO2. Boschi, C., Bonatti, E., Ligi, M., Brunelli, D., Cipriani, A., Dallai, L.,
D'Orazio, M., Früh-Green, G.L., Tonarini, S., Barnes, J.D., and Bed-
ini, R.M., 2013, Serpentinization of mantle peridotites along an
ACKNOWLEDGMENTS uplifted lithospheric section, Mid Atlantic Ridge at 11°N. Lithos,
178, 3–23. https://doi.org/10.1016/j.lithos.2013.06.003
We gratefully acknowledge Gerhard Bringmann, Mudogo Braun, J.J., Pagel, M., Muller, J.P., Bilong, P., Michard, A., and Guillet, B.,
Virima, and Karine Ndjoko Ioset through the BEBUC program 1990, Cerium anomalies in lateritic profiles. Geochimica et Cosmo-

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
46 Douxdoux K. Makutu and Jung Hun Seo

chimica Acta, 54, 781–795. https://doi.org/10.1016/0016-7037(90)90373-S zoic to Neoproterozoic growth and evolution of the eastern Congo
Brigatti, M.F., Malferrari, D., Laurora, A., and Elmi, C., 2011, Structure Craton: its role in the Rodinia puzzle. Precambrian Research, 160,
and mineralogy of layer silicates: recent perspectives and new 127–141. https://doi.org/10.1016/j.precamres.2007.04.020
trends. In: Brigatti, M.F. and Mottana, A. (eds.), Layered Mineral Debret, B., Andreani, M., Godard, M., Nicollet, C., Schwartz, S., and
Structures and their Application in Advanced Technologies. Euro- Lafay, R., 2013, Trace element behavior during serpentinization/de-
pean Mineralogical Union Notes in Mineralogy. https://doi.org/ serpentinization of an eclogitized oceanic lithosphere: a LA-ICPMS
10.1180/EMU-notes.11.1 study of the Lanzo ultramafic massif (Western Alps). Chemical
Bruno, H., Heilbron, M., Morisson V.C., Strachan, R., Fowler, M., Ber- Geology, 357, 117–133. https://doi.org/10.1016/j.chemgeo.2013.08.025
san, S., Moreira, H., Motta, R., Almeida, J., Almeida, R., Carvalho, Debruyne, D., Dewaele, S., Muchez, P., and Oliveira, E.P., 2019, Detrital
M., and Storey, C., 2021, Evidence for a complex accretionary history zircon U-Pb ages from the Paleoproterozoic Lulua and Luiza volca-
preceding the amalgamation of Columbia: the Rhyacian Minas- nosedimentary Groups in the Kasai Shield, Congo Craton: implications
Bahia Orogen, southern São Francisco Paleocontinent, Brazil. Gond- for the source of sediments and the Kasai-Ntem and São Francisco
wana Research, 92, 149–171. https://doi.org/10.1016/j.gr.2020.12.019 Craton relationship. Precambrian Research, 333, 1–17. https://doi.org/
Cahen, L., Snelling, N.J., Delhal, J., and Vail, J.R., 1987, The geochronology 10.1016/j.precamres.2019.105448
and evolution of Africa. Precambrian Research, 36, 181–183. https:// Delhal, J., Deutsch, S., and Denoiseux, B., 1986, A Sm/Nd isotopic study
doi.org/10.1016/0301-9268(87)90090-8 of heterogeneous granulites from the Archean Kasai-Lomami gab-
Cahen, L., Snelling, N.J., Delhal, J., Vail, J.R., Bonhomme, M., and bro-norite and charnockite complex (Zaire, Africa). Chemical Geol-
Ledent, D., 1984, The Geology of Africa: The Geochronology and ogy, 57, 235–245. https://doi.org/10.1016/0009-2541(86)90105-1
Evolution of Africa. Oxford University Press, Oxford, UK, 512 p. Delina, R.E., Arcilla, C., Otake, T., Garcia, J.J., Tan, M., and Ito, A., 2020,
Cailteux, J., Binda, P.L., Katekesha, W.M., Kampunzu, A.B., Intiomale, Chromium occurrence in a nickel laterite profile and its implica-
M.M., Kapenda, D., Kaunda, C., Ngongo, K., Tshiauka, T., and Wen- tions to surrounding surface waters. Chemical Geology, 558, 1–14.
dorff, M., 1994, Lithostratigraphical correlation of the Neoproterozoic https://doi.org/10.1016/j.chemgeo.2020.119863
Roan Supergroup from Shaba (Zaire) and Zambia, in the central Deschamps, F., Godard, M., Guillot, S., and Hattori, K., 2013, Geo-
African copper-cobalt metallogenic province. Journal of African Earth chemistry of subduction zone serpentinites: a review. Lithos, 178,
Sciences, 19, 265–278. https://doi.org/10.1016/0899-5362(94)90014-0 96–127. https://doi.org/10.1016/j.lithos.2013.05.019
Carmignano, O., Vieira, S., Brandão, P.R., Bertoli, A., and Lago, R., 2020, Duffin, C., 2006, Silicate minerals: an overview. BMS Occasional Paper,
Serpentinites: mineral structure, properties and technological British Micromount Society, Hastings, UK, 21, 38 p.
applications. Journal of the Brazilian Chemical Society, 31, 2–14. Faust, G.T. and Fahey, J.J., 1962, The serpentine group minerals: stud-
https://doi.org/10.21577/0103-5053.20190215 ies of the natural phases in the system MgO-SiO2-H2O and the sys-
Carvalho, H.D., Tassinari, C., Alves, P.H., Guimaraes, F., and Simoes, tems containing the congeners of magnesium. USGS Professional
M.C., 2000, Geochronological review of the Precambrian in west- Paper, 384-A, United States Geological Survey, Washington, D.C.,
ern Angola: links with Brazil. Journal of African Earth Sciences, 31, 92 p. https://doi.org/10.3133/pp384A
383–402. https://doi.org/10.1016/S0899-5362(00)00095-6 Fernandez-Alonso, M., Cutten, H., De Waele, B., Tack, L., Tahon, A.,
Chen, Y.K., Ni, P., Pan, J.Y., Cui, J.M., Li, W.S., Fang, G.J., Zhao, Z.H., Baudet, D., and Barritt, S.D., 2012, The Mesoproterozoic Karagwe-
Xu, Y.M., Ding, J.Y., and Han, L., 2023, Fluid evolution and metal- Ankole Belt (formerly the NE Kibara Belt): the result of prolonged
logenic mechanism of the Xianghualing skarn-type Sn deposit, South extensional intracratonic basin development punctuated by two
China: evidence from petrography, fluid inclusions and trace-element short-lived far-field compressional events. Precambrian Research,
composition of cassiterite. Ore Geology Reviews, 154, 1–20. https:/ 216, 63–86. https://doi.org/10.1016/j.precamres.2012.06.007
/doi.org/10.1016/j.oregeorev.2023.105351 Fernandez-Alonso, M., Mupande, J.F., Badosa, T., Baudet, D., Dewaele,
Cheng, Y., Spandler, C., Kemp, A., Mao, J., Rusk, B., Hu, Y., and Blake, S., Kalenga, H., Kampata, D., Kanda, N.V., Lahmouch, M., Lahogue,
K., 2019, Controls on cassiterite (SnO2) crystallization: evidence P., Luamba, M., Mashagiro, H., Mawaya, P., Mpoi, J., Mwanza, B.,
from cathodoluminescence, trace-element chemistry, and geochro- and Onya, F., 2016, New 1/2,500,000 scale geologic and mineral occur-
nology at the Gejiu Tin District. American Mineralogist, 104, 118– rences maps of the Democratic Republic of Congo. Royal Museum
129. https://doi.org/10.2138/am-2019-6466 for Central Africa (RMCA), Tervuren, Belgium, 2 p.
Coleman, R.G., 1971, Petrologic and geophysical nature of serpentinites. Frost, B.R., 1985, On stability of sulfides, oxides and native metals in
Geological Society of America Bulletin, 82, 897–918. https://doi.org/ serpentinites. Journal of Petrology, 26, 31–63. https://doi.org/10.1093/
10.1130/0016-7606(1971)82[897:PAGNOS]2.0.CO;2 petrology/26.1.31
Dai, S., Graham, I.T., and Ward, C.R., 2016, A review of anomalous rare Frost, B.R. and Beard, J.S., 2007, On silica activity and serpentinization.
earth elements and yttrium in coal. International Journal of Coal Journal of Petrology, 48, 1351–1368. https://doi.org/10.1093/petrol-
Geology, 159, 82–95. https://doi.org/10.1016/j.coal.2016.04.005 ogy/egm021
Daval, D., Hellmann, R., Martinez, I., Gangloff, S., and Guyot, F., 2013, Frost, B.R., Evans, K.A., Swapp, S.M., Beard, J.S., and Mothersole, F.E.,
Lizardite serpentine dissolution kinetics as a function of pH and 2013, The process of serpentinization in dunite from New Caledo-
temperature, including effects of elevated pCO2. Chemical Geol- nia. Lithos, 178, 24–39. https://doi.org/10.1016/j.lithos.2013.02.002
ogy, 351, 245–256. https://doi.org/10.1016/j.chemgeo.2013.05.020 Galí, S., Soler, J.M., Proenza, J.A., Lewis, J.F., Cama, J., and Tauler, E.,
De Waele, B., Johnson, S.P., and Pisarevsky, S.A., 2008, Palaeoprotero- 2012, Ni enrichment and stability of Al-free garnierite solid-solu-

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 47

tions: a thermodynamic approach. Clays and Clay Minerals, 60, Hermann, J., Muntener, O., and Scambelluri, M., 2000, The importance
121–135. https://doi.org/10.1346/CCMN.2012.0600203 of serpentinite mylonites for subduction and exhumation of oceanic
Garrido, C.J., Sánchez-Vizcaíno, V.L., Gómez-Pugnaire, M.T., Tromms- crust. Tectonophysics, 327, 225–238. https://doi.org/10.1016/S0040-
dorff, V., Alard, O., Bodinier, J.L., and Godard, M., 2005, Enrich- 1951(00)00171-2
ment of HFSE in chlorite-harzburgite produced by high-pressure Honnorez, J. and Kirst, P., 1975, Petrology of Rodingites from the equa-
dehydration of antigorite-serpentinite: implications for subduction torial mid-Atlantic fracture zones and their geotectonic significance.
magmatism. Geochemistry, Geophysics, Geosystems, 6, 1–15. https:// Contributions to Mineralogy and Petrology, 49, 233–257. https://
doi.org/10.1029/2004GC000791 doi.org/10.1007/BF00376590
Gervilla, F., Padrón-Navarta, J.A., Kerestedjian, T., Sergeeva, I., González- Hostetler, P.B., Coleman, R.G., and Evans, B.W., 1966, Brucite in alpine
Jiménez, J.M., and Fanlo, I., 2012, Formation of ferrian chromite in serpentinites. The American Mineralogist, 51, 75–98.
podiform chromitites from the Golyamo Kamenyane serpentinite, Huang, R., Lin, C.T., Sun, W., Ding, X., Zhan, W., and Zhu, J., 2017, The
eastern Rhodopes, SE Bulgaria: a two-stage process. Contributions production of iron oxide during peridotite serpentinization: influence
to Mineralogy and Petrology, 164, 643–657. https://doi.org/10.1007/ of pyroxene. Geoscience Frontiers, 8, 1311–1321. https://doi.org/
s00410-012-0763-3 10.1016/j.gsf.2017.01.001
González-Mancera, G., Ortega-Gutiérrez, F., Proenza, J., and Atudorei, Inogwabini, B.I., Sandokan, B.M., and Ndunda, M., 2006, A dramatic
V., 2009, Petrology and geochemistry of Tehuitzingo serpentinites decline in rainfall regime in the Congo basin: evidence from a thirty
(Acatlan Complex, SW Mexico). Boletín de la Sociedad GeolóGica four years data set from the Mabali scientific research center, Dem-
Mexicana, 61, 419–435. https://doi.org/10.18268/BSGM2009v61n3a9 ocratic Republic of Congo. The International Journal of Meteorol-
Guillong, M., Meier, D.L., Allan, M.M., Heinrich, C.A., and Yardley, B., ogy, 31, 278–285.
2008, Appendix A6: SILLS: A matlab-based program for the reduc- Iseppi, M., Sevin, B., Cluzel, D., Maurizot, P., and Bayon, B.L., 2018,
tion of laser ablation ICP-MS data of homogeneous materials and Supergene nickel ore deposits controlled by gravity-driven faulting and
inclusions. Mineralogical Association of Canada Short Course, 40, slope failure, peridotite nappe, New Caledonia. Economic Geology,
328–333. 113, 531–544. https://doi.org/10.5382/econgeo.2018.4561
Guillot, S., Hattori, K., Agard, P., Schwartz, S., and Vidal, O., 2009, Kadima, E., Delvaux, D., Sebagenzi, S.N., Tack, L., and Kabeya, S.M.,
Exhumation processes in oceanic and continental subduction con- 2011, Structure and geological history of the Congo Basin: an inte-
texts: a review. In: Lallemand, S. and Funiciello, F. (eds.), Subduc- grated interpretation of gravity, magnetic and reflection seismic
tion Zone Geodynamics. Frontiers in Earth Sciences, p. 175–205. data. Basin Research, 23, 499–527. https://doi.org/10.1111/j.1365-
https://doi.org/10.1007/978-3-540-87974-9_10 2117.2011.00500.x
Guillot, S., Schwartz, S., Reynard, B., Agard, P., and Prigent, C., 2015, Kawahara, H., Endo, S., Wallis, S.R., Nagaya, T., Mori, H., and Asahara,
Tectonic significance of serpentinites. Tectonophysics, 646, 1–19. Y., 2016, Brucite as an important phase of the shallow mantle
https://doi.org/10.1016/j.tecto.2015.01.020 wedge: evidence from the Shiraga unit of the Sanbagawa subduction
Hamdy, M.M., Gamal El Dien, H., Abd El-Wahed, M.A., and Mor- zone, SW Japan. Lithos, 254–255, 53–66. https://doi.org/10.1016/
ishita, T., 2018, Garnierite-bearing serpentinite from the central j.lithos.2016.02.022
Eastern Desert of Egypt: a signature of paleo-weathering in the Kelemen, P.B. and Hirth, G., 2012, Reaction-driven cracking during ret-
Arabian Nubian Shield? Journal of African Earth Sciences, 146, rograde metamorphism: olivine hydration and carbonation. Earth and
95–117. https://doi.org/10.1016/j.jafrearsci.2017.10.007 Planetary Science Letters, 345–348, 81–89. https://doi.org/10.1016/
Hanson, R.E., 2003, Proterozoic geochronology and tectonic evolution j.epsl.2012.06.018
of southern Africa. In: Yoshida, M., Windley, B.E., and Dasgupta, S. Kierczak, J., Neel, C., Bril, H., and Puziewicz, J., 2007, Effect of mineral-
(eds.), Proterozoic East Gondwana: Supercontinent Assembly and ogy and pedoclimatic variations on Ni and Cr distribution in ser-
Breakup. Geological Society, London, Special Publications, 206, p. pentine soils under temperate climate. Geoderma, 142, 165–177.
427–463. https://doi.org/10.1144/GSL.SP.2003.206.01.20 https://doi.org/10.1016/j.geoderma.2007.08.009
Harvey, J., Garrido, C.J., Savov, I., Agostini, S., Padrón-Navarta, J.A., Klein, F., 2009, Petrology of serpentinite and rodingites in the oceanic
Marchesi, C., Sánchez-Vizcaíno, L.V., and Gómez-Pugnaire, M.T., lithosphere. Ph.D. Thesis, University of Bremen, Bremen, Germany,
2014, 11B-rich fluids in subduction zones: the role of antigorite 175 p.
dehydration in subducting slabs and boron isotope heterogeneity Klein, F., Bach, W., and McCollom, T.M., 2013, Compositional controls
in the mantle. Chemical Geology, 376, 20–30. https://doi.org/10.1016/ on hydrogen generation during serpentinization of ultramafic
j.chemgeo.2014.03.015 rocks. Lithos, 178, 55–69. https://doi.org/10.1016/j.lithos.2013.03.008
Haskin, L.A., Wang, A., Rockow, K.M., Jolliff, B.L., Korotev, R.L., and Klein, F. and Garrido, C.J., 2011, Thermodynamic constraints on min-
Viskupic, K.M., 1997, Raman spectroscopy for mineral identification eral carbonation of serpentinized peridotite. Lithos, 126, 147–160.
and quantification for in situ planetary surface analysis: a point count https://doi.org/10.1016/j.lithos.2011.07.020
method. Journal of Geophysical Research, 102, 19293–19306. https:// Kodolányi, J., Pettke, T., Spandler, C., Kamber, B.S., and Gméling, K.,
doi.org/10.1029/97je01694 2012, Geochemistry of ocean floor and fore-arc serpentinites: con-
Herman, P. and Raucq, P., 1962, Données complémentaires sur les chro- straints on the ultramafic input to subduction zones. Journal of Petrol-
mites du Kasaï. Bulletin de la Société Belge de Géologie, de Paléon- ogy, 53, 235–270. https://doi.org/10.1093/petrology/egr058
tologie et d'Hydrologie, 3, 336–357. Kröner, A. and Stern, R.J., 2005, Pan-African Orogeny. In: Selley, R.C.,

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2
48 Douxdoux K. Makutu and Jung Hun Seo

Cocks, L.R.B., and Plimer, I.R. (eds.), Encyclopedia of Geology. 1, 10.2138/am-2003-8-922

1–12. https://doi.org/10.1016/B0-12-369396-9/00431-7 Nozaka, T., 2005, Metamorphic history of serpentinite mylonites from
Kumarathilaka, P., Dissanayake, C.B., and Vithanage, M., 2014, Geo- the Happo ultramafic complex, central Japan. Journal of Metamorphic
chemistry of serpentinite soils: a brief overview. Journal of Geologi- Geology, 23, 711–723. https://doi.org/10.1111/j.1525-1314.2005.00605.x
cal Society of Sri Lanka, 16, 53–63. Nozaka, T., Wintsch, R.P., and Meyer, R., 2017, Serpentinization of oliv-
Lafay, R., Montes-Hernandez, G., Janots, E., Chiriac, R., Findling, N., ine in troctolites and olivine gabbros from the Hess Deep Rift.
and Toche, F., 2012, Mineral replacement rate of olivine by chryso- Lithos, 282, 201–214. https://doi.org/10.1016/j.lithos.2016.12.032
tile and brucite under high alkaline conditions. Journal of Crystal Okamoto, A., Ogasawara, Y., Hirano, N., and Tsushiya, N., 2013, Effect
Growth, 347, 62–72. https://doi.org/10.1016/j.jcrysgro.2012.02.040 of silica transport on serpentinization in the Ol-Opx-H2O system.
Li, X.H., Chen, Y., Li, J., Yang, C., Ling, X.X., and Tchouankoue, J.P., 2016, Procedia Earth and Planetary Science, 7, 628–631. https://doi.org/
New isotopic constraints on age and origin of Mesoarchean char- 10.1016/j.proeps.2013.03.015
nockite, trondhjemite and amphibolite in the Ntem Complex of Oyanagi, R., Okamoto, A., and Tsuchiya, N., 2017, Mechanisms of ser-
NW Congo Craton, southern Cameroon. Precambrian Research, 276, pentinization utilizing olivine-plagioclase-H2O system under hydrother-
14–23. https://doi.org/10.1016/j.precamres.2016.01.027 mal conditions. Procedia Earth and Planetary Science, 17, 686–
Li, Y. and Audétat, A., 2012, Partitioning of V, Mn, Co, Ni, Cu, Zn, As, 689. https://doi.org/10.1016/j.proeps.2016.12.153
Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulfide phases and hydrous Oyarzún, J., Oyarzun, R., Lillo, J., Higueras, P., Maturana, H., and
basanite melt at upper mantle conditions. Earth and Planetary Sci- Oyarzún, R., 2016, Distribution of chemical elements in calc-alka-
ence Letters, 355, 327–340. https://doi.org/10.1016/j.epsl.2012.08.008 line igneous rocks, soils, sediments and tailings deposits in northern
Luolavirta, K., Hanski, E., Maier, W., and Santaguida, F., 2018, Charac- central Chile. Journal of South American Earth Sciences, 69, 25–42.
terization and origin of dunitic rocks in the Ni-Cu-(PGE) sulfide https://doi.org/10.1016/j.jsames.2016.03.004
ore-bearing Kevitsa intrusion, northern Finland: whole-rock and Page, N.J., 1968, Chemical differences among the serpentine “poly-
mineral chemical constraints. Bulletin of the Geological Society of morphs”. American Mineralogist, 53, 201–215.
Finland, 90, 5–32. https://doi.org/10.17741/bgsf/90.1.001 Pasteris, J.D., 1981, Occurrence of graphite in serpentinized olivines in
Malvoisin, B., 2015, Mass transfer in the oceanic lithosphere: serpentiniza- kimberlites. Geology, 9, 356–359. https://doi.org/10.1130/0091-
tion is not isochemical. Earth and Planetary Science Letters, 430, 7613(1981)9<356:OOGISO>2.0.CO;2
75–85. https://doi.org/10.1016/j.epsl.2015.07.043 Peters, D., Bretscher, A., John, T., Scambelluri, M., and Pettke, T., 2017,
Malvoisin, B., Brantut, N., and Kaczmarek, M.A., 2017, Control of ser- Fluid-mobile elements in serpentinites: constraints on serpentinisa-
pentinisation rate by reaction-induced cracking. Earth and Planetary tion environments and element cycling in subduction zones. Chemical
Science Letters, 476, 143–152. https://doi.org/10.1016/j.epsl.2017.07.042 Geology, 466, 654–666. https://doi.org/10.1016/j.chemgeo.2017.07.017
McDonough, W.F. and Sun, S.S., 1995 The composition of the Earth. Petriglieri, J.R., Salvioli-Mariani, E., Mantovani, L., Tribaudino, M., Lot-
Chemical Geology, 120, 223–253. https://doi.org/10.1016/0009- tici, P.P., Laporte-Magoni, C., and Bersani, D., 2015, Micro-Raman
2541(94)00140-4 mapping of the polymorphs of serpentine. Journal of Raman Spec-
McLennan, S.M., Hemming, S.R., Taylor, S.R., and Ericksson, K.A., troscopy, 46, 953–958. https://doi.org/10.1002/jrs.4695
1995, Early Proterozoic crustal evolution: geochemical and Nd-Pb Poncelet, G., Jacobs, P., Delannay, F., Genet, M., Gérard, P., and Herbil-
isotopic evidence from metasedimentary rocks, southwestern North lon, A.J., 1979, Étude préliminaire sur la localisation du nickel dans une
America. Geochimica et Cosmochimica Acta, 59, 1153–1177. https:// garniérite naturelle. Bulletin de Minéralogie, 102, 379–385. https://
doi.org/10.1016/0016-7037(95)00032-U doi.org/10.3406/bulmi.1979.7333
Mizukami, T., Yokoyama, H., Hiramatsu, Y., Arai, S., Kawahara, H., Nagaya, Proenza, J.A., Ortega-Gutiérrez, F., Camprubı?, A., Tritlla, J., Elı?as-Her-
T., and Simon, W.R., 2014, Two types of antigorite serpentinite con- rera, M., and Reyes-Salas, M., 2004, Paleozoic serpentinite-enclosed
trolling heterogeneous slow-slip behaviours of slab-mantle interface. chromitites from Tehuitzingo (Acatlán Complex, southern Mexico): a
Earth and Planetary Science Letters, 401, 148–158. https://doi.org/ petrological and mineralogical study. Journal of South American
10.1016/j.epsl.2014.06.009 Earth Sciences, 16, 649–666. https://doi.org/10.1016/j.jsames.2003.12.003
Mohanty, N., Singh, S.P., Satyanarayanan, M., Jayananda, M., Kora- Raucq, P., 1961, Note préliminaire sur les massifs ultrabasiques du Kasaï
koppa, M.M., and Hiloidari, S., 2019, Chromian spinel compositions central et certains de leurs constituants métalliques. Annale de la
from Madawara ultramafics, Bundelkhand Craton: implications on Sociète Gélogique de Belgique, 84.
petrogenesis and tectonic evolution of the southern part of Bun- Reynard, B., 2013, Serpentine in active subduction zones. Lithos, 178,
delkhand Craton, central India. Geological Journal, 54, 2099–2123. 171–185. https://doi.org/10.1016/j.lithos.2012.10.012
https://doi.org/10.1002/gj.3286 Richter, E.D., Berdugo, M., Laster, R., Westin, J.B., and Fischbein, A.,
Nicholson, W.J., 2001, The carcinogenicity of chrysotile asbestos – a 1995, Chrysotile and crocidolite asbestos in Israel: uses, exposures
review. Industrial Health, 39, 57–64. https://doi.org/10.2486/ind- and risks. La Medicina del Lavoro, 86, 449–456.
health.39.57 Rollinson, H. and Adetunji, J., 2016, Comment on ‘Podiform chromi-
Nicholson, W.J. and Raffn, E., 1995, Recent data on cancer due to asbestos tites do form beneath mid-ocean ridges’ by Arai, S. and Miura, M.
in USA and Danemark. La Medicina del Lavoro, 86, 393–410. Lithos, 254–255, 131–133. https://doi.org/10.1016/j.lithos.2015.10.023
Nozaka, T., 2003, Olivine in thermally metamorphosed serpentinite Roqué-Rosell, J., Villanova-de-Benavent, C., and Proenza, J.A., 2017,
from Japan. American Mineralogist, 88, 1377–1384. https://doi.org/ The accumulation of Ni in serpentines and garnierites from the

https://doi.org/10.1007/s12303-023-0037-2 https://www.springer.com/journal/12303
 The petrography and geochemistry of the Nkonko serpentinites, DRC 49

Falcondo Ni-laterite deposit (Dominican Republic) elucidated by tion of the continental crust: rare earth element evidence from sed-
means of μXAS. Geochimica et Cosmochimica Acta, 198, 48–69. imentary rocks. Philosophical Transactions of the Royal Society,
https://doi.org/10.1016/j.gca.2016.11.004 301, 381–399. https://doi.org/10.1098/rsta.1981.0119
Rouméjon, S., Williams, M.J., and Früh-Green, G.L., 2018, In-situ oxy- Torres-Sánchez, S.A., Carita, A., Uwe, J., Barboza-Gudiño, J.R., Alemán-
gen isotope analyses in serpentine minerals: constraints on ser- Gallardo, E., Ramírez Fernández, J.A., Torres-Sánchez, D., and
pentinization during tectonic exhumation at slow- and ultraslow- Abratis, M., 2017, Petrology and geochemistry of meta-ultramafic
spreading ridges. Lithos, 323, 156–173. https://doi.org/10.1016/j.lithos. rocks in the Paleozoic Granjeno Schist, northeastern Mexico: rem-
2018.09.021 nants of Pangaea ocean floor. Open Geosciences, 9, 361–384. https://
Rudge, J.F., Kelemen, P.B., and Spiegelman, M., 2010, A simple model doi.org/10.1515/geo-2017-0029
of reaction-induced cracking applied to serpentinization and car- Treloar, P.J., 1987, The Cr-minerals of Outokumpu—their chemistry
bonation of peridotite. Earth and Planetary Science Letters, 291, and significance. Journal of Petrology, 28, 867–886. https://doi.org/
215–227. https://doi.org/10.1016/j.epsl.2010.01.016 10.1093/petrology/28.5.867
Rudnick, R.L., 1992, Restites, Eu anomalies, and the lower continental Ulrich, M., Cathelineau, M., Muñoz, M., Boiron, M.C., Teitler, Y., and
crust. Geochimica et Cosmochimica Acta, 56, 963–970. https:// Karpoff, A.M., 2019, The relative distribution of critical (Sc, REE)
doi.org/10.1016/0016-7037(92)90040-P and transition metals (Ni, Co, Cr, Mn, V) in some Ni-laterite deposits
Smith, A.H. and Wright, C.C., 1996, Chrysotile asbestos is the main of New Caledonia. Journal of Geochemical Exploration, 197, 93–
cause of pleural mesothelioma. American Journal of Industrial Medicine, 113. https://doi.org/10.1016/j.gexplo.2018.11.017
30, 252–266. https://doi.org/10.1002/(SICI)1097-0274(199609)30:3 Villanova-de-Benavent, C., Proenza, J.A., Galí, S., García-Casco, A.,
<252::AID-AJIM2>3.0.CO;2-0 Tauler, E., Lewis, J.F., and Longo, F., 2014, Garnierites and garn-
Smith, K.S. and Huyck, H.L.O., 1999, An overview of the abundance, ierites: textures, mineralogy and geochemistry of garnierites in the
relative mobility, bioavailability and human toxicity of metals. In: Falcondo Ni-laterite deposit, Dominican Republic. Ore Geology
Plumlee, G.S., Logsdon, M.J., and Filipek, L.F. (eds.), The Environ- Reviews, 58, 91–109. https://doi.org/10.1016/j.oregeorev.2013.10.008
mental Geochemistry of Mineral Deposits: Part A: Processes, Tech- Villanova-de-Benavent, C., Proenza, J.A., Galí, S., Tauler, E., García-
niques, and Health Issues Part B: Case Studies and Research Topics. Casco, A., Lewis, J.F., and Longo, F., 2013, “Garnierite” ore and Ni-
The Society of Economic Geologists, 6, p. 29–69. https://doi.org/ serpentine mineralizations from the Falcondo Ni-laterite deposit
10.5382/Rev.06.02 (Dominican Republic): an approach from quantitative XR element
Stalder, R. and Ulmer, P., 2001, Phase relations of a serpentine composi- imaging. The 12th Biennial SGA Meeting on Mineral Deposit
tion between 5 and 14 GPa: significance of clinohumite and phase E as Research for a High-tech World, The Society for Geology Applied
water carriers into the transition zone. Contributions to Mineralogy to Mineral Deposits, Uppsala, Sweden, Aug. 12–13, p. 1–5.
and Petrology, 140, 670–679. https://doi.org/10.1007/s004100000208 Yang, L., Hao, Z., Li, H., Jiang, X.-W., and Die, L., 2020, Application of
Syverson, D.D., Tutolo, B.M., Borrok, D.M., and Seyfried, W.E., 2017, SILLS software in data processing of single fluorite fluid inclusion
Serpentinization of olivine at 300 °C and 500 bars: an experimen- LA-ICP-MS trace element analysis. Rock and Mineral Analysis, 39,
tal study examining the role of silica on the reaction path and oxi- 300–310. https://doi.org/10.15898/j.cnki.11-2131/td.201812260141
dation state of iron. Chemical Geology, 475, 122–134. https:// Yang, S.J., Koh, S.M., Park, S.W., and Lee, G.J., 2012, Geology and mineral
doi.org/10.1016/j.chemgeo.2017.11.006 resources of DR Congo. Journal of the Mineralogical Society of Korea,
Tang, M., Rudnick, R.L., McDonough, W.F., Gaschnig, R.M., and Huang, 25, 175–184. (in Korean) https://doi.org/10.9727/jmsk.2012.25.3.175
Y., 2015, Europium anomalies constrain the mass of recycled lower
continental crust. Geology, 43, 703–706. https://doi.org/10.1130/ Publisher’s Note Springer Nature remains neutral with regard to jurisdic-
G36641.1 tional claims in published maps and institutional affiliations.
Taylor, S.R. and McLennan, S.M., 1981, The composition and evolu-

https://www.springer.com/journal/12303 https://doi.org/10.1007/s12303-023-0037-2