Energy and Earth Science Vol. 3, No. 2, 2020 www.scholink.org/ojs/index.php/ees ISSN 2578-1359 (Print) ISSN 2578-1367 (Online) 80 Original Paper Mantle Xenoliths from Ibal-Oku (Oku massif, North-west Region, Cameroon): Imprints of Superimposed Carbonatitic and Silicic Metasomatisms Sylvin S. T. Tedonkenfack 1 , Jules Tamen 1 , David G. Nkouathio 1 *, Bertrand T. Aziwo 1,2 , Kagarabi P. Mulimbi 1,3 , Yangouo F. Kimoun 1 , Tabengo M. Ziada 1 & Sylvie N. F. Djukem 1 1 Department of Earth Sciences, Faculty of Sciences, University of Dschang, Dschang, Cameroon 2 Local Materials Promotion Authority (MIPROMALO), Ministry of Scientific Research and Innovation, Yaounde, Cameroon 3 Official University of Bukavu, Democratic Republic of Congo * Corresponding author: David G. Nkouathio, Department of Earth Sciences, Faculty of Sciences, University of Dschang, P.O. Box 67, Dschang, Cameroon Received: August 15, 2020 Accepted: September 1, 2020 Online Published: October 29, 2020 doi:10.22158/ees.v3n2p80 URL: http://dx.doi.org/10.22158/ees.v3n2p80 Abstract Mantle xenoliths have been discovered in Ibal-Oku basalts from Oku Massif, Cameroon Volcanic Line. These xenoliths analyzed in term of major elements by scanning electron microscope, atomic emission spectrometry, traces and rare earth elements by mass spectrometry are peridotites and pyroxenites. Peridotites comprise Fe-rich lherzolites, harzburgites and wehrlites. Pyroxenites comprise websterites, olivine-websterites, clinopyroxenites and olivine-clinopyroxenites. Mineralogically, olivine Fo% values and NiO content vary from 85 to 91 and 0.26 to 0.43 wt.%, respectively. Orthopyroxene is enstatite, Mg# values and Al content ranging from 0.83 to 0.92 and 0.12 to 0.27 atom per formula unit (apfu), respectively. Clinopyroxene is augite and diopside, Mg# values and Al content ranging from 0.83 to 0.93 and 0.23 to 0.37 apfu, respectively. Spinel is aluminous, Cr# and Mg# values ranging from 0.07 to 0.23 and 0.67 to 0.82, respectively. Micas are biotites (Fe#: 0.52-0.76). Feldspars, which are secondary are sanidine, andesine and labradorite. Geochemically, peridotite Mg# values vary from 82.7 to 89.9 and pyroxenites from 80.1 to 83.6. The major element variations and some compatible elements are described in terms of partial melting (14-15 vol.% in lherzolites and 17-18 vol.% in harzburgites), whereas the heterogeneities in trace elements are related to carbonatitic/silicic metasomatism. www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 81 Published by SCHOLINK INC. Keywords Oku massif, Cameroon Volcanic Line, ultramafic xenoliths, partial melting, metasomatism 1. Introduction The Cameroon Volcanic Line (CVL) yields the opportunity to studying the Sub-Continental Lithospheric Mantle (SCLM). This has been the concern of several works based either on volcanic rocks (Fitton, 1987; Halliday et al., 1988, 1990; Marzoli et al., 2000) or on mantle xenoliths (Lee et al., 1996; Matsukage & Oya, 2010; Tedonkenfack et al., 2019). In general, the SCLM is heterogeneous and it is considered as a result of proportionate mixing of HIMU, DM and EM types (Princivalle et al., 2000; Njilah et al., 2013; Asaah et al., 2014). A few areas along CVL enclose mantle xenoliths dominantly lherzolitic. Among these mantle xenoliths bearing areas are the Oku Massif which have so far been studied: the Enep area (Nana, 1991, 2001; Lee et al., 1996; Princivalle et al., 2000; Matsukage & Oya, 2010), the Bafmeng area (Chenyi, 2015; Chenyi et al., 2017), the Nyos sector (Lee et al., 1996; Nana, 2001; Temdjim et al., 2004; Matsukage & Oya, 2010; Teitchou et al., 2011; Temdjim, 2012; Pinter et al., 2015; Liu et al., 2017), the Wum area (Aziwo, 2015) and the Ibal-Oku sector (Tedonkenfack, 2016; Tedonkenfack et al., 2019). In fact, the Oku volcanic group (Figure 1), located on CVL continental part is built upon pan African (Lasserre, 1978; Dunlop 1983) plutono-metamorphic basement rocks (Dumort et Péronne 1966; Nana, 1991, 2001; Njilah et al., 2004; Aziwo, 2015; Manjeh, 2016) cross cutted by numerous faults and cracks striking the N30°E, N70°E and N120°E directions. Plutonic rocks are dominantly granites and accessorily gabbros and diorites meanwhile metamorphic rocks are dominantly gneisses associated to micaschists and quartzites. Oligocene to Present volcanic eruption (Marzoli et al., 2000; Njilah et al., 2004) made up of felsic and mafic lavas yielded through three major volcanic events: 31 to 28 Ma, 23 to 21 Ma and <1 Ma. Basically, the first sequence is effusive yielded aphyritic basaltic flows, meanwhile the second one is a mixture of effusive and explosive dynamisms on the one hand and basaltic and trachy-rhyolitic flows associated with rhyolitic tuffs on the other hand. The last sequence, solely explosive, generated tephras. Among these three sequences, the second one is characterized by porphyritic basaltic flows which are the host to ultramafic xenoliths. In general, the volcanic products are constituted of basanites, picrobasalts, hawaites, mugearites, benomorites, ignimbrites, trachy-andesites and trachy-basalts (Lissom, 1991; Nana, 1991, 2001; Njilah, 1991; Lee et al., 1996; Marzoli et al., 1999; Asaah et al., 2014; Aziwo, 2015; Chenyi, 2015; Tedonkenfack, 2016; Chenyi et al., 2017; Wotchoko et al., 2017). Ultramafic xenoliths from Ibal-Oku sector are mainly pyroxenitic (Tedonkenfack, 2016; Tedonkenfack et al., 2019), unlike other CVL localities (Temdjim et al., 2004; Wandji et al., 2009; Nkouandou & Temdjim, 2011; Temdjim, 2012; Aziwo, 2015; Tamen et al., 2015). Pyroxenites are worldwide described in veined-peridotites massifs and as peridotite-associated xenoliths in Sierra Nevada (Ghent et al., 1980; Ducea, 2002; Lee et al., 2006), Hannuoba (Xu, 2002; Liu et al., 2005), Hawaii (Frey, 1980; Sen & Leeman, 1991), Rio Puerco (Porreca et al., 2006), Kimberley (Hills & Haggerty, 1989; Taylor & Neal, 1989; Schmickler et al., 2004), www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 82 Published by SCHOLINK INC. Patagonia (Laurora et al., 2001; Dantas, 2007) etc... Along the CVL, the pyroxenites so far studied are websterites, olivine-websterites, ortho-and clinopyroxenites (Caldeira et Munha, 2002, 2007; Wandji et al., 2009; Matsukage et Oya, 2010; Aziwo, 2015; Tamen et al., 2015; Tedonkenfack, 2016; Tedonkenfack et al., 2019). Basically, on textural point of view, theses pyroxenites display cumulative derivation (Caldeira et Munha, 2002, 2007; Wandji et al., 2009; Matsukage et Oya, 2010; Aziwo, 2015). Petrologically, we intend in this paper to characterize the SCLM of the Ibal-Oku area. Figure 1. Geological Map of the Study Area Note. The inset on the left shows the position of the Oku Volcanic Group along the Cameroon Volcanic Line. The volcanic rocks cut through basement rocks of Precambrian age (Asaah et al., 2015, modified). 2. Method Mineral compositions were determined on 10 samples (01 for basaltic host lavas and 09 for ultramafic xenoliths) using SEM-EDS (Scanning Electron Microscope-Energy Dispersive Spectrometry) method, follow the general standard conditions. Analyses were carried out in the laboratory of experimental petrology from institute of geological sciences (Poland). For major, trace and rare earth geochemistry, ten samples were selected. The analyses were carried out in the laboratory ALS minerals of Vancouver (Canada). Major elements were analyzed through the ICP-AES method meanwhile trace and rare earth elements were analyzed thanks to ICP-MS. Detection limits are low: 0.01 wt. % for major elements, 0.01 to 20 ppm for trace elements and 0.01 to 0.5 ppm for rare earth elements. The lost on ignition are also low (less than 0.5 wt. %). www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 83 Published by SCHOLINK INC. 3. Result 3.1 Petrography 3.1.1 Host Basalt The mantle xenolith host lavas are porphyritic basalts displaying olivine and pyroxene phenocrysts. A few olivine (Ol) and pyroxene, both clinopyroxene (Cpx) and orthopyroxene (Opx) however constitute with spinel (Spl), mantle xenocrysts with oxydated and spongious rims. Olivine grains are automorphic to sub-automorphic and vary from 0.05 to 2.5 mm in size. They sometimes enclose oxyde crystals. Cpx grains are also automorphic and vary from 0.04 to 2.3 mm in size. Their crystals are usually zoned, poikiilitic and enclose small oxyde, plagioclase and apatite grains. Plagioclase crystals are automorphic to xenomorphic. The size varies from 0.05 to 0.3 mm. Xenomorphic crystals are usually enclose in Cpx. Oxyde grains are sub-automorphic to xenomorphic. The grain size varies from 0.01 to 0.1 mm and they are sometimes zoned. Apatite grains are automorphic, ranging from 0.01 to 0.1 mm in size. 3.1.2 Ultramafic Xenoliths Twenty-six ultramafic xenolith (5-9 cm) were selected for petrography. Their modal composition, determined by point counting and projected onto the Ol-Opx-Cpx triangular diagram (Figure 2) discriminates them as peridotites and pyroxenites. Peridotites are made up of wehrlites (T8), lherzolites (OKU11, OKU12, OKU13, OKU20, T9 and T10) and harzburgites (OKU17 and OKU18). Pyroxenites are made up of olivine-websterites (OKU6, T3, T4 and T7), websterites (OKU38B, T1, T2, T5 and T6), clinopyroxenites (OKU1, OKU2, OKU3, OKU5, OKU7, OKU10 and OKU38A) and olivine-clinopyroxenite (OKU4). Figure 2. Nomenclature of the Ibal-Oku Ultramafic Rocks (LeMaitre, 2002) www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 84 Published by SCHOLINK INC. 3.1.2.1 Peridotites Lherzolites display porphyroclastic and secondary protogranular textures, and enclose 50 to 81.72 vol.% of olivine, 7.78 to 23.6 vol.% of clinopyroxene, 8 to 26.51 vol.% of orthopyroxene, 0 to 4.90 vol.% of spinel, 0 to 0.28 vol.% of biotite and 0 to 1.39 vol.% of feldspar. Crystals span a wide range of dimension and are in equilibrium, thus showing franc borders. Nevertheless, they are spongy-textured when in contact with intraxenolitic melt veinlets. Olivine crystals are the largest in size as they range from 0.1 to 6 mm. They are mostly xenomorphic and subsidiarily sub-automorphic. Olivine crystals from protogranular rocks display no sign of internal deformation on the contrary of porphyroblastic rock ones which often exhibit kink-bands. Crystals often develop polygonal or triple junction (Figure 3A). Similar to other mineral phases, some crystals enclose fluide inclusions (Figure 3B). Clinopyroxene crystals also are auto- to xenomorphic, ranging from 0.1 to 5 mm. A few of them are poikilitic and enclose small spinel grains. Orthopyroxene crystals are auto- to xenomorphic, often rounded and interstitial and ranging in dimension between 0.05 and 3 mm. They enclose small rounded spinel grains. Spinel crystals (0.05-1 mm) are most often anhedral and exhibit several habits: crystal in contact with melt veinlets are compositionally textured, with brown core and thick-oxidized spongy rims meanwhile the others are either dark. Moreover, these spinel crystals are string beans-textured or mechanically dispersed, thus interstitial or included in other mineral phases. Biotite crystals (0.1-0.5 mm) are automorphic with good longitudinal cleavages (Figure 3C). Grains are in interstice between all the other mineral phases. Feldspar crystals are the smallest crystals (0.05-0.1 mm). They are automorphic to xenomorphic and are either interstice or included in the other mineral phases (Figure 3D). Wehrlites are porphyroblastic and made up of 77.74 vol.% of olivine, 16.26 vol.% of clinopyroxene, 3.5 vol.% of orthopyroxene and 2.5 vol.% of spinel. Olivine and clinopyroxene have coarse grains than orthopyroxene and spinel. The latter is often included in the silicates phases or form strings along the other mineral borders. Olivine crystals (up to 5 mm in size) are often enclose the three other minerals. On the contrary, it is never found as inclusion. Its borders are either curvy or rectilinear and franc unless when in contact with glass veinlets or spongious mineral phases (Figure 3E). Cpx have similar borders and its crystals are sub- to anhedral and exsolution-free. It displays spongy borders along the contact with glass veinlets and a few crystals are poikilitic. Opx exhibit similar habits with Cpx, but is at most 1 mm in size, thus found sometimes as interstitial mineral, as well as spinel grains which dimensions are comparable. Wehrlite spinel habits follow that of lherzolites and harzburgites from every point of view. However, when they are included in olivine crystal, spinel develop radial cracks in the host (Figure 3F). Glass veinlets radiate along intracrystalline cracks or percolate along grain boundaries, thus inducing spongy-borders. Harzburgites display porphyroclastic and secondary protogranular textures, and enclose 73.68 to 81.72 vol.% of olivine, 13.02 to 22.97 vol.% of orthopyroxene, 2.49 to 2.51 vol.% of clinopyroxene and 0.84 to 2.77 vol.% of spinel. Olivine crystals are the largest in size as they range from 0.1 to 5 mm. They are www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 85 Published by SCHOLINK INC. xenomorphic to sub-automorphic. Similar to lherzolite olivine porphyroblasts, porphyroblastic olivine often exhibit kink-bands (Figure 3G). Orthopyroxene crystals vary from 0.1 to 4 mm in size. A few of them are poikilitic and enclose small clinopyroxene grains. They are sub-automorphic. Clinopyroxene crystals vary from 0.01 to 1 mm in size. They are xenomorphic to sub-automorphic. A few of them are also poikilitic and enclose small orthopyroxene and spinel grains. Spinel crystals vary from 0.1 to 3 mm in size. They are xenomorphic to sub-automorphic. In contact with glass, they usually exhibit spongious borders (Figure 3H). 3.1.2.2 Pyroxenites Olivine-websterites and websterites exhibit cumulative texture. They differ mainly in their mineral modal proportions and in the presence of calcite and apatite in websterites. In this light, Ol-websterites display compositions in the frame of 40.13 to 65.65 vol.% of Cpx, 23.27 to 46.37 vol.% of Opx, 9.5 to 14.63 vol.% of Ol and 0 to 1.11 vol.% of feldspars, meanwhile websterites enclose 71.95 to 86.84 vol.% of Cpx, 12.16 to 24 vol.% of Opx, 0.1 to 4 vol.% of Ol, and <1 vol.% of apatite and calcite (~0.4 vol.% each). Porphyroblasts of the three mineral phases are sub-automorphic and comparable in size (2 to 5 mm across). Some Cpx porphyroblasts exsolve Opx as lamellae along their cleavages and/or enclose Opx microcrysts forming string grains. Besides, a few Cpx crystals are poikilitic and enclose small rounded spinel grains and fine orthopyroxenes exsolution lamellae (Figure 3I). Opx porphyroblasts on their own show Cpx lamellae and needle-like exsolutions often accompanied by randomly distributed microcrysts of the same nature. Their neoblasts are sub- to circular and aligned along Opx-Cpx porphyroblast boundaries. Olivine crystals are sometimes iddingsitized. Apatite (0.39 to 0.52 mm) and calcite (0.52 mm) are the smaller crystals and they are most often anhedral and enclose in the websterite clinopyroxene crystals (Figure 3J). Host basaltic melt veins sometimes infiltrate the xenoliths. Feldspar crystals (0.01-0.1 mm) are automorphic to xenomorphic and are either interstice or included in the other mineral phases. Clinopyroxenites and olivine-clinopyroxenites differ mainly in their mineral modal proportions and the absence of orthopyroxene in olivine-clinopyroxenites. Clinopyroxenites enclose 89.47 to 99.44 vol.% of clinopyroxene, 0.56 to 7.55 vol.% of orthopyroxene, 1.21 to 2.49 vol.% of olivine and 1.11 vol.% of feldspar. Olivine-clinopyroxenites enclose 77.25 vol.% of clinopyroxene, 21.07 vol.% of olivine and 1.68 vol.% of feldspar. In both of them, Cpx are poikilitic and enclose Opx grains. Few clinopyroxene crystals exhibit spongious rims in with small plagioclase grains are present (Figure 3K). Feldspar, olivine and oxide crystals are interstitial between pyroxene grains or present in the mineral pocket (Figure 3L). They are porphyroclastic. However, few rocks exhibit cumulative texture. www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 86 Published by SCHOLINK INC. Figure 3. Photomicrographs of Ultramafic Xenoliths. (a) Polygonal Triple Junction between Ol Grains. (b) Fluid Inclusions in Ol. (c) Biotite Grain. (d) Plagioclase and Sanidine Grains. (e) Ol-Opx Interaction. (f) Inclusion of Spl Crystal. (g) Kink-Bands in Ol Crystals. (h) Spl with Spongeous Rims in Contact with Glass. (i) Opx Exsolution. (j) Inclusion of Cal Crystals. (k) Cpx with Spongeous Rims. (l) Opx Pocket 3.2 Mineral Chemistry 3.2.1 Host Lavas Olivine phenocrysts (Fo75.48-84.04) are always more forsteritic than microcrysts (Fo75.48-76.70). CaO and NiO content vary from 1455 to 2182 wt.% and 0.1 to 0.3 wt.%. respectively (Table 1). Olivine xenocrysts are relatively more forsteritic (Fo85.66) than those of the host lavas. CaO and NiO content are 1455 wt.% and 0.4 wt.%. respectively. Clinopyroxenes are calcic and made up of diopside (Wo45.07-48.57En39.16-43.43Fs10.82-13.42; Mg#: 0.75-0.80) and augite (Wo43.30-44.42En39.77-44.92Fs10.66-16.06; Mg#: 0.71-0.81). Al, Cr, Ca, Na and Ti content vary from 0.15 to 0.39 apfu, 0.01 to 0.02 apfu, 0.80 to 0.87 apfu, 0.04 to 0.07 apfu and 0.05 to 0.10 apfu respectively (Table 3). Feldspars are plagioclases. They are made up of labradorite (An50.13-62.20Ab36.02-47.56Or1.16-2.32). Fe 2+ content varies from 0.03 to 0.04 apfu (Table 5). www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 87 Published by SCHOLINK INC. 3.2.2 Ultramafic Xenoliths 3.2.2.1 Peridotites Olivine Fo varies from 86 to 90 (Table 1; Figure 4A). These values are positively correlated with coexisting pyroxene Mg#. NiO and Ca content are 0.03 wt.% and 727-1455 wt.% respectively. Orthopyroxenes are enstatite (En83.15-87.77Fs12.23-16.85). Mg# values ranging from 0.83 to 0.92 (Table 2; Figure 4C). Al content varies from 0.12 to 0.27 apfu and are negatively correlated with Mg# values. Cr content varies from 0.004 to 0.022 apfu. On contrary to Al content, Cr content are positively correlated with Mg# values. Clinopyroxenes are calcic and made up of augite (Wo35.52-43.35En49.39-60.25Fs5.49-10.59). Mg# values vary from 0.84 to 0.93 (Table 3; Figure 4D). Al content varies from 0.23 to 0.37 apfu and are negatively correlated with Mg# values. Cr content varies from 0.007 to 0.038 apfu and are positively correlated with Mg# values. Ca content varies from 0.63 to 0.85 apfu. Na content varies from 0.06 to 0.15 apfu and are positively correlated with Mg# values and Al content. Ti content varies from 0.007 to 0.030 apfu. Spinels are aluminous (Al2O3: 46.10-60.70 wt.%). Cr# (Cr#=Cr/Cr+Al) and Mg# (Mg#=Mg/Mg+Fe) vary from 0.10 to 0.23 and 0.67 to 0.71, respectively (Table 4; Figure 4B). Fe 2+ content varies from 0.15 to 0.27 apfu. Ti content varies from 0.001 to 0.016 apfu. Micas are biotite with Fe# (Fe/Fe+Mg) ranging from 0.52 to 0.76 (Table 4; Figure 4E-F). Si, Ti and Al content vary from 6.27 to 7.99 apfu, 0.04 to 0.16 apfu and 1.01 to 1.81 apfu respectively. Feldspars are sanidine (Or35.64-45.04Ab51.13-56.98An3.32-7.60) and andesine-labradorite (An30.41-55.28Ab42.99-64.49Or1.73-5.09). Fe 2+ content varies from 0.02 to 0.04 apfu (Table 5). 3.2.2.2 Pyroxenites Olivine Fo vary from 85 to 87 (Table 1; Figure 4A). NiO and Ca content are 0.03 wt.% and 727-2182 wt.% respectively. Orthopyroxenes are enstatite (En83.15-87.77Fs12.23-16.85). Mg# values vary from 0.85 to 0.88 (Table 2; Figure 4C). Al, Cr, Ca, Na and Ti content vary from 0.15 to 0.39 apfu, 0.01 to 0.02 apfu, 0.80 to 0.87 apfu, 0.04 to 0.07 apfu and 0.05 to 0.10 apfu, respectively. Clinopyroxenes are calcic and made up of augite (Wo35.52-43.35En49.39-60.25Fs5.49-10.59; Mg#: 0.83-0,87; Table 3; Figure 4D). Al content varies from 0.23 to 0.37 apfu. On contrary, Cr content varies from 0.007 to 0.038 apfu. Ca content varies from 0.63 to 0.72 apfu. Na content varies from 0.06 to 0.09 apfu. Ti content varies from 0.007 to 0.030 apfu. Feldspars are andesine-labradorite (An30.41-55.8Ab42.99-64.49Or1.73-5.09). Fe 2+ content varies from 0.02 to 0.04 apfu (Table 5). www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 88 Published by SCHOLINK INC. Figure 4. Variation Diagram of Mineral Analyses. (a) Relationship between NiO and Fo[%] Content in Olivine. (b) Relationship between Cr# and Mg# in Spinel. (c) Relationship between Al (apfu) and Mg# in Orthopyroxene. (d) Relationship between Al (apfu) and Mg# in Clinopyroxene. (e) and (f) Relationships between Fe# and Si (apfu) and Al (apfu) in Biotite www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 89 Published by SCHOLINK INC. Table 1. Selected Olivine Analyses Types Lher Lher Lher Harz Harz Clin Ol-clin Ol-clin Ol-clin Basalt Basalt OKU11 OKU11 OKU12 OKU17 OKU18 OKU38A OKU4 OKU4 OKU4 OKU39 OKU39 1 2 3 4 5 6 7 8 9 10 11 SiO2 40.2 39.9 40 40.1 40.6 39.4 39.3 39.5 39.4 39.4 39 FeO 12.6 12.6 12.5 9.5 9.1 14.4 14.2 13.7 13.8 15.7 15.8 NiO 0.3 0.3 0.3 0.3 0.3 0.2 0.3 0.3 0.3 0.3 0.2 MgO 46.7 47.1 47.1 49.7 50 45.9 46.1 46.3 46.3 44 44.6 CaO 0.2 0.1 0.1 0.1 0.1 0.2 0.1 0.2 0.3 0.2 0.3 Total 100 100 100 99.7 100.1 100.1 100 100 100.1 99.6 99.9 Si 4+ 0.9987 0.9919 0.9937 0.9855 0.9921 0.9872 0.9853 0.9879 0.9855 0.996 0.9862 Fe 2+ 0.2618 0.262 0.2597 0.1953 0.186 0.3017 0.2977 0.2865 0.2887 0.3319 0.3341 Mn 2+ 0 0 0 0.0042 0 - - - - - - Ni 2+ 0.006 0.006 0.006 0.0059 0.0059 0.004 0.0061 0.006 0.006 0.0061 0.0041 Mg 2+ 1.7295 1.7455 1.7443 1.8209 1.8214 1.7145 1.723 1.7262 1.7263 1.6581 1.6813 Ca 2+ 0.0053 0.0027 0.0027 0.0026 0.0026 0.0054 0.0027 0.0054 0.008 0.0054 0.0081 Total 3.0013 3.0081 3.0063 3.0145 3.0079 3.0128 3.0147 3.0121 3.0145 2.9976 3.0138 Fo% 86.8 86.9 87.0 90.1 90.7 85.0 85.2 85.7 85.6 83.0 83.4 Ca (ppm) 1455 727 727 727 727 1455 727 1455 2182 1455 2182 Table 2. Selected Orthopyroxene Analyses Types Lher Lher Harz Harz Webs Ol-webs Clin Clin OKU11 OKU12 OKU17 OKU18 OKU38B OKU6 OKU38A OKU7 1 2 3 4 5 6 7 8 SiO2 52.4 52.8 53.6 54.1 52.7 53 53.4 53.2 TiO2 0.4 0.4 0.2 0.2 0.4 0.3 0.3 0.4 Al2O3 6.3 6.2 5.4 5 6.1 5.9 5.4 4.8 Cr2O3 0.5 0.4 0.7 0.8 - 0.3 - 0.3 FeO 7.8 8.2 6.2 5.7 9.4 8.4 8.9 9.1 MnO - - - - - 0.2 - - MgO 31.1 30.7 32.6 32.9 29.9 30.4 30.4 30.5 CaO 1.5 1.4 1.3 1.4 1.5 1.5 1.6 1.6 Total 100 100.1 100 100.1 100 100 100 99.9 Si +4 1.7442 1.7575 1.7842 1.8008 1.7542 1.7642 1.871 1.7709 Ti +4 0.01 0.01 0.005 0.005 0.01 0.0075 0.008 0.01 Al +3 0.1854 0.1824 0.1589 0.1471 0.1795 0.1736 0.223 0.1412 www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 90 Published by SCHOLINK INC. Cr +3 0.0099 0.0079 0.0138 0.0158 - 0.0059 - 0.0059 Fe +2 0.1086 0.1141 0.0863 0.0793 0.1308 0.1169 0.261 0.1267 Mn +2 - - - - - 0.0028 - - Mg +2 0.7716 0.7617 0.8088 0.8163 0.7418 0.7542 1.588 0.7567 Ca +2 0.0267 0.025 0.0232 0.025 0.0267 0.0267 0.06 0.0285 Total 2.8564 2.8587 2.8802 2.8893 2.8431 2.852 4.0099 2.8399 Mg# 0.8767 0.8697 0.9036 0.9114 0.8501 0.8658 0.8589 0.8566 Table 3. Selected Clinopyroxene Analyses Types Lher Lher Harz Harz Ol-webs Clin Clin Ol-clin Basalt Basalt OKU11 OKU12 OKU17 OKU18 OKU6 OKU7 OKU38A OKU4 OKU39 OKU 39 1 2 3 4 5 6 7 8 9 10 SiO2 50.2 50.2 51.6 51.8 51 51.6 51.3 50.8 48.1 48.5 TiO2 0.9 0.9 0.4 0.4 0.8 0.7 0.5 0.9 1.8 1.8 Al2O3 7.7 7.8 6.5 6.3 7.1 5.9 6.7 6.4 7 6.5 Cr2O3 0.7 0.6 1.1 1.2 0.4 0.3 0.3 0.3 - 0.8 FeO 5.4 4.7 3.6 3.3 4.9 6 5.9 4.7 7.8 6.3 MnO - 0.3 - - - - - 0.3 - - MgO 16.8 16.8 17.5 17.8 17.1 18 17.8 17.6 12.9 14.9 CaO 17.3 17.8 18.2 18.1 17.6 16.4 16.3 19.1 21.8 20.5 Na2O 1.1 1 1.2 1.1 1 1 1.1 - 0.6 0.6 Total 100.1 100.1 100.1 100 99.9 99.9 99.9 100.1 100 99.9 Si 4+ 1.8215 1.8197 1.861 1.8665 1.8473 1.8715 1.8592 1.8416 1.7928 1.7944 Ti 4+ 0.0246 0.0245 0.0108 0.0108 0.0218 0.0191 0.0136 0.0245 0.0505 0.0501 Al 3+ 0.3293 0.3332 0.2763 0.2675 0.3031 0.2522 0.2862 0.2734 0.3075 0.2834 Cr 3+ 0.0201 0.0172 0.0314 0.0342 0.0115 0.0086 0.0086 0.0086 0 0.0234 Fe 2+ 0.1639 0.1425 0.1086 0.0994 0.1484 0.182 0.1788 0.1425 0.2431 0.1949 Mn 2+ - 0.0092 - - - - - 0.0092 - - Mg 2+ 0.9087 0.9078 0.9409 0.9561 0.9234 0.9732 0.9617 0.9511 0.7168 0.8218 Ca 2+ 0.6726 0.6913 0.7033 0.6988 0.6831 0.6373 0.633 0.7419 0.8706 0.8126 Na + 0.0774 0.0703 0.0839 0.0768 0.0702 0.0703 0.0773 0 0.0434 0.043 Total 4.018 4.0157 4.0162 4.0102 4.0087 4.0142 4.0184 3.9929 4.0247 4.0237 Mg# 0.8472 0.8643 0.8965 0.9058 0.8615 0.8425 0.8432 0.8697 0.7467 0.8083 www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 91 Published by SCHOLINK INC. Table 4. Selected Spinel and Micas Analyses Spinel Micas Types Lher Lher Harz Harz Harz Lher Lher Lher Lher OKU11 OKU12 OKU17 OKU18 OKU18 OKU12 OKU12 OKU12 OKU12 1 2 3 4 5 6 7 8 9 SiO2 - - - - - 58.7 54.5 54.4 41.7 TiO2 0.6 0.6 0.3 0.4 0.3 - 0.4 0.4 1.4 Al2O3 53.1 54.5 50.2 46.6 46.5 6.9 7.7 7.4 10.2 Cr2O3 11.1 9.4 16.3 20.4 20.6 - - - 0.8 FeO 16.1 15.7 12.5 12.3 12.2 19.6 23.4 24.1 35.3 NiO - - 0.3 - - - - 0.5 - MgO 19 19.7 20.4 20.3 20.4 8.9 7.9 7.1 6.2 CaO - - - - - 0.7 0.6 0.6 0.7 K2O - - - - - 5.3 5.4 5.4 3.8 Total 99.9 99.9 100 100 100 100.1 99.9 99.9 100.1 Si 4+ - - - - - 7.904 7.558 7.589 6.265 Ti +4 0.012 0.012 0.006 0.008 0.006 - 0.042 0.042 0.158 Al +3 1.653 1.681 1.565 1.472 1.469 1.095 1.258 1.217 1.806 Cr +3 0.232 0.195 0.341 0.432 0.437 - - - 0.095 Fe +2 0.356 0.344 0.277 0.276 0.273 2.207 2.714 2.811 4.435 Ni +2 - - 0.006 - - - - 0.056 - Mg +2 0.748 0.769 0.805 0.811 0.815 1.786 1.633 1.476 1.389 Ca 2+ - - - - - 0.101 0.089 0.09 0.113 K + - - - - - 0.91 0.955 0.961 0.728 Total 3 3 3 3 3 14.004 14.249 14.242 14.99 Fe +3 calc 0.092 0.101 0.082 0.079 0.083 - - - - Fe +2 calc 0.264 0.243 0.195 0.197 0.191 - - - - Mg/(Mg+Fe 2+ ) 0.739 0.76 0.805 0.805 0.81 0.447 0.376 0.344 0.238 Mg/(Mg+Fetot) 0.678 0.691 0.744 0.746 0.749 - - - - Cr# 0.123 0.104 0.179 0.227 0.229 - - - - Fe# - - - - - 0.553 0.624 0.656 0.762 www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 92 Published by SCHOLINK INC. Table 5. Selected Feldspar Analyses Types Lher Ol-webs Clin Ol-clin Basalt OKU12 OKU6 OKU38A OKU4 OKU39 1 2 3 4 5 6 7 8 9 10 11 12 SiO2 57.5 63.8 64.5 57.7 57.3 59 57.6 52.9 55.8 51.7 54.3 51.3 TiO2 - 0.5 0.5 0.6 0.3 0.3 - - - - - - Al2O3 26.9 20.7 19.9 25.7 26.7 25.5 26.7 29.6 27.8 30.6 28.6 29.4 FeO 0.8 0.6 0.5 0.8 0.7 0.4 0.4 0.9 0.7 0.9 1 - CaO 7.6 1.6 0.8 7.4 7.9 6.5 7.8 11.4 8.8 12.5 10.3 16.7 Na2O 6.8 6.6 5.9 7.1 7 7.4 6.8 4.9 6.4 4 5.4 0.6 K2O 0.5 6.3 7.9 0.7 0.4 0.8 0.7 0.3 0.5 0.3 0.4 0.2 Total 100.1 100.1 100 100 100.3 99.9 100 100 100 100 100 98.2 Si +4 2.58 2.874 2.916 2.598 2.57 2.644 2.587 2.404 2.518 2.354 2.461 2.37 Ti +4 - 0.017 0.017 0.02 0.01 0.01 - - - - - - Al +3 1.423 1.099 1.06 1.364 1.412 1.347 1.413 1.585 1.478 1.642 1.528 1.601 Fe +2 0.03 0.023 0.019 0.03 0.026 0.015 0.015 0.034 0.026 0.034 0.038 - Ca +2 0.365 0.077 0.039 0.357 0.38 0.312 0.375 0.555 0.425 0.61 0.5 0.827 Na + 0.592 0.576 0.517 0.62 0.609 0.643 0.592 0.432 0.56 0.353 0.474 0.054 K + 0.029 0.362 0.456 0.04 0.023 0.046 0.04 0.017 0.029 0.017 0.023 0.012 Total 5.019 5.029 5.023 5.03 5.03 5.017 5.023 5.028 5.037 5.01 5.024 4.863 An (%) 37 8 4 35 38 31 37 55 42 62 50 93 Ab (%) 60 56 51 61 60 64 59 43 55 36 48 6 Or (%) 3 36 45 4 2 5 4 2 3 2 2 1 3.3 Geochemistry 3.3.1 Major Elements Major elements ranges as shown by Table 6 portray the broad ultramafic rocks suite described here. MgO varies thus widely between 15.85 and 40.5 wt. %. The variation is however reasonable in each of the petrographic type: 29 to 40.5 wt. % in peridotites, 15.85 to 26.6 wt. % in pyroxenites. Although peridotites display the highest deviation, it should be noted that one sample show an uncommon (29 wt. %) content for peridotites. The mg# varies between 82.7 and 89.9 for peridotites and 80.1 to 83.6 for pyroxenites. These peridotite mg# are rather low when compared to values so far recorded along the CVL. They however reveal their iron-rich nature, similarly to Fe-rich lherzolites and wehrlites from Tok, SE Siberia (Ionov et al., 2005) or from HorníBory, Bohemian Massif (Ackerman et al., 2009). MgO correlates variably with the other major elements. Figure 5 shows that, Refractory Lithophiles Elements (RLE) Al2O3, CaO and Na2O and to a lesser extend SiO2 display a negative correlation with www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 93 Published by SCHOLINK INC. MgO. Contrarily, FeOt and K2O exhibit a rough positive trend. Al2O3 and CaO alike MgO display a wide range of contents (2.25-7.55 wt. % and 1.57-16.5 wt. % respectively). Peridotites show the smallest contents. Two significant observations arise from the behavior of these two RLE: (i) CaO portrays a horizontal rather than the Al2O3 negative trend, and (ii) Al2O3 contents are typical of fertile lherzolites meanwhile Cao contents are close (2.28 wt. %) or even similar (1.57-1.89 wt. %) to harzburgites compositions (Palme and O’Neill, 2014). P2O5and K2O contents range in the order of almost two magnitude (0.03-0.13 wt. % and 0.03-0.16 wt. % respectively), characterized by the greatest scatter in the MgO variation diagram. Notwithstanding the broad suite contents, peridotites display PM comparable contents, except for FeOt, P2O5 and K2O which are slightly enriched. Figure 5. Variation Diagram of Selected Oxides vs MgO. Primordial Mantle (PM) Composition after McDonough and Sun (1995) www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 94 Published by SCHOLINK INC. 3.3.2 Trace and Rare Earth Elements Table 6 shows that over the rocks suite, trace elements display extensive concentrations and often, pyroxenites are richer: Cr (740-2340 ppm in peridotites vs 1380-2640 ppm in pyroxenites) and V (60-110 ppm in peridotites vs 134-240 ppm in pyroxenites). Rb however has similar values in both petrographic rock types. Figure 6 which portrays variation of MgO vs a selected set of trace elements reveals that V is the sole element perfectly correlated to MgO. Cr, Zr, Sr and Ba despite their extensive concentrations are either vertically aligned (websterites) or scattered (olivine-websterites), likely as a result of the close range mainly of pyroxenites MgO contents. Figure 6. Variation Diagram of Selected Traces Elements vs MgO Chondrite-normalized spidergram yields mirroring spectra for the two petrographic facies (Figure 7a), though sections of overlapping or detachment may exist (Figure 7b). Rb, K and P depict severe negative anomalies of a factor of 45, 50 and 300 respectively, meanwhile Ba exhibits a rough positive anomaly of a factor of 4.5. Chondrite-normalized diagram (Figure 7c and 7d) show an overall LREE enrichment relative to HREE. The (La/Lu)n ratios vary between 4.2 and 10 for peridotites and between 2.9 and 9.52 for pyroxenites. It is obvious to note that the pyroxenites LREE enrichment over HREE is more spread. On the other hand, all the Oku rocks are REE enriched with respect to chondrite but its order of magnitude is far beyond two units (35). The pyroxenites spectra have a more regular pattern than that of peridotites and moreover, they all have higher contents. Some of the peridotites display rough Ce and Tm positive anomalies of a factor of 1.7 and 2 respectively. www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 95 Published by SCHOLINK INC. Figure 7. Chondrite-normalized Diagrams for the Oku Ultramafic Rocks. (a) and (b) Curves and Redrawn Shaded Fields for the Same Rocks with the Traces Elements. (c) and (d) Curves and Redrawn Shaded Fields for the Same Rocks with the Rare Earth Elements. Normalization Values after Sun and McDonough (1989) Table 6. Bulkrock Major, Trace and REE Compositions of the Oku Mantle Xenoliths Peridotites Pyroxenites Wehrlite Lherzolites Olivine-websterites Websterites Samples T8 T9 T10 T3 T4 T7 T1 T2 T5 T6 SiO2 42.1 48.4 40 46.3 49.9 43.9 48.7 50.1 49.8 47.6 TiO2 0.25 0.36 0.39 0.56 0.62 0.89 0.69 0.78 0.79 1.09 Al2O3 2.25 4.8 3.74 4.17 6.05 4.33 6.15 6.37 6.75 7.55 Cr2O3 0.3 0.1 0.32 0.19 0.36 0.19 0.3 0.35 0.24 0.25 a FeOT 10.65 14.15 15.05 12.9 9.51 12.25 9.1 8.09 8.49 9.21 MnO 0.14 0.21 0.21 0.17 0.16 0.16 0.16 0.14 0.15 0.16 MgO 40.5 29 35.5 26.6 20.7 26.2 17.5 17.65 16.65 15.85 CaO 1.57 1.89 2.28 7.91 12.3 9.76 13.85 15.3 16.5 15.05 Na2O 0.16 0.18 0.16 0.39 0.67 0.47 0.84 0.79 0.82 0.82 K2O 0.09 0.07 0.06 0.08 0.03 0.16 0.06 0.05 0.06 0.1 P2O5 0.03 0.04 0.07 0.05 0.04 0.13 0.03 0.03 0.05 0.11 b LOI 0.7 0.44 1.63 1.05 0.98 1.25 0.72 0.9 1.07 1.47 Total 98.74 99.64 99.41 100.37 101.32 99.69 98.1 100.56 101.37 99.26 Mg# 89.9 82.7 84.6 82.8 83.6 83.3 81.8 83.6 82.1 80.1 Nb 2.4 1.7 2.4 4 2.1 9.7 2.1 2.3 3.2 6.9 Zr 12 13 17 25 20 43 28 31 29 48 Sr 30.5 15 11.3 60.4 32 122 52.5 66.6 60.8 101 Ga 3.4 7 6.1 6.6 8.3 7.1 8.6 8.6 8.6 10.8 Cr 2180 740 2340 1440 2640 1380 2200 2580 1730 1870 V 60 110 100 139 212 145 240 225 254 260 Ba 29.2 27.1 34.6 44.6 15.6 95.7 38.1 21.7 107 66.4 Rb 1.9 2.9 3 2.1 1.2 2.3 1.9 1.9 2 1.4 www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 96 Published by SCHOLINK INC. Cs 0.02 0.05 0.06 0.1 0.02 0.05 0.07 0.06 0.08 0.11 Y 2 1.8 3.8 6.3 7 8 9.3 8.7 9 12.8 Hf 0.3 0.4 0.6 0.8 0.8 1.2 0.9 1.1 1.1 1.7 Sn 1 1 1 1 1 1 1 1 1 3 Ta 0.1 0.1 0.1 0.2 0.1 0.5 0.1 0.1 0.2 0.4 Th 0.17 0.15 0.32 0.29 0.17 0.63 0.2 0.19 0.25 0.5 U 0.05 0.06 0.1 0.11 0.07 0.18 0.1 0.07 0.1 0.15 La 2.8 1.2 2.8 4.3 1.9 8 5.3 3.3 3.9 8.3 Ce 4.5 3.4 6.2 7.6 5.3 15.9 6.5 7.9 9.3 16.2 Pr 0.61 0.32 0.68 1.33 0.79 2.25 1.54 1.24 1.44 2.41 Nd 2.6 1.2 2.9 6.5 4.4 10.3 7.4 6.8 7.1 11.8 Sm 0.53 0.37 0.76 1.66 1.39 2.16 2.33 1.95 2.33 3.2 Eu 0.17 0.1 0.21 0.55 0.53 0.81 0.62 0.66 0.68 1.02 Gd 0.54 0.33 0.79 1.72 1.58 2.18 2.3 2.24 2.25 3.3 Tb 0.07 0.06 0.12 0.26 0.27 0.31 0.35 0.37 0.34 0.47 Dy 0.43 0.34 0.69 1.41 1.56 1.75 2.06 2 1.98 2.64 Ho 0.08 0.07 0.16 0.26 0.3 0.33 0.37 0.37 0.39 0.51 Er 0.18 0.18 0.38 0.64 0.73 0.75 0.99 0.87 0.97 1.22 Tm 0.04 0.05 0.06 0.09 0.11 0.1 0.12 0.14 0.11 0.17 Yb 0.24 0.18 0.35 0.49 0.58 0.59 0.73 0.68 0.63 0.89 Lu 0.03 0.03 0.05 0.07 0.07 0.09 0.1 0.1 0.11 0.12 Note. a FeOT: Fe total; b LOI: Loss On Ignition. 4. Discussions The Ibal-Oku ultramafic rocks described here are included in dismantled basaltic flows. A few of these xenoliths are veined by the host basalt meanwhile the outer contact is sometimes reactive, leading to the development of augitic clinopyroxene. Contrarily to the other ultramafic xenolith reservoirs along the CVL, pyroxenites are more represented than peridotites and although their textures are similar to the main ones recorded elsewhere in Cameroon, their petrology and iron-rich signature are specific features that request thorough considerations. 4.1 Petrographic Evolution 4.1.1 Origin of Peridotites Ultramafic xenolith sizes are very important. In fact, small size are problematic as far as their magmatic or mantellic origin is concerned. Magmatic xenoliths have either to do with a precocious crystallization from the host lava or with the phenomenon at the origin of the host magma itself meanwhile mantellic origin is fragment detached either from the source region or from the wall rocks along the magma’s route to the surface. Because the latter are accidentally sampled, not all depth intervals are necessarily represented in a xenolith population; nevertheless, their pressures and temperatures estimates provide some spatial context amongst samples within a xenolith population, which may perhaps be divisible according to their textures and/or compositions (Pearson et al., 2014). One of the discriminative features of the two origins is their texture, cumulative in the first case, metamorphic in the broad sense since they result from the combination of thermo-barometric and differential stress conditions for the www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 97 Published by SCHOLINK INC. second. Magmatic ultramafic xenoliths have been described along CVL (Caldeira & Munha, 2002; Ngounouno et al., 2006; Wandji et al., 2009; Matsukage & Oya, 2010) and they all fit in this distinctive cumulative signature. The Oku samples however display metamorphic textures and low whole rocks and silicate mg#. In the latter view, Ionov et al. (2005) define two types of lherzolite series: (i) a Lherzolite-Wehrlite series (L-W) characterized by low mg# [Mg/(Mg+Fe) at 0.84-0.89 in olivine, high modal olivine (66-84 vol.%) and Cpx (7-22 vol.%) substituting for Opx (0-12 vol.%) and for spinel and (ii) a Lherzolite-Harzburgite (L-H) series in which mg# are high (>0.89), with high Opx and representing melting residues partially metasomatized. The Ibal-Oku peridotites mainly plot in OSMA (Olivine Spinel Mantle Area) and LW fields (Figure 8-9), confirming their mantellic origin. Furthermore, the two samples plotting in the LW field exhibit Cr content of 2180 and 2340 ppm, far above critical value characteristic of mantle peridotites. Figure 8. Relationship between Fo[%] Content in Olivine and Cr-number in Spinel. OSMA (Olivine Spinel Mantle Area) Field from Arai (1994) Figure 9. Co-variation Plots of Modal Abundances of Cpx (a) and Opx (b) vs Ol of the Oku Peridotites. Lherzolite–Wehrlite (L-W) Series and Lherzolite–Harzburgite (L-H) Series Are after Ionov et al. (2005). Arrows Outline Inferred Trends for Transformation of Refractory L-H Series Rocks into L-W Series Rocks (Ionov et al., 2005) www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 98 Published by SCHOLINK INC. 4.1.2 Origin of Pyroxenites Pyroxenite origin and formation processes are challenging questions highly discuted. In this way, Dantas (2007) summarized the literature major formation processes into four modes: (i) oceanic crust fragments recycling (Dick & Sinton, 1979; Kornprobst et al., 1990), (ii) cumulates from early magmatic crystallization (Frey, 1980; Schiano et al., 2000; Puziewicz et al., 2011), (iii) fluid/melt and upper mantle peridotite interaction (Menzies, 1983; Navon & Stolper, 1987; Smith & Riter, 1997; Ackerman et al., 2009), and (iv) high pressure segregation of mafic silicate melts yielding a fluid that later on crystallizes pyroxenites (DeBari et Coleman, 1989; Downes, 2005). Along the CVL, several pyroxenites occurrences, mainly cumulative have been described (Caldeira & Munha, 2002; Wandji et al., 2009; Matsukage & Oya, 2010; Aziwo, 2015). The Ibal-Oku pyroxenites however display modal Cpx/Opx ratios in the range of 0.9 to 7.2, i.e., greater than 1, characteristic of mantle reactive pyroxenites (Murad & Shoji, 2007). Alike the Ksieginki (Poland) websterite (Puziewicz et al., 2011) and the Tok LW series, the Oku pyroxenites plot at the right of LW-LH line (Figure 9), close to the curve modelling the melt-host reaction parameters of 0.99 liq0 + 0.01 Opx fi 0.98 liqr+ 0.01782 Cpx + 0.00198 Ol (Eq. 1) after Ionov et al. (2005) and can indeed be considered as mantle metasomatic products from early magmatic crystallization, or cumulates. However, petrographic observations show that the majority of pyroxenite display cumulative texture. This characteristic means that they could also be cumulates from early magmatic crystallization. Figure 10. A Plot of Whole-Rock Mg# vs Modal Cpx/Opx (wt %) in Oku Peridotites Compared with Results of Numerical Modelling of Mg# Variations Produced by Interaction of a Refractory Peridotite (Mg#=0.91; Cpx/Opx=0.32) with Percolating Basaltic Liquids Involving Cpx-forming Reactions at Decreasing Melt Mass www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 99 Published by SCHOLINK INC. The modelling was done using the ―Plate Model‖ of Vernières et al. (1997) initially designed for trace-element applications and modified here for Mg–Fe modelling. Olivine/melt and inter-mineral Kd values for Mg and Fe were fixed for T=1,200 C and P=1.5 GPa from experimental calibrations (Brey & Köhler, 1990; Ulmer, 1989). Furthermore, the olivine/melt Kd are adjusted as a function of melt composition. The initial peridotite composition (protolith) was obtained by averaging compositions of LH series rocks [with Mg# >0.90 to avoid samples possibly affected by small degrees of melt–rock reaction (Ionov et al., 2005)]. Numerical experiments were performed with two extreme compositions for infiltrated melt: (1) a primitive, high-Mg# (0.76) liquid in equilibrium with the protolith and (2) an evolved, low Mg# (0.63) liquid similar to the host basalt. All modelling results obtained with the primitive melt composition plot in the shaded area. Modelling results for the evolved melt compositions are shown for R values (mass ratio of crystallised minerals to infiltrated melt) ranging from 0.02 to 0.3. Based on Eq. 1 in text and constant ƒ (residual melt fraction)=0.99, the melt-host reaction parameters range from [0.99 liq0+0.01 Opx fi 0.98 liqr+0.01782 Cpx+0.00198 Ol] for R=0.02 to [0.769 liq0+0.231 Opx fi 0.761 liqr+0.215 Cpx+0.023 Ol] for R=0.3. After Ionov et al. (2005). 4.2 Textural Evolution The Ibal-Oku wehrlites are protogranular, with as lherzolites few olivine crystals displaying straight boundaries that sometimes form triple junctions. Lherzolites and harzburgites are either secondary protogranular or porphyroclastic. Kink-bands are often observed on some olivine crystals. The typology of mantle rocks textures (Mercier et Nicolas, 1975; Coisy et Nicolas, 1978) reveal that xenoliths displaying protogranular textures derive from tectonically inactive mantle areas meanwhile porphyroclastic textures are typical of mantle active zones. As a consequence of the high deformation, a rock can experience a complete process of textural evolution leading to a secondary protogranular texture, characterized by mechanically dispersed spinel which may be included in the rock silicate mineral or form string-grains and/or atolls. Such a secondary protogranular texture thus portrays active mantle areas. The Oku SCLM is likely active, a phenomenon which in the exception of the Kumba SCLM (Teitchou et al., 2007) is almost general along the CVL. Deformation textures are known to indicate the presence of shear zones in the mantle, likely resulting from (i) the replay of large horizontal shear zones during oceanic opening, (ii) asthenospheric diapirism within the lithosphere (Coisy et Nicolas, 1978; Witt et Seck, 1987) or (iii) the mechanic response to lithosphere/asthenosphere fluxes coupling (Kennedy et al., 2002; Tikoff et al., 2004). Along the CVL where the crust in thin (36 km after Tokam et al., 2010) however, the basal lithospheric erosion by the asthenosphere seems to explain the origin of the mantle shearing (Elsheikh et al., 2014). In addition to protogranular and porphyroclastic textures in Oku, poikilitic spongy microtextures are sometimes superimposed. Such microtextures originate either from local melting through metasomatism prior to the sampling by the host magma or from melt/xenolith interaction during host magma ascent (Ionov et al., 1994; Qi et al., 1995; Carpenter et al., 2002). Poikilitic and spongy Cpx are often associated to festooned border spinel and vugs, but unlike the Dibi (Dautria & Girod, 1986), Kapsiki (Tamen et al., 2015), Wum (Aziwo, www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 100 Published by SCHOLINK INC. 2015) and Bafmeng xenoliths (Chenyi et al., 2017) feldspar (plagioclase and sanidine) are from basalt or products of basaltic melt crystallisation, which percolated in xenoliths. 4.3 Chemical and Geochemical Evolution Using the degree of partial melting (F) from the relation of Hellebrand et al. (2001; F=10×ln(Cr#)+24), we obtain 14 to 15 vol.% in lherzolites and 17 to 18 vol.% in harzburgites. The Ibal-Oku peridotites show high Al2O3 content (2.25 and 3.74 to 4.8 wt.% in wehrlites and lherzolites respectively), coupled with high Cpx modal contents (16.26 and 20.95 to 22 vol.% in wehrlites and lherzolites respectively) and lherzolite spinel Cr#, depicting a fertile mantle. Contrarily, CaO contents are relatively low (1.57-2.28 wt.%) and harzburgite spinel Cr#, characteristic of refractory rocks. This refractory character is also confirmed on the Al2O3-MgO-CaO triangular diagram (Figure 11) where the Oku rocks evolve from primordial mantle composition to the MgO enriched edge. Obviously, pyroxenites show an opposite trend, likely as a result of metasomatism. In this light it is worth recalling the modal composition of these rocks which include calcite and apatite. The portion of the mantle sampled at Ibal-Oku is strikingly veined by diversified pyroxenites. As we pointed out in a previous section, the origin of pyroxenites is highly debated. We have however, partially discarded the magmatic origin for our samples. The presence of numerous fluid inclusions in Opx and Cpx crystals together with the occurrence of calcite and apatite are strong arguments for mantle metasomatism. In fact, the presence of minerals such as biotite, apatite and calcite is characteristic of modal metasomatism (Pearson et al., 2003 and references there in). Along the CVL, phlogopite and pargasite on contrary to that last three mineral phases are usually discuted for modal metasomatism (Nana, 2001; Temdjim et al., 2004; Matsukage et Oya, 2010; Temdjim, 2012). The nature of the agents involved in the metasomatism is of chief importance and the contribution of mineral compositions (trace, REE and isotope) is paramount in the modelling of this phenomenon. In the mantle, melt and fluids circulating are of various signatures, ranging from silicic to carbonate-rich with associated CO2 and brines (Stagno & Frost, 2010; Stagno et al., 2013; Frezzotti & Touret, 2014). These fluids/melts enrich the mantle and modify chemical compositions, Cpx will react with carbonate to produce calcite (Ackerman et al., 2012). In some cases, minerals of the same nature as those present in the primary rock may be added through metasomatism, like known as ―stealth metasomatism‖ (O’Reilly & Griffin, 2012) which is difficult to identify but is likely accountant for the genesis of a certain number of pyroxenites. In other respects, the Oku xenoliths are rich in HFSE (Ti, Nb, Hf, Zr, Th, U and Ce), LILE (Rb, Ba and Sr) and LREE (Figure 7) likely significant of cryptic metasomatism as it is the case for Nunivak (Brown et al., 1980; Pearson et al., 2003), Kumba (Teitchou et al., 2007), Ataq (Al-Malabeh, 2009), Nyos (Temdjim, 2012) and Ngao Bilta (Temdjim et al., in press). www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 101 Published by SCHOLINK INC. Figure 11. Al2O3-MgO-CaO Diagram. Primordial Mantle (PM) Composition after McDonough and Sun (1995) Calcite and apatite represent up to 0.5 vol. % of some Ibal-Oku rocks. The carbon form prevailing in the mantle is depth and oxygen fugacity dependent. From the lithospheric mantle down to ca. 150 km in the asthenospheric mantle, carbon is oxidized and is present as CO2 in the lithospheric mantle and as carbonate either mineral or melt, depending on the thermal regime in the asthenosphere, between approximately 90 and 150 km. Beneath 150 km, the high redox state favours diamond formation and/or reduced C-H fluids if sufficient hydrogen available (Hammouda & Keshav, 2016). Carbonates and CO2-bearing minerals such as apatite (especially type A apatite which is believed to result from metasomatism by CO2- and H2O-rich fluids derived from a primitive mantle source region, O’Reilly & Griffin, 2000) are significant of patent metasomatism through carbonatitic agents. Moreover, carbonatitic fluids are able to modify the modal composition by adding of diopside and olivine through reactions such as: 2Mg2Si2O6+CaMg(CO3)2=CaMgSi2O6+2Mg2SiO4+2CO2, producing wehrlitic fronts or channels (Lustrino et al., 2016). This likely explains the origin of the wehrlites described in Ibal-Oku on the one hand and their generation at great depth (since the carbonate inclusions are in the crystalline state) on the other hand. Cpx crystallization directly from the metasomatic agent are also reported in mantle xenoliths from the Calatrava Volcanic District (Spain), the phenomenon occurring plausibly at greater depths in the presence of residual garnet, from peridotite or eclogite starting materials (Bianchini et al., 2010). The FeO contents of the Ibal-Oku lherzolites are high (14.15-15.05 wt. %) compared to (i) the other Oku xenoliths described either on the flank at Wum with a range of 9.24 to 10.8 wt. % (Aziwo, 2015) or at the foot at Nyos where they vary between 8.02 and 8.88 wt. % (Nana, 2001; Liu et al., 2017) on the one hand and (ii) many other areas along the CVL namely Kumba where they are comparable to the Nyos contents (8.66-8.66 wt. %, Asaah unpublished data), N’gaoundere (10.20-10.38 wt. %, Nkouandou et al., 2015), Kapsiki (8.09-13.25 wt. %, Tamen et al., 2015) on the other hand. Moreover, a lot of fluid inclusions are in mineral phases and biotite crystals (Fe#: 0.52-0.76) are present in peridotites. These unusual FeO contents are however comparable to that of the Fe-rich www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 102 Published by SCHOLINK INC. lherzolite-wehrlite xenoliths from Tok (Ionov et al., 2005) and likely result from Fe-enrichment. Various elements enrichments have been described in mantle rocks worldwide. Fe-improvement in particular can be achieved through either solid-state diffusion by Mg-Fe equilibration between mantle rocks and Fe-rich cumulus veins (Kempton, 1987; Abe et al. 2003) or exchange with percolating melts (Navon & Stolper, 1987; Kelemen et al., 1990, 1992; Takazawa et al., 1992; Nielson & Wilshire, 1993; Ionov et al., 2005; Ackerman et al., 2009, 2013). Mg-Fe solid-state equilibration of the Oku peridotites with their veining pyroxenites as prospective origin of Fe-enrichment is uncertain for the host rocks have FeO contents slightly higher than that of the pyroxenites, unless they originate from different depths, the equilibrating rocks actually missing or yet to be sampled. Melt-rocks interaction potentially fits well with Fe-enrichment as witnessed by comparable amounts of FeO in both the peridotites and their host basaltic lavas (12.96-14.99 wt. %, Asaah et al., 2015, 2019). In this case, post-entrainment modification as well as in situ long-term impregnation and equilibration can be evoked. Post-entrainment enrichments are often associated with textural modification such as spongy and sieve textures, reaction borders or compositional zoning on crystals (Shaw & Edgar, 1997; Carpenter et al., 2002; Wang et al., 2012), features almost absent in the Ibal-Oku samples. Thus, Fe-enhancement through melt percolation is more likely at the origin of high FeO contents. If so doing, it appears preoccupying that such a process is restricted to Ibal-Oku, giving the ubiquitous melt/mantle rock time and the physical contact intimacy beneath the CVL. All the xenoliths plot in silicate metasomatism field, which is also an indicator of interaction between xenoliths and silicate melt (Figure 12-13). Figure 12. La/Sm vs La Plot of the Oku Nodules. Also Included Are Data from the Kapsiki (Tamen et al., 2015) for Comparison. Field Boundaries after Ionov et al. (2002) www.scholink.org/ojs/index.php/ees Energy and Earth Science Vol. 3, No. 2, 2020 103 Published by SCHOLINK INC. Figure 13. Relationship between Ratio Ca/Al and Mg# in Clinopyroxene. Carbonatitic and Silicate Fields Are from Zong et Liu (2018) 5. Conclusion The Ibal-Oku SCLM is heterogenous and veined by pyroxenites. Major elements in general and Al2O3/CaO decoupling in particular are significant of mantle enrichment/depletion. Alike several sections of the mantle underlining the CVL, this sector is tectonically active and metasomatized. The metasomatism here, probably carbonatitic and silicate has acted cryptically, modally and likely stealthily. Hydrous (biotite) and anhydrous (apatite and calcite) metasomatic minerals are present, feature which together with the prevalence of pyroxenites on peridotites are specific of signatures of Oku SCLM that deserve further consideration. 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