UNIVERSITY OF THE PHILIPPINES

Master of Science in Geology

Florence Annette Cruspero Labis

Petrology and geochemistry of the ultramafic and mafic rocks in southern Palawan: Insights to magmatic
processes in the oceanic lithosphere

Thesis Adviser:
Betchaida D. Payot, Ph.D.
National Institute of Geological Sciences
University of the Philippines Diliman

Date of Submission
December 2019
Thesis Classification:
P
ABSTRACT

PETROLOGY AND GEOCHEMISTRY OF THE ULTRAMAFIC

AND MAFIC ROCKS IN SOUTHERN PALAWAN:

INSIGHTS TO MAGMATIC PROCESSES IN THE OCEANIC LITHOSPHERE

Melt-rock interactions are important rock-forming processes often observed in the

upper mantle which typically results to chemical refertilization in the peridotites. Peridotites

formed through this process are commonly observed in extensional settings, such as in rift

zones and spreading centers, but are less frequently documented in arc settings. In the

Philippines, one of the well-studied ophiolitic complexes is the Palawan Ophiolite. Previous

studies have identified two ophiolitic terranes in the island, a younger Eocene is assigned to
the ophiolitic rocks in central Palawan Ophiolite and a much older Cretaceous southern

Palawan Ophiolite. Earlier works classified Palawan Ophiolite as a SSZ type ophiolite.

However, much of the published information mainly focused on the ophiolitic rocks in

central Palawan and its southern counterpart remains to be examined. In this study, the

petrographic and geochemical characteristics of the ultramafic and mafic rocks of the

southern Palawan Ophiolite are investigated. The occurrence of plagioclase peridotite

gabbroic dike suite of the southern Palawan Ophiolite is being reported for the first time in

this work. The objective is to provide insights on the petrogenetic processes related to the

formation of the ultramafic and mafic rocks in southern Palawan.

The mantle section of the southern Palawan Ophiolite is composed of spinel

harzburgites, with minor dunites and plagioclase peridotites. The spinel harzburgites and

dunites generally exhibit porphyroclastic and protogranular textures which typify mantle

peridotites. These peridotites represent highly depleted mantle wedge materials characterized

ix
by high Cr# (=0.53-0.78) and low TiO2 (<0.02 wt.%) content in spinel, highly magnesian

olivine (Fo90-92) and low concentrations of Al2O3 and Cr2O3 in the pyroxenes. In addition,

clinopyroxene trace element concentrations of these harzburgites are significantly low in

MREE-HREE while the LREEs are slight enriched indicating mantle depletion and

metasomatism, respectively. Their calculated oxygen fugacities (fO2) are relatively high

[Δlog(fO2)FMQ = -1.75 to+2.2] consistent with suprasubduction zone peridotites formed

under oxidizing conditions. These petrological features further suggest that the spinel

harzburgites and dunites were formed after high degrees of partial melting (~30%) with

addition of subduction components (e.g. fluids and melts from the subducting slab) beneath

the forearc or main arc region.

Meanwhile, the plagioclase peridotites range from plagioclase wehrlites, lherzolites

and harzburgites. They show distinct petrographic evidence characterized by peculiar textures

composed of: (1) resorbed and corroded contacts between olivines and pyroxenes, (2)

anhedral plagioclases surrounded by interstitial clinopyroxene set in an olivine matrix. These

textures indicate late stage origin affected by melt-rock interaction processes. Their
geochemical compositions differ from those spinel harzburgites and dunites which are

characterized by a narrower range of Cr# (0.60-0.62), higher Fe 3+ and TiO2 (0.98-1.54 wt.%)

contents in spinel and lower Fo content (83-87) in olivine compared to the spinel harzburgites

and dunite. Clinopyroxenes in these peridotites also contain higher Al 2O3 and TiO2 contents

compared with the clinopyroxenes in residual spinel harzburgites. Clinopyroxenes and

orthopyroxenes in the plagioclase peridotites also exhibit higher trace element concentration

compared to the other peridotites. One notable sample of spinel harzburgite (sample PALB

05) also records similar signatures to that of the plagioclase peridotites. The petrological

characteristics of these peridotites suggest multi-stage processes which involve fractional

x
crystallization from a basaltic melt migrating through the upper mantle and its reaction with

the surrounding peridotite wall rock. The plagioclase peridotites and PALB-05 were

originally derived from the same highly depleted spinel harzburgites and subsequently

reacted with percolating MORB-like melts now preserved as the gabbroic intrusions. The

gabbroic intrusions (PALB-02, PALB-03 and PALF-04) are mainly identified as olivine

gabbros and troctolites which are characterized by irregular and ragged textures commonly

interpreted as dissolution textures evidence for melt-rock interaction. The crystallization

order of these gabbroic rocks suggests early crystallization of plagioclase before

clinopyroxene which is a characteristic of anhydrous MOR-derived melts. Moreover, the

anorthite content of plagioclase in the plagioclase peridotites (An71-75) and gabbros (An80-87)

also straddle the boundary between MOR and arc-related gabbros comparable to back-arc

basin gabbros. Furthermore, the plagioclase peridotites and olivine gabbros (PALB-03)

exhibit parallel middle to heavy REE further supporting their genetic relationship.

Petrographic and geochemical characterization reveal that the plagioclase peridotites

troctolite-olivine gabbro rock suites of the southern Palawan Ophiolite are products of the

interaction between highly depleted mantle peridotites and migrating MOR-derived melts

from higher pressures to the shallow mantle. The intrusion of olivine gabbro and troctolite

dikes with signatures comparable to back-arc basin rocks provides new constraints on the

origin of the Palawan Ophiolite.

 We therefore propose that the plagioclase peridotites were formed as the result of the

reaction between highly depleted mantle peridotites beneath an intraoceanic arc and

migrating BABB-like magmas during the incipient stages of back-arc rifting possibly related

to the back-arc spreading during Eocene in response to the subduction of proto-South China

Sea Basin (SCSB) beneath a proto-Cagayan arc.

xi
TABLE OF CONTENTS

Abstract ix List of Figures xiv List of Tables xvi Chapter 1: Introduction 1 1.1 Introduction 2 1.2 Statement of

the problem 5 1.3 Significance of the study 5 1.4 Objectives of the study 6 1.5 Scope and limitations 6 Chapter 2:

Literature review 7 2.1 Ophiolites 8 2.2 Plagioclase-bearing peridotites 12 2.3 Regional geology and tectonic setting

16 2.4 Models on the origin of Palawan Ophiolite 18 Chapter 3: Methodology 20 3.1 Geologic mapping and

sampling 21 3.2 Petrography 21 3.3 Mineral chemistry and trace elements 24 Chapter 4: Petrological

characteristics of the ultramafic and mafic rocks from the southern Palawan Ophiolite 28 4.1 Field occurrence

29 4.2 Petrography 31

4.2.1 Peridotites 31 4.2.2 Gabbros 35

xii
4.3 Mineral chemistry 38 4.3.1 Olivine and Spinel 38 4.3.2 Orthopyroxene 39 4.3.3 Clinopyroxene 46 4.3.4

Plagioclase 51

4.4 Trace element concentration 51 4.5 Geothermometry and oxygen fugacity 57 Chapter 5: Mantle depletion and

melt-rock interaction 60 5.1 Petrogenesis of spinel harzburgites and dunites 61 5.2 Petrogenesis of plagioclase

peridotites 63 5.3 Petrogenetic model and nature of the impregnating melts 67 Chapter 6: Tectonic significance of

the ultramafic and mafic rocks

from the southern Palawan Ophiolite 75 6.1 Comparison with the ophiolitic units in central Palawan 76 6.2

Possible origin of the Palawan Ophiolite 82 Chapter 7: Conclusions 87 Appendices 91

A. Line analysis of plagioclase in plagioclase lherzolite 92 B. Mineral LA-ICP-MS analysis 94 C. Geologic map 96
D. Sample location map 98 E. Sample index 100

F. Petrographic reports 104 G. Mineral chemistry of Palawan Ophiolite peridotites 141 H. Mineral chemistry of
Palawan Ophiolite gabbros 153 References 160
xiii
LIST OF FIGURES

Chapter 1
1.1 Tectonic map of the Philippines and geologic map of Palawan 4 Chapter 2

2.1 Idealized ophiolite section 8 2.2 Spinel Mg# vs. Cr# diagram 11 2.3 Photomicrographs of plagioclase peridotites

from various works 14 Chapter 3

3.1 Sample location map in southern Palawan 22 3.2 Petrographic instruments used (Pelcon machine and 23

Olympus petrographic microscope)

3.3 Geochemical machines used (EPMA and LA-ICP-MS) 25 Chapter 4

4.1 Field photographs of peridotites and gabbros 30 4.2 Peridotites of the southern Palawan Ophiolite 32 4.3

Photomicrographs of the peridotites 33 4.4 Gabbros of the southern Palawan Ophiolite 36 4.5 Photomicrographs of

the gabbros 37 4.6 Mineral chemistry of spinel and olivine in peridotites 45 4.7 Pyroxene ternary diagram of

peridotite and gabbros 49 4.8 Mineral chemistry of pyroxene in peridotites and gabbros 50 4.9 Mineral chemistry of

olivine, plagioclase and clinopyroxene 52 in plagioclase peridotites and gabbros

4.10 Chondrite-normalized trace element diagram 56 4.11 Histograms of the calculated oxygen fugacity 59

xiv
Chapter 5

5.1 Ti vs Dy composition of clinopyroxene 64 5.2 Schematic diagram of the petrogenetic processes 68 5.3 Calculated

melt in equilibrium of clinopyroxene 73 Chapter 6

6.1 Comparison of the olivine and spinel major oxide compositions 79 of peridotites in central and southern Palawan

6.2 Comparison of the pyroxene major oxide compositions 80 of peridotites and gabbros in central and southern

Palawan

6.3 Comparison of the plagioclase and pyroxene major oxide compositions 81 of peridotites and gabbros in central

and southern Palawan

6.4 Tectonic evolution of the southern Palawan Ophiolite 86

xv
LIST OF TABLES

Chapter 4

4.1 Major oxide compositions of representative minerals in peridotites 40 4.2 Major oxide compositions of

representative minerals in gabbros 47 4.3 Trace element compositions of representative minerals in peridotites 54 and

gabbros

xvi

Chapter 1
Introductio
 n

1
Chapter 1

INTRODUCTION

1.1 Introduction

The oceanic lithosphere is an important component of the earth system. This crust

mantle rock assemblage records different processes that occur beneath the surface, such as

mantle-melt interaction and magmatic differentiation. As a consequence of its depth, direct

investigations of the oceanic lithosphere are limited to either xenolith studies, deep sea

drilling and dredging or investigations of exposed sections of an oceanic lithosphere, i.e.,

ophiolites. Ophiolites are identified as fragments of ancient oceanic crust and upper mantle

that were tectonically emplaced through different mechanisms (Dewey and Bird, 1971; Dilek

and Furnes, 2014; Rizeli et al., 2016). Compared to xenoliths, drill core and dredged samples,
well-preserved ophiolite sequences provide the opportunity to completely observe spatial,

temporal and structural relationships of diverse lithologies comprising the oceanic

lithosphere. These suites of rocks are therefore considered important sources of information

on the composition and the different magmatic-metamorphic processes that control the

tectonomagmatic evolution of the oceanic lithosphere (Dilek and Furnes, 2014). The

gabbroic-ultramafic sections of an ophiolite, for example, are typically known to preserve

records of melt-migration and differentiation, as well as melt-rock interaction (e.g. Bodinier

et al., 2008). These processes have constantly modified the mineralogical and chemical

compositions of the ascending melt and residual peridotites (e.g. Dilek and Yang, 2018). In

particular, the rare occurrence of plagioclase-bearing peridotites in the mantle section is

considered an important geodynamic marker related to either melt-residual peridotite reaction

(e.g. Rampone et al., 1997; Barth et al., 2003; Whattam et al., 2011; Dygert et al., 2016) or

2
metamorphic recrystallization of peridotite under plagioclase facies conditions (e.g. Hamlyn

and Bonatti, 1980; Rampone et al., 1993; Borghini et al., 2010).

The Palawan Ophiolite exposed in central and southern Palawan is among the

ophiolites and ophiolitic complexes which comprise the basement of the Philippine island arc

system (Fig. 1.1). Exposures of the ophiolitic units of the central Palawan Ophiolite are

observed in the municipalities of Narra, Aborlan, Quezon and Puerto Princesa. The southern

Palawan Ophiolite extends south of Quezon in the municipalities of Brooke’s Point and

Bataraza. Previous works postulated the occurrence of two distinct ophiolites in the island

based on the varied ages of radiometric dating. An Eocene age is assigned to the ophiolitic

lithologies in central Palawan (Raschka, 1985; Encarnación et al., 1995). On the other hand,

an older Cretaceous age is obtained for the chert samples associated with the pillow lavas in

southern Palawan (Muller, 1991). The origin of the ophiolite exposed in central and southern

Palawan is also debated. Some authors have suggested that the Palawan Ophiolite represented

a young marginal basin that is hosted in older Cretaceous proto-South China Sea basin

(SCSB) (e.g. Encarnación et al., 1995; Fernandez, 2001; Keenan et al., 2016). In contrast,

other works have speculated that the Palawan Ophiolite represented a single NW Sulu Sea

forearc basin of Cretaceous to Eocene age that wasthrusted onto the Palawan island (e.g. Hinz
 et al., 1991; Schlüter et al., 1996). While this ophiolite is generally regarded as a

suprasubduction zone (SSZ) ophiolite (Encarnación et al., 1995; Fernandez, 2001), much of

the published information were on the ophiolitic lithologies in central Palawan. The

petrological signatures of its southern counterpart are yet to be elucidated.

In this study, field mapping conducted in the southwestern portion of Palawan island,

particularly in the localities of Brooke’s Point and Bataraza, revealed extensive exposures of

(b)

Figure 1.1. (a) Tectonic map of the Philippines. Two tectonostratigraphic terranes are recognized: the seismically active-zone,

Philippine Mobile Belt (PMB) and the aseismic region of the Palawan Microcontinental Block (PCB). The boundary between

the PMB and PCB is delineated by the red dashed line (adopted from Manalo et al., 2016). The extent of the ophiolitic

lithologies in the island is indicated by the yellow fill. The black box refers to the map shown in panel b. (b) Map showing the

distribution of ophiolitic lithologies in central and southern Palawan and the localities sampled in this study. Geologic map was

modified from MMAJ-JICA (1990) and Aurelio et al. (2013). Abbreviations: CR=Cagayan Ridge, NT=Negros Trench,

ST=Sulu Trench, CT=Cotabato Trench.

4
well-preserved peridotites, basalts, and sparse gabbro outcrops. These ophiolitic lithologies are thrusted onto the

Eocene turbidites of the Panas Formation (Aurelio et al., 2013; Steuer et al., 2013). Plagioclase-bearing peridotites

intruded by gabbroic dikes are reported for the first time in this work. The petrographic and geochemical

characteristics of the ultramafic and mafic rocks in southern Palawan were investigated. The characterization of the

petrological signatures of these ultramafic and mafic units contributed to the understanding of the magmatic

processes including melt migration and evolution from the upper mantle to the crustal sections. This study provided

new petrological and geochemical constraints which suggest the possibility of two ophiolitic terranes preserved in the

island.

1.2 Statement of the problem

Previous petrological studies on the Palawan Ophiolite were mainly focused on the ophiolitic rocks exposed in

central Palawan. However, the petrological signatures of its southern counterpart remain to be examined. In this

study, the petrological characteristics of the ultramafic and mafic rocks in southern Palawan will be investigated to

determine the petrogenetic processes involved in their formation.

1.3 Significance of the study

The current understanding of the origin and evolution of the Palawan Ophiolite is limited by the available

petrological and geochemical information which were mostly from the lithologies in central Palawan. This study

generated new petrographic and geochemical data on the peridotites and gabbros exposed in southern Palawan.

Geologic mapping and initial sampling in the study area revealed the presence of plagioclase-bearing peridotites

which were not

5
reported in previous works. Since these rocks are rarely preserved in ophiolites, they are considered as good markers

to further investigate different petrogenetic processes affecting the upper mantle in subduction zones or in mid-

oceanic ridges. Correlation of geochemical data on the southern Palawan samples with the existing available

petrological data in central Palawan revealed the possibility of two contrasting ophiolitic terranes preserved in the

island.

1.4 Objectives of the study

This study aims to provide insights on the petrogenetic processes related to the formation of the ultramafic and mafic

rocks in southern Palawan. It specifically aims to:

a. Determine the petrographic and geochemical characteristics of the ultramafic and mafic rocks in southern Palawan

b. Correlate the petrographic and geochemical characteristics of these rocks with the ophiolitic lithologies in central

Palawan.

1.5 Scope and limitations

This study focused on the petrographic and geochemical characterization of ultramafic and mafic rocks from

southern Palawan, particularly from Brooke’s Point and Bataraza. Existing data on central Palawan from previous

works, such as those from Raschka et al. (1985), Claveria and Fischer (1991a; 1991b), Santos (1997) and Fernandez

(2001) were utilized for comparison with the data generated in this work. The volcanic rocks and other sedimentary

and metamorphic formations in southern Palawan were not included in the study.

Chapter 2
Literature Review
 7
CHAPTER 2

LITERATURE REVIEW

2.1 Ophiolites

Ophiolites are known to represent tectonically emplaced fragments of an ancient

oceanic lithosphere that are temporally and spatially related (e.g. Dewey and Bird, 1971;

Miyashiro, 1975; Dilek and Furnes, 2014). An idealized ophiolite section is composed, from

bottom to top, of a distinctive assemblage of ultramafic tectonites, layered mafic-ultramafic

cumulates, layered to isotropic gabbros, sheeted dike complex, and an extrusive section of

massive and pillowed lavas overlain by radiolarian chert or pelagic sediments (Fig. 2.1;

Anonymous, 1972; Moores, 1982; Dilek and Furnes, 2014).

Figure 2.1. An idealized ophiolite sequence according to the 1972 Penrose Conference (Anonymous,

1972). From top to bottom, it consists of a sedimentary carapace, massive and pillowed lavas, sheeted

dike complex, isotropic and layered gabbros, ultramafic cumulates, and mantle peridotites.

8
The study of ophiolites has contributed significantly to the understanding of the

formation and evolution of the oceanic lithosphere. Ophiolites are originally thought to

represent lithospheric materials formed at mid-ocean ridges (MOR) (Miyashiro, 1975).

However, Pearce and others (1984) have postulated that new oceanic crust can also be

formed in supra-subduction zones (SSZ). At present, ophiolites are broadly categorized into

either subduction-related or subduction-unrelated types. The subduction-unrelated ophiolites

have included mid-ocean ridge (MOR), continental margin (CM), and plume (P)-type

ophiolites (Dilek and Furnes, 2014). On the other hand, subduction-related ophiolites have

included supra-subduction zone (SSZ) and volcanic arc (VA) ophiolites. Distinct petrological

and geochemical differences exist between SSZ and MOR ophiolites. In particular, the SSZ

type is characterized by the presence of boninites lavas formed by partial melting of hydrated

refractory mantle peridotites (Ishikawa et al., 2002; Skylarov et al., 2016). In contrast, basalts

dredged from MOR are characterized by a low K2O (<0.2 %) and moderate to high TiO2

content. Its tholeiitic composition resulted from adiabatic decompression beneath mid-ocean

spreading centers. The gabbroic sections of these ophiolites have also shown distinct

crystallization order of olivine and clinopyroxene as the early crystallizing minerals followed

by late forming plagioclase (Pearce et al., 1984; Greene et al., 2006). The crystallization

order observed in MOR however, has shown olivine and plagioclase crystallizing prior to the

formation of clinopyroxene (Rollinson et al., 2017). The difference in fractionation patterns is

interpreted to be indicative of melts with different water content inhibiting the crystallization

of plagioclase over clinopyroxene in an arc environment (MacLeod et al., 2013). In terms of

trace element geochemistry, MOR-type ophiolites have displayed flat patterns between V and

Zr, and an increase toward the most incompatible elements (i.e., Ba, Rb, Cs) (Dilek and

Furnes, 2014). The volcanic and gabbroic rocks of SSZ ophiolites have shown much larger

variability; they are generally enriched in large ion lithophile elements

9
(LILEs) such as Cs, Rb, Ba, Th, K, Sr and Pb relative to high field strength elements

(HFSEs) such as Ta, Nb, Hf, Zr and Ti (Pearce et al., 1984; Bonev and Stampfli, 2008;

Guotana et al., 2017). This compositional heterogeneity is related to the input of slab-derived

components that modify the mantle region beneath arcs (Pearce, 2014). Furthermore, the

mantle section of SSZ ophiolites is composed principally of dunites and harzburgites with

occasional pyroxenite dikes and chromite deposits (Pearce et al., 1984; Guo et al., 2014). The

abyssal peridotites, on the other hand, are typically composed of lherzolites and
clinopyroxene-rich harzburgites formed by melt-extraction as a result of 5-15% partial

melting of fertile mantle under dry conditions (Uysal et al., 2014).

Mineralogical and chemical characteristics of peridotites have also been used to

constrain the tectonic origin of ophiolites. Primary spinel is considered an important

petrogenetic indicator whose chemical composition depended on the degree of partial melting

and interaction of melts with the host peridotites (Dick and Bullen, 1984; Arai, 1994; Choi et

al., 2008; Uysal et al., 2014). The Olivine-Spinel Mantle Array (OSMA) of Arai (1994) in

particular has been used to distinguish between residual mantle peridotites and ultramafic

cumulates. Increasing chromium number (Cr# = Cr/(Cr+Al)) of spinel and forsterite (Fo)

content of olivine is interpreted to indicate progressive partial melting of mantle peridotites

within the residual trend, while deviation from this trend may have suggested fractional

crystallization or metasomatism of mantle peridotites (e.g. Whattam et al., 2011; Uysal et al.,

2014). SSZ peridotites are characterized by spinels with higher Cr# ranging from around 38

to over 80, which indicated significantly higher degrees of partial melting compared to

abyssal peridotites having much lower Cr# (=0.10-0.60) (Fig. 2.2) (Dick and Bullen, 1984;

Arai, 1994; Choi et al., 2008). Due to higher degrees of partial melting, pyroxenes in SSZ type

peridotites are depleted in moderately incompatible elements, such as Al, Ti, and Na

10
Figure 2.2. Spinel compositions plotted on a Mg# [100xMg/(Mg+Fe2+)] vs. Cr# [100xCr/(Cr+Al)]

diagram which distinguishes forearc from abyssal peridotites. Fields are from Dick and Bullen (1984).

(Uysal et al., 2014; Rizeli et al., 2016). Olivine in these peridotites is characterized by higher

Fo contents and NiO wt.% indicating residual composition.

It is generally accepted that the upper mantle is dominantly composed of spinel

peridotites as supported by entrained xenoliths in volcanic rocks and ophiolitic peridotite

masses (Arai, 1994). However, ophiolites may also contain peridotites which reflect other

magmatic processes. Peridotites that are known to contain trace quantities of plagioclase, for

example, are thought to represent mantle sections that either equilibrated in the plagioclase

peridotite facies (e.g. Rampone et al., 1993; Takazawa et al., 1996; Borghini et al., 2010) or

were formed as products of melt impregnation and melt segregations (e.g. Barth et al., 2003;

Whattam et al., 2011; Dygert et al., 2016). Studying these peridotites will, therefore, provide

11
insights on the history of melt evolution and dynamics of the upper mantle in different

tectonic settings.
2.2 Plagioclase-bearing peridotites

Plagioclase-bearing peridotites are commonly observed in ophiolites, oceanic core

complexes, slow spreading centers and fracture zones (e.g. Dick, 1989; Tartarotti et al., 2002;

Loocke et al., 2013; Dygert et al., 2016). Petrogenetic models have suggested that plagioclase

peridotites are related either to the interaction of percolating melt through a depleted residual

peridotite (e.g. Rampone et al., 1997; Bodinier et al., 2008; Dygert et al., 2016) or to the

metamorphic recrystallization during subsolidus decompression of mantle peridotites, i.e.

from spinel to plagioclase-facies assemblage (e.g. Hamlyn and Bonatti, 1980; Rampone et al.,

1993; Takazawa et al., 1996; Borghini et al., 2010).

Melt-rock interaction is considered an important process in the shallower parts of the

mantle where unsaturated melts percolated through depleted peridotites (Saper and Liang,

2014). Modal and geochemical heterogeneities observed in mantle rocks such as the

formation of podiform chromitites are generally regarded as the product of interaction with

such ascending melts (Payot et al., 2014). Such process might also result in the chemical

refertilization of the lithospheric mantle to attain equilibrium with compositionally modified

impregnating melts, the result of which is known to be the plagioclase-bearing peridotites

(Rampone et al., 1997; Barth et al., 2003; Dygert et al., 2016). Discrete mineralogical

textures of plagioclase and clinopyroxene characterize impregnated peridotites. The

plagioclase formed through this process typically has occurred as interstitial patches or

veinlets that are confined within the grain boundaries of the preexisting minerals (Nicolas and

Dupuy, 1984; Rampone et al., 1997; Müntener et al., 2010) (Fig. 2.3). Clinopyroxene grains

are noted to occur as either small xenomorphic crystals that tend to be interstitial

12
between larger olivine and orthopyroxene grains (Figs. 2.3a-b) (Rampone et al., 1997;

Müntener et al., 2010; Dygert et al., 2016) or as large euhedral porphyroclasts (Nicolas and

Dupuy, 1984; Dygert et al., 2016). These textures are considered suggestive of melt

impregnation and melt-rock reaction (Rampone et al., 1997).

On the other hand, recrystallized plagioclase peridotites are formed by subsolidus re

equilibration under spinel- to plagioclase-facies conditions within the mantle. This type of
peridotite is considered indicative of cold tectonic exhumation of lithospheric mantle related

to thinning of the overlying lithosphere during rifting (e.g. Rampone et al., 1993; Takazawa

et al., 1996; Borghini et al., 2010). Unlike impregnated peridotites, plagioclase crystals are

formed as retrograde breakdown products from the reaction of clinopyroxene, orthopyroxene,

and spinel (Takahashi, 1996; Pirnia et al., 2018). This textural evidence is interpreted to

suggest a subsolidus origin for plagioclase, associated with spinel breakdown (e.g. Bodinier

et al., 2008; Pirnia et al., 2018) (Figs. 2.3c-d). Other textural evidence includes a progressive

decrease in modal pyroxene abundances with an increase in olivine and plagioclases. This is

interpreted to be the result of the re-equilibration of peridotites under plagioclase facies

conditions (Kornprobst and Tabit, 1988; Rampone et al., 1993; Pirnia et al., 2018). In

addition, crystal zoning may also be present in some of the minerals in plagioclase

peridotites. The zonation is interpreted to be the result of the progressive decrease in pressure

(~2.5-1 GPa) and temperature (1160-1050 C) conditions (Kornprobst and Tabit, 1988;

Takazawa et al., 1996).

Plagioclase peridotites are also identified to be compositionally different from spinel

and garnet peridotites (Dick and Bullen, 1984). In terms of bulk rock major composition,

impregnated plagioclase peridotites are enriched in fusible components such as SiO2, Al2O3,

CaO, and TiO2, and depleted in MgO content (Menzies and Allen, 1974; Piccardo et al.,

13
Figure 2.3. (a-b) Photomicrographs of plagioclase peridotite showing the assemblage of interstitial

clinopyroxene and highly altered plagioclase. (c-d) Highly dissolved spinel surrounded by slightly

altered plagioclase rim in plagioclase lherzolite. (a) and (b) are from Müntener et al. (2010) while (c)

and (d) are from Pirnia et al. (2018). Abbreviations: ol=olivine, plg=plagioclase, alt-pl=altered

plagioclase, spl=spinel, cpx=clinopyroxene, opx=orthopyroxene.

2007). Mineral chemistry is also considered a reliable means to distinguish plagioclase

peridotites. In particular, the spinel compositions of these peridotites have provided strong

constraints in determining the origin of plagioclase peridotites (Barth et al., 2003).

Plagioclase peridotites formed by melt rock interaction are characterized by higher Cr# of

spinel and lower forsterite (Fo) content of olivine and lower Mg# of clinopyroxene (Dick and

Bullen, 1984; Batanova et al., 1998; Tartarotti et al., 2002). Moreover, these peridotites have

14
exhibited higher TiO2 contents both in spinel and clinopyroxene, suggesting incomplete

chemical equilibration with the impregnating melts (Barth et al., 2003). Ti enrichment in

spinels in plagioclase peridotites is thought to be the result of the preferential partitioning of

Ti by the impregnating melts to spinel and pyroxene (Kornprobst and Tabit, 1988; Rampone

et al., 1993; Piccardo et al., 2007). The rare earth element (REE) concentrations of
clinopyroxene are also affected by melt impregnation. This can be seen from the LREE

depletion, higher contents of HREE and MREE, and a negative Eu anomaly (e.g. Batanova et

al., 1998; Barth et al., 2003; Piccardo et al., 2007).

Conversely, the re-equilibrated plagioclase peridotite is characterized by high Cr and

low Al contents consistent with the replacement texture of spinel with plagioclase rims

(Rampone et al., 1993). The spinel compositions within these peridotites are generally zoned

where Al and Ni concentrations decrease and Cr, Ti, and Fe concentrations increase from

core to rim attributed by the equilibration of the spinels with the plagioclase, whereby the Ni

depletions were the result of chemical exchange between spinel and coexisting olivine (Dick

and Bullen, 1984; Pirnia et al., 2018). These plagioclase grains have also shown

compositional variations in An content related to pressure changes (Rampone et al., 1993;

Borghini et al., 2010). The pyroxenes are chemically zoned as well, where Al and Ca

decrease from core to rim as a result of combination of cooling and plagioclase crystallization

(Pirnia et al., 2018). The whole-rock geochemical compositions have also supported the

metamorphic origin of these peridotites with similar compositions to that of the spinel

peridotites despite having significantly different modal abundance (Pirnia et al., 2018). This

is shown by similar concentrations of HREE and MREE/HREE ratios relative to the spinel

peridotites. The plagioclase peridotites, however, contain lower concentrations of the LREE,

reflecting lower modal abundance of pyroxene. In addition, concentrations of REE and trace

15
elements (e.g. Ti, V, Cr, Sr, Y, Zr) in clinopyroxenes are also varied from the core towards

the rim (Kornprobst and Tabit, 1988; Takazawa et al., 1996).

Studies of plagioclase peridotites, therefore, have provided evidence for the textural

and compositional varieties of peridotites at different mantle depths (e.g. Barth et al., 2008;

Pirnia et al., 2018; Rampone et al., 2018). Moreover, these peridotites are considered

important markers as they provide crucial information on the geodynamic processes related to

the evolution of the lithospheric mantle in various tectonic settings (e.g. Müntener et al.,

2008; Pirnia et al., 2018).

2.3 Regional geology and tectonic setting

Palawan is a northeast-southwest trending island located at the western portion of the

Philippines (Fig. 1.1). The island is bordered by two marginal basins, the South China Sea

(SCS) to the north and the Sulu Sea to the south. The Cagayan de Sulu ridge or simply,

Cagayan Ridge (CR) is an extinct Miocene arc which divides the Sulu Sea into Southeast

(SE) Sulu Sea and Northwest Sulu Sea basins, respectively. The Manila Trench along which

the South China Sea Basin subducts beneath the Philippine Mobile Belt is located to the

northeast of the island. To the east, the Sulu Sea Basin subducts along the Negros and Sulu

Trenches. Palawan island is divided into two major terranes: the North Palawan Continental

Terrane (NPCT) and the Southwestern Palawan Terrane (SPT) (e.g. Encarnación et al., 1995;

Keenan et al., 2016). The NPCT which includes the northern section of Palawan and the

islands further northeast (e.g. Busuanga), is underlain mainly by a succession of Mesozoic

sedimentary and metamorphic rocks of continental provenance. This is regarded as a

fragment of the Eurasian eastern margin that rifted off due to the opening of the South China

Sea during early Oligocene to early Miocene (e.g. Taylor and Hayes, 1980; Holloway, 1982).

Provenance analysis has indicated that the sediments comprising the NPCT were derived

16
from the South China margin and deposited during the Cretaceous (e.g. Almasco et al., 2000;

Suggate et al., 2014).

The SPT, on the other hand, includes the central and southern portions of the island. It

is dominated by ophiolitic lithologies thrusted onto turbidite sequences (Hamilton, 1979;

Raschka et al., 1985; Encarnación et al., 1995). Northwest of central-southern Palawan is

identified as the Palawan Trough which is connecteds to the Borneo Trough to the south

(Hamilton, 1973). This is interpreted as the extinct trench along which the proto-South China

Sea Basin (SCSB) subducted to accommodate the stress from the southeastward drifting of

the Asian continental fragment (Hamilton, 1979; Hinz and Schlüter, 1985). This zone of

convergence has led to the formation of the Cagayan arc and the opening of Sulu Sea, both of

which are considered as arc-backarc pair (Rangin and Silver, 1991). New geophysical

constraints, however, has suggested that the Palawan Trough did not reflect an extinct trench
(e.g. Liu et al., 2014), but rather corresponded to the continent-ocean transition at the

southeast edge of the modern SCS (Hall and Breitfeld, 2017).

The tectonic evolution of the Palawan island is related to the continental rifting which

occurred during the Late Cretaceous period. This eventually has led to the opening of the

South China Sea Basin from early Oligocene to early Miocene (32 Ma to 17 Ma) (e.g. Taylor

and Hayes, 1980; Briais et al., 1993). The southward motion of the NPCT required a zone of

shortening which is believed to have occurred further south of Palawan, although the timing

and nature of the shortening are yet to be constrained (Mitchell et al., 1986). Continued

opening of the SCSB and southward motion of the rifted NPCT have led to the collision

between the Palawan Microcontinental Block (PCB) and Philippine Mobile Belt (PMB)

(Hamilton, 1979; Yumul, 2007).

17
2.4 Models on the origin of Palawan Ophiolite

The Palawan Ophiolite is characterized to consist, from bottom to top, of amphibolite

grade metamorphic sole, tectonized peridotites, massive and isotropic gabbros, and an

uppermost unit of pillow basalts with intercalated shale and chert (Fig. 1.1b; MMAJ-JICA,

1990; Aurelio et al., 2013). Earlier works have identified two distinct ophiolites with different

ages exposed in the island. The ophiolite in the southwestern part is assigned a Cretaceous

age based on nannoplanktons found in calcareous clay associated with pillow lavas (Muller,

1991). Much of the ophiolitic lithologies in central Palawan, on the other hand, were

determined to be significantly younger, with an Eocene age (~34 Ma) based on radiometric

dating of the plagiogranite (Fernandez, 2001; Keenan et al., 2016). The origin of the Palawan

Ophiolite, however, is still debated. Some authors have proposed that the Palawan Ophiolite

represented a young marginal basin that is hosted in older Cretaceous proto-SCSB (e.g.

Encarnación et al., 1995; Fernandez, 2001; Keenan et al., 2016). Much of the available data

on the petrology and geochemistry of the Palawan Ophiolite are focused in the central portion

of the island. Basalts and dike samples from the central Palawan are interpreted to have a
predominantly MORB to transitional MORB-IAT geochemistry (Fernandez, 2001; Keenan et

al., 2016). Raschka et al. (1985) also performed major element analyses of the pillow basalts

and gabbro units exposed in central Palawan showing tholeiitic signature, with some plotting

in the calc-alkaline field. Furthermore, petrological characteristics of the chromitite pods and

lenses in the Ulugan Bay are identified as metallurgical in grade and have shown typical

composition of chromites found in alpine type peridotite with a Cr# ranging from 0.50-0.75

(Claveria and Fischer, 1991a).

On the basis of radiometric analysis of hornblende samples from the metamorphic

sole of the Palawan Ophiolite, Encarnación et al. (1995) has reported a 40Ar 39Ar age of 34.0

± 0.6 Ma. The metamorphic age was interpreted to be the age of the subduction initiation of

18
the proto-SCSB beneath an Eocene oceanic lithosphere which led to the formation of an arc

trench system, i.e. Cagayan arc. Complete consumption of the proto-SCSB have led to the

emplacement of the forearc basin now exposed as the Palawan Ophiolite.

Other models explaining the origin of the Palawan Ophiolite have speculated that the

ophiolite formed part of a trapped forearc oceanic lithosphere of the Cagayan ridge

continuous with the northwest Sulu Sea basin thrusted onto the continental turbidites (e.g.

Hutchison, 1992; Schlüter et al., 1996). Based on paleomagnetism, southern Palawan is

determined to have originated near the present location of Celebes Sea that underwent

northward displacement and counterclockwise rotation during the Eocene and Oligocene

period (Almasco et al., 2000). The Bouguer anomaly map of Cullen et al. (2010) has also

noted an ophiolitic basement beneath the islands of Palawan and northeast Sabah, which

implied a different origin from that of proto-SCSB. Recent geophysical techniques such as

gravity, seismic and magnetics also have confirmed that spreading of the Southeast Sulu Sea

occurred during Oligocene times due to the subduction of the proto-SCSB beneath the proto

NW Sulu Sea (Liu et al., 2014). This terminated during Middle Miocene due to the obduction

of NW Sulu Sea basin onto the PCB leading eventually to the emplacement of onland

ophiolite in southern Palawan.

 19

Chapter 3
Methodolog
y

20
CHAPTER 3

METHODOLOGY

3.1 Geologic mapping and sampling

Topographic maps from NAMRIA with 1:50,000 scale were utilized as base maps for

the field mapping. In this study, the ophiolitic lithologies comprising the southern Palawan
Ophiolite are exposed in the southwestern portion of the island. The southern Palawan

Ophiolite refers to the ophiolitic rocks which are mostly observed in the southern parts of the

island, particularly in the localities of Brooke’s Point and Bataraza. Exposures of well

preserved peridotites, basalts and sparse gabbro outcrops were commonly observed in these

localities. Sample locations are shown in Figure 3.1. Most of the peridotites in Bataraza were

identified as massive spinel harzburgites. In Brooke’s Point, the peridotites were mostly

spinel harzburgites with minor dunites. In particular, the occurrence of plagioclase peridotite

gabbroic dike suite in Brgy. Maainit, Brooke’s Point is being reported for the first time in this

work.

3.2 Petrography

Twelve (12) gabbros and twenty four (24) peridotites from the southern Palawan

Ophiolite were subjected to petrographic analyses. Thin sections of gabbros and peridotites

were made using the Pelcon automatic thin section machine installed at the University of the

Philippines-National Institute of Geological Sciences (UP-NIGS) (Fig. 3.2a). The hand

samples were cut into 28 mm x 48 mm and 100 mm thick slabs and polished to a thickness of

30 μm. Thin sections were then polished using the Struers automatic diamond polisher with a

21
Figure 3.1. Sampling localities of the peridotites and gabbros in southern Palawan. Most of the peridotites in Bataraza were
classified as spinel harzburgites.

Exposures of plagioclase peridotites were observed in Brgy. Maasin, Brooke’s Point.

22
Figure 3.2. (a) Rock samples were cut into slabs and thin sections using the Pelcon automatic thin

section machine at UP-NIGS. (b) Thin sections of peridotites and gabbros were examined and

analyzed using an Olympus BX53 petrographic microscope at UP-NIGS.

1 μm diamond polishing solution in order to obtain well-polished thin sections. Textural

characteristics of each sample were observed using an Olympus BX53 petrographic

microscope at UP-NIGS (Fig. 3.2b). Point counting of at least 2,000 mineral grains per

23
sample with regular spacing of 0.5 mm per step was done to accurately determine the mineral

modal abundance of each sample. The modal percentages were then plotted in diagrams after

the International Union of Geological Sciences (IUGS) for proper rock identification.

Minerals showing peculiar textures such as bleb-like texture of plagioclase, corroded and

resorbed shapes of pyroxene were prioritized for the mineral analysis.

3.3 Mineral chemistry and trace elements

Fifteen (15) double-polished thin sections of peridotite and seven (7) gabbros were selected

and subjected to mineral chemistry analysis. Major element compositions of primary minerals

(e.g. olivine, orthopyroxene, clinopyroxene, plagioclase and spinel) we re determined using

the Jeol JXA-8230 Electron Probe Microanalyzer (EPMA) at UP-NIGS (Fig. 3.3a). The

polished thin sections were carbon coated using the Cressington carbon coater at UP-NIGS to
 enhance the conductive properties of the samples. The EPMA is a technique for in situ and

non-destructive chemical analysis of small selected areas in solid samples. X-rays are

generated by focused electron beam. The X-ray spectrum contains lines characteristic of the

elements present. Comparison of these intensities with those emitted from standard samples

has allowed the determination of the concentrations of the elements quantitatively (Reed,

2005). The EPMA is a powerful tool for characterizing the composition of the mineral phases

in the analyzed samples. It is also capable of providing individual spot analysis and in situ

imaging for detailed microtextures such as zoning, minute inclusions, exsolution lamellae and

other compositional variations within minerals. In addition, the EPMA allows both qualitative

and quantitative analyses of individual mineral grains at a very small scale of 1 to 2 microns.

In this study, wavelength-dispersive spectrometer (WDS)

24
Figure 3.3. (a) The Electron Probe Microanalyzer (EPMA) (Jeol JXA-8230) at UP-NIGS was utilized

to determine major element composition of the primary minerals constituting the peridotites and

gabbros of the southern Palawan Ophiolite. (b) MicroLas laser ablation system in combination with

inductively coupled plasma-mass spectrometry (ICP-MS) (Agilent 7500s, Yokogawa Analytical

Systems) was used to obtain the trace element concentrations in clinopyroxene and orthopyroxene of

the peridotites and gabbros.

25
was used to obtain major element concentrations of the minerals. Line analysis from core to

rim of selected plagioclase and clinopyroxenes were done to test for intra-grain chemical

heterogeneity. The analyses were done using an acceleration voltage of 20 kV, a probe

current of 10-20 nA and a probe diameter of 5 or 10 μm. The counting time for each peak and

background was 5s and 10s, respectively. Natural and synthetic standards were used while

maintaining accuracy at <1%. ZAF correction was employed using JEOL software to correct

for matrix effects (e.g. Goldstein et al., 2003). All Fe was assumed to be Fe 2+ in silicates

while spinel stoichiometry was employed to compute for ferrous and ferric iron content of

chromian spinel.

Trace-element concentrations of selected clinopyroxene and orthopyroxene grains

were determined using the Agilent 7500s (Yokogawa Analytical Systems) inductively

coupled plasma-mass spectrometer outfitted with a GeoLas Q-Plus, MicroLas laser ablation

system at the Kanazawa University, Japan (Fig. 3.3b). Laser ablation (LA) in combination

with inductively coupled plasma-mass spectrometry (ICP-MS) is considered a powerful

technique for elemental and isotopic analysis (Fryer et al., 1993). It is widely used in many

applications, particularly for geochemical analysis of geological samples such as powder

pellets or polished thin sections. This instrument is capable of determining trace elements and

isotope ratios with extremely low detection limits. Analyses were performed at 6 Hz with

energy density of 8 J/cm2by ablating spots of 50 and 120 µm for clinopyroxene and

orthopyroxene, respectively. Time-resolved data was inspected to ensure that no inclusions

are considered in the analysed volume. National Institute of Standards and Technology

(NIST) standard reference materials (SRM) 612 and 614 glasses were used for calibration and

Si value from EPMA as an internal standard. Accuracy and precision of the concentration

values were determined using the NIST SRM 614. Further analytical techniques are discussed

in Morishita et al. (2005). Mineral chemistry and trace element data were plotted in

26
bivariate and tertiary plots, and normalized multi-element spider diagrams, respectively. The

major element compositions of the minerals are plotted in various diagrams to further

constrain the tectonomagmatic processes involved in their formation. Some of the commonly

used diagrams for the major element compositions of the minerals in the peridotites include

the following, spinel Mg# (Mg/[Mg+Fe2+]) vs. Cr# (Cr/[Cr+Al]) which is widely used to

discriminate peridotites formed either in forearc and abyssal settings (Fig. 2.2; Dick and

Bullen, 1984). The olivine-spinel-mantle array (OSMA) of Arai (1994) is used to measure the

degree of depletion of the mantle peridotites formed after partial melting and those peridotites

affected by magmatic and metasomatic processes. In addition, the association of these

characteristics with high degrees of partial melting is also reflected in their pyroxene

composition. Highly incompatible elements (e.g. Ti, Al, Na) and more compatible element,

such as Mg in pyroxenes, are often used in bivariate plots in order to further constrain

between refractory and fertile peridotites.

 27

Chapter 4
Petrological characteristics
of the ultramafic and mafic
rocks from the southern
Palawan Ophiolite

28
CHAPTER 4

PETROLOGICAL CHARACTERISTICS OF THE ULTRAMAFIC AND MAFIC ROCKS

FROM THE SOUTHERN PALAWAN OPHIOLITE

4.1 Field occurrence

 The ophiolitic lithologies comprising the Palawan Ophiolite are exposed in central

and southern parts of the island. Exposures of the ophiolitic units of the central Palawan

Ophiolite are observed in the municipalities of Narra, Aborlan, Quezon and Puerto Princesa.

The southern Palawan Ophiolite extends south of Quezon in the municipalities of Brooke’s

Point and Bataraza. Previous studies of the Palawan Ophiolite mainly focused on the rock

exposures found in the central parts of the island and only few studies have been conducted in

its southern counterpart. The lithologies comprising the southern Palawan Ophiolite,

therefore, remain to be examined. In order to better understand the magmatic processes

involved in the formation of the Palawan Ophiolite, the petrological characteristics of the

ultramafic and mafic rocks of its southern counterpart are investigated in this work.

In the field, wide exposures of peridotites and relatively sparse gabbroic rocks are

observed particularly in the localities of Brooke’s Point and Bataraza. The ultramafic

sequence mainly consists of spinel harzburgites with limited exposures of plagioclase

peridotites and dunites (Figs. 4.1a-f). Plagioclase peridotites in Maasin, Brooke’s Point range

from harzburgites, lherzolites and wehrlites (Fig. 4.1a). There is an apparent increase in the

modal abundances of clinopyroxene and plagioclase farther from the dike. Plagioclase

harzburgites and plagioclase lherzolites occur close to the gabbroic dike while plagioclase

wehrlite is situated rather far from the dike. Cutting the plagioclase peridotites with sharp

29
Figure 4.1. Field photographs of peridotite and gabbro outcrops. (a-b) Massive outcrop of plagioclase

peridotites intruded by gabbroic dikes and pods exposed at Brgy. Maasin, Brooke’s Point. (c) Close up

of the inset (white box) showing the sharp planar contact between gabbroic intrusions and plagioclase

peridotite. (d) Spinel harzburgites cut by several gabbroic dikes. (e) Massive dunites are observed

along a river in Brooke’s Point. (f) Highly fractured and serpentinized spinel harzburgites exposed in

Bataraza.

30
planar contacts are 3-5 cm subparallel troctolite dikes (PALB-02) and olivine gabbro pods

(PALB-03) generally oriented northeast with a gentle dip towards the northwest (Fig. 4.1b).

The olivine gabbro pods are continuous with the gabbroic dikes (Fig. 4.1c). Proximal to this

exposure are spinel harzburgites (PALB-05) also intruded by tabular gabbroic dikes (PALF
04) (Fig. 4.1d). A massive but heavily serpentinized dunite (PALF-10) outcrop is noted

across this outcrop (Fig. 4.1e). Elsewhere in southern Palawan, only massive, serpentinized

spinel harzburgites are observed, particularly in Bataraza (Fig. 4.1f).

4.2 Petrography

4.2.1 Peridotites

The peridotites in southern Palawan Ophiolite consist of spinel harzburgites, dunites

and plagioclase peridotites (Fig. 4.2). The spinel harzburgites are characterized by

protogranular to porphyroclastic texture (Mercier and Nicolas, 1975; Fig. 4.3a). They are

composed of coarse olivine (78-87%), orthopyroxene (10-22%), clinopyroxene (1-3%), and

accessory spinel (0.5-2%). Olivine is subhedral and mostly kinked with curvilinear

boundaries indicating ductile deformation. Orthopyroxene porphyroclasts of up to 3 mm size

with bent lamellae were also present (Fig. 4.3a). Subhedral clinopyroxenes are also deformed

although smaller (0.1-0.3 mm) than the orthopyroxenes. Chromian spinel is anhedral and

shows vermicular growth with orthopyroxene porphyroclast (Fig. 4.3b). One notable sample

of spinel harzburgite (PALB-05) shows textural characteristics different from the others. This

sample is dominantly composed of olivine (84%), orthopyroxene (12%), minor

clinopyroxene (3%) and accessory spinel (1%). It is characterized by resorbed and corroded

texture (Fig. 4.3c). Olivine is up to 2-3 mm across. Intergrowth of large olivine with

orthopyroxene is commonly observed in the sample (Fig. 4.3c). Orthopyroxene is often

31
Figure 4.2. The mantle section of the southern Palawan Ophiolite mainly consists of spinel
harzburgites, dunites and plagioclase peridotites (e.g. plagioclase wehrlite, plagioclase lherzolite and
plagioclase harzburgite).

partly corroded and sharp boundaries of resorbed grains are also present. Clinopyroxene

appears as small and discrete grain (0.25 mm). Vermicular spinel (0.5-1 mm) is closely

associated with orthopyroxene. Most of the dunite samples are highly serpentinized and only

a few coarse olivine and spinel grains are preserved. It is interesting to note that one dunite

(PALF-10) sample shows peculiar texture different from other dunites. The sample is

dominantly composed of olivine (85-90%) with few clinopyroxene (2-3%) and minor spinel

(<1%). It is characterized by interstitial clinopyroxene set in an olivine matrix and is

commonly associated with spinel (Fig. 4.3d). Olivine in dunite reaches up to 3-4 mm in size.

Olivine is heavily serpentinized; however, some parts are still recognizable showing

32
Figure 4.3. (a) Heavily kinked orthopyroxene porphyroclast containing olivine and small spinel

inclusions in spinel harzburgite. (b) Vermicular growth of spinel within orthopyroxene in spinel

harzburgite. (c) Spinel harzburgite (PALB-05) showing corroded texture of orthopyroxene in contact

with olivine and anhedral clinopyroxenes. (d) Dunite (PALF-10) is characterized by an intergrowth of

interstitial clinopyroxene around spinel. (e) Plagioclase blebs are surrounded by interstitial

clinopyroxenes set in olivine matrix in the plagioclase lherzolite. (f) Anhedral orthopyroxenes

surrounding plagioclase in plagioclase harzburgite. Abbreviations: ol= olivine; sp= spinel; opx=

orthopyroxene; cpx= clinopyroxene; plg= plagioclase.

33
kinked structures that indicated deformation. Clinopyroxene is preserved as an interstitial

mineral surrounding spinel (Fig. 4.3d). Spinel is usually black and has rounded and/or

vermicular habit.
 The plagioclase peridotites have variable amounts of clinopyroxene and are classified

as plagioclase wehrlite, plagioclase lherzolite and plagioclase harzburgite. Plagioclase

wehrlite consists of olivine (75-78%), clinopyroxene (9-12%), orthopyroxene (4%),

accessory spinel (<2%), and significant amounts of plagioclase (<4%). This sample is

moderately to highly serpentinized showing mesh texture and magnetite trails between

olivine grains (0.5 to 2 mm). Clinopyroxenes (0.5 to 1.5 mm) and orthopyroxenes (1 to 2

mm) are anhedral and often show elongated shapes and irregular curved grain boundaries

similar to that of PALB-05. Clinopyroxenes are typically interstitial between plagioclase and

other minerals in the sample (Fig. 4.3e). Compared to those in the spinel harzburgites, these

clinopyroxenes are undeformed. Plagioclases (0.5 mm) are anhedral and are locally

associated with clinopyroxene and/or orthopyroxene, and spinel (Fig. 4.3f). Spinels in

plagioclase wehrlite are black and are commonly rounded. Plagioclase lherzolite is composed

dominantly of olivine (78-88%), orthopyroxene (3-7%) with varying amounts of

clinopyroxene (6%), plagioclase (6-7%), and trace spinel (<2%). Similar to plagioclase

wehrlite, plagioclase lherzolite is also characterized by irregular shapes and corroded texture

of olivine, orthopyroxene and/or clinopyroxene. Olivines (1 to 3 mm) are highly

serpentinized showing mesh texture and trails of magnetite. Some of the olivine grains are

altered to serpentine. Orthopyroxenes are anhedral and huge reaching up to 3 mm across.

Some of the grains are slightly deformed, although less commonly than in spinel harzburgites

and dunites. Clinopyroxene grains range in size from 0.5 to 1.5 mm. They usually occur as

interstitial grain, some of which are developed around rounded spinel and are highly

comparable to the peculiar texture of clinopyroxene observed in dunite (PALF-10).

34
Plagioclases in this sample are anhedral and typically associated with orthopyroxene and/or

clinopyroxene. They also show lamellar twinning similar to the plagioclase in plagioclase

wehrlite (Fig. 4.3e). Some of the plagioclase grains are relatively fresh in the sample but most

are locally altered to fine grained saussurites. Spinel in plagioclase lherzolite is opaque and

subhedral to anhedral.

4.2.2 Gabbros
 Extensive gabbro exposures were not found in the southern Palawan Ophiolite.

Instead, the gabbroic rocks mainly occur as intrusions of dikes or pods cutting the peridotites

in Maasin, Brooke’s Point. Some are found as boulder-size floats in the riverbed. These

gabbros are classified as olivine gabbro and troctolite (Fig. 4.4). All of the gabbro floats

studied are olivine gabbro. The olivine gabbros typically exhibit equigranular to

hypidiomorphic granular texture and contain mostly plagioclase (40-57%), olivine (13-20%),

intercumulus clinopyroxene (17-33%) and minor orthopyroxene (3-8%) (Figs. 4.5a-d).

Plagioclase (1-4 mm) is euhedral to subhedral and exhibit polysynthetic twinning and shows

adcumulate texture (Fig. 4.5a). Some of these grains are poikilitically enveloped by huge

clinopyroxene and olivine (Fig. 4.5b). Olivine grains reach up to 4 mm across and are

moderately serpentinized (Figs. 4.5b-c). Clinopyroxene is euhedral to subhedral and contains

exsolved orthopyroxene. Some of the clinopyroxene shows ophitic texture which envelopes

well-developed plagioclase (Fig. 4.5b). Anhedral clinopyroxene as well as coexisting

orthopyroxene occur as interstitial minerals between olivine and plagioclase suggesting late

crystallization following olivine and plagioclase (Fig. 4.5c). Subsequently, the gabbroic

intrusions are identified as olivine gabbro (PALB-03 and PALF-04) and troctolite (PALB-02).

These gabbros however show distinct textural characteristics different from other samples.

Sample PALB-03 is particularly characterized by irregular and embayed mineral

35
Figure 4.4.
 The

gabbros are mainly classified as olivine gabbro and troctolite. grains. This sample is coarse-
grained and contains mostly plagioclase (48%), olivine (18%),
clinopyroxene (17%), and minor amounts of orthopyroxene (3%). Plagioclase is subhedral to

anhedral, 0.5 to 2 mm sized, and has ragged and irregular contacts with clinopyroxene (Fig.

4.5d). Although relatively fresh, few plagioclases are partly sericitized (Fig. 4.5e). Olivines

(1-2 mm) are anhedral and slightly serpentinized. Clinopyroxene is up to 4 mm across and

characterized by highly irregular and embayed texture with coexisting minerals. Intergrowth

of clinopyroxene grains is commonly present in the sample. Orthopyroxene is interstitial

between other minerals suggesting late crystallization. In altered parts of the sample,

clinopyroxene and plagioclase are replaced by fine-grained aggregates of amphibole. These

secondary minerals are locally developed along grain boundaries and/or cracks in plagioclase

and clinopyroxene. Tabular gabbroic dikes (PALF-04) cutting the spinel harzburgite (PALB-

05) are also identified as olivine gabbro. Sample PALF-04 is medium grained and comprised

of plagioclase (50%), clinopyroxene (26%), olivine (16%),

36
 Fig

ure 4.5. (a-c) Olivine gabbros are equigranular to hypidiomorphic containing mostly of plagioclase,
olivine, clinopyroxene and minor orthopyroxene. (a-b) Ophitic clinopyroxene envelopes small and
well-developed plagioclases. (c) Intercumulus clinopyroxene and orthopyroxene are common in the
sample. (d-e) PALB-03 shows irregular and corroded minerals along grain boundaries. (f) Troctolite
is generally medium-grained and the minerals present are extensively altered. Photomicrographs taken
under cross polarized light. Abbreviations: ol= olivine; sp= spinel; opx= orthopyroxene; cpx=
clinopyroxene; plg= plagioclase; alt plg=altered plagioclase; ser plg=sericitized plagioclase.
37
and minor orthopyroxene (2%). Most of the plagioclases (0.3 to 1mm) are altered to

saussurites and only few grains are preserved. Clinopyroxene (0.5 to 1 mm) is anhedral and

generally being replaced by amphibole (0.5 to 1.2mm) and shows intergrowth texture with

the amphibole. Olivine grains (1 to 1.5 mm) are anhedral and are slightly serpentinized.

Minor orthopyroxenes (0.2 to 0.5 mm) occur as small and anhedral grains.

Nearly all the gabbro samples from southern Palawan Ophiolite are olivine gabbros,

except for PALB-02, which is identified as a troctolite. Sample PALB-02 is generally

medium-grained and the minerals present are extensively altered (Fig. 4.5f). Olivine (50%) is

highly altered to serpentine, whereas plagioclase (48%) is completely altered to clay

minerals. Clinopyroxenes (2%) and minor orthopyroxene (<1%) occur as small subhedral to

anhedral grains (Fig. 4.5f).

4.3 Mineral chemistry

The compositions of the mineral phases are interpreted to reflect the evolution of the

melt from which they have crystallized and the different tectonomagmatic processes involved

in the formation of various lithologies (Dick and Bullen, 1984; Arai, 1994; Choi et al., 2008;

Uysal et al., 2014). As such, it is necessary to characterize the chemical composition of

minerals present in the peridotites and gabbroic rocks of the southern Palawan Ophiolite. The

major element compositions of olivine, spinel, orthopyroxene, clinopyroxene, and plagioclase

are presented in Tables 1-2.

4.3.1 Olivine and Spinel

Olivine in spinel harzburgites and dunite is more magnesian (Fo 90-92) than those in

plagioclase peridotites (Fo83-87) (Fig. 4.6a). Olivine gabbro and troctolite are the least

magnesian (Fo76-85). The NiO content of olivine in spinel harzburgites and dunite is also

38
higher (0.34-0.43 wt.%) compared to those in plagioclase peridotites (0.20-0.26 wt.%), and

gabbroic rocks (0.14-0.23 wt.%). The spinel harzburgite (sample PALB-05), however,

consists of olivine with NiO and Fo contents comparable to those in plagioclase peridotites

(Fig. 4.6a). Spinel Cr# (= Cr/[Cr+Al]) in spinel harzburgites and dunite is high (0.53-0.78)

while their Mg# is low (Mg/[Mg+Fe2+] = 0.40-0.60) (Fig. 4.6b). They also contain low

concentration of TiO2 (<0.05 wt.%) (Fig. 4.6c). These peridotites are noted to fall in the

highly depleted end of the olivine-spinel mantle array (e.g. Arai, 1994) and are comparable to

peridotites of suprasubduction zone ophiolites. Spinel in plagioclase peridotites, on the other

hand, is characterized by a narrower range of Cr# (0.60-0.62) and lower Mg# (0.28-0.39)

(Fig. 4.6b). They are also characterized by higher Fe3+ and TiO2 (0.98-1.54 wt.%) compared

to the spinel harzburgites and dunites (Figs. 4.6c-d). These peridotites have signatures similar
 to some of the impregnated plagioclase peridotites formed after melt-rock interaction

processes as well as other back-arc basin (BAB) peridotites. Those in the spinel harzburgite

(PALB-05) also exhibit enrichment in TiO2 (0.12-0.47 wt.%) and Fe3+ consequently becoming

less magnesian (Mg# = 0.37-0.46) similar to plagioclase peridotites (Figs. 4.6c d).

4.3.2 Orthopyroxene

On the pyroxene ternary diagram (Morimoto et al., 1988), the orthopyroxenes in all

the samples are enstatite. Orthopyroxene in spinel harzburgites have a narrow range of Mg#

(=0.90-0.92) and low Al2O3 and Cr2O3 (Figs. 4.8a-b) concentration. They are considered

comparable to highly depleted mantle peridotites such as those from forearc peridotites of

Arai and Ishimaru (2008). Orthopyroxene in plagioclase peridotites and in PALB-05 are

significantly less magnesian (=0.84-0.88) albeit with similar concentration of Al2O3 (Fig. 4.8a)

and Cr2O3 (Fig. 4.8b). They are noted to be similar to some back-arc peridotites and

39
Table 4.1 Representative microprobe analysis of olivine, spinel, clinopyroxene, orthopyroxene and plagioclase in the plagioclase peridotites, spinel
harzburgites and dunite from southern Palawan Ophiolite. Total iron as FeO*. (-) means below detection limit.
Plagioclase lherzolite
Spinel Olivine Clinopyroxene Orthopyroxene Sample PALB-01 PALB-01 PALB-01 PALB-01 PALB-01 PALB-01 PALB-01 PALB-01 PALB-01
PALB-01 PALB-01 PALB-01 C7-5 C12-4 C9-11 C2-5 C5-2 C6-2 C1-3 C11-3 C14-2 C10-4 C7-3 C7-4 SiO 2 - 0.06 0.01 39.66 39.83 39.73 52.69
52.59 52.56 55.76 55.48 55.43 TiO2 1.41 1.41 1.55 0.05 0.01 - 0.40 0.44 0.44 0.18 0.21 0.19 Al 2O3 15.86 16.60 15.03 0.02 0.02 0.01 2.65 2.41 2.34
1.37 1.58 1.48 Cr2O3 36.44 36.32 38.18 0.04 - - 1.12 0.81 0.84 0.38 0.43 0.44 FeO 39.97 38.67 39.00 15.43 14.81 14.95 5.15 4.72 4.35 9.94 10.09
10.36 MnO 0.42 0.41 0.43 0.22 0.29 0.22 0.15 0.13 0.13 0.25 0.25 0.27 MgO 5.75 6.53 6.44 45.29 45.33 45.37 17.32 17.44 16.62 31.80 31.07 31.38
CaO - - 0.03 - 0.02 - 20.20 21.04 22.00 0.72 1.48 1.00 Na 2O 0.03 0.03 0.02 - - 0.01 0.43 0.38 0.40 0.01 0.03 0.01 K 2O - 0.01 - - 0.01 0.01 - - - - 0.02
0.02 NiO 0.12 0.13 0.17 0.25 0.26 0.27 0.06 0.08 0.07 0.08 0.12 0.09 Total 100.00 100.16 100.86 100.96 100.57 100.55 100.16 100.05 99.73 100.51
100.75 100.68

Mg# 0.28 0.32 0.31 0.86 0.87 0.87 0.85 0.85 0.84 Cr# 0.61 0.59 0.63
Fo 83.95 84.50 84.39
An

40
Table 4.1 (continued)
Plagioclase lherzolite Plagioclase wehrlite
Plagioclase Spinel Olivine Clinopyroxene Sample PALB-01 PALB-01 PALB-01 PALB-04 PALB-04 PALB-04 PALB-04 PALB-04 PALB-04
PALB-04 PALB-04 PALB-04 C5-3 C7-2 C7-1 C6-7 C3-2 C4-7 C6-4 C7-5 C14-12 C3-2 C3-3 C9-5 SiO 2 49.64 49.28 49.52 0.06 - 0.02 39.88 39.33
39.56 52.02 52.35 51.60 TiO2 - 0.01 0.03 1.09 1.10 1.21 - 0.01 0.02 0.39 0.33 0.47 Al2O3 31.79 31.64 31.76 16.85 16.04 15.80 0.01 - 0.01 2.67 2.24
2.78 Cr2O3 0.03 - - 38.05 38.39 38.12 - 0.02 0.05 1.07 0.90 1.11 FeO 0.23 0.20 0.21 36.47 37.42 38.09 13.63 13.69 13.31 3.65 3.44 3.89 MnO 0.02
0.01 - 0.41 0.40 0.46 0.20 0.19 0.17 0.10 0.09 0.08 MgO 0.02 0.02 0.02 6.85 6.47 6.26 46.27 45.75 46.73 16.14 16.25 15.97 CaO 15.05 14.95 14.84 -
- - 0.02 0.04 0.02 22.07 22.47 22.32 Na2O 2.86 2.99 2.96 0.02 0.04 0.04 - 0.02 - 0.51 0.42 0.39 K 2O 0.01 - 0.01 - - - - - 0.01 0.01 0.01 0.01 NiO 0.05
0.06 0.04 0.14 0.16 0.14 0.24 0.31 0.26 0.09 0.04 0.05 Total 99.69 99.16 99.38 99.94 100.01 100.14 100.26 99.34 100.13 98.71 98.55 98.68

Mg# 0.33 0.32 0.31 0.89 0.89 0.88 Cr# 0.60 0.62 0.62
Fo 85.82 85.62 86.22
An 74.33 73.43 73.45

41
Table 4.1 (continued)
Plagioclase wehrlite Plagioclase harzburgite
Plagioclase Spinel Olivine Clinopyroxene Sample PALB-04 PALB-04 PALB-04 PALJ-01 PALJ-01 PALJ-01 PALJ-01 PALJ-01 PALJ-01 PALJ-01
51.10 50.10 50.61 39.40 39.36 39.51
PALJ-01 PALJ-01 C2-3 C1-9 C2-4 C1-9 C3-3 C12-2 C5-8 C9-4 C11-4 C1-3 C2-7 C9-2 SiO 2 - 0.01 0.01 52.60
- 0.01 0.05 - 0.01 - 31.03 31.52 30.74 - - 0.01 - 0.04 -
52.44 52.20 TiO2 1.53 1.29 1.72 0.23 0.34 0.24 Al2O3 15.77 17.12 16.49 2.46 2.39 2.62 Cr2O3
- 0.02 -
37.68 37.12 36.12 0.50 0.44 0.53 FeO 0.18 0.19 0.21 39.36 37.71 39.04 16.38 16.09 15.90 4.59 3.92 4.19 MnO 0.02 0.04 0.03 0.52 0.42 0.42
0.24 0.25 0.21 0.11 0.18 0.14 MgO 0.03 0.01 0.03 5.69 7.02 6.41 44.62 44.74 45.12 16.37 16.14 16.36 CaO 13.84 14.41 14.02 - - - 0.01 0.01 0.01
O 3.55 2.95 3.57 0.01 0.01 0.01 O - 0.02 0.02 ---
22.35 22.91 22.27 Na2 0.03 0.01 0.01 0.45 0.48 0.44 K2 - 0.01 0.01 - - 0.01 NiO 0.05 0.01 0.02
0.13 0.12 0.13 0.16 0.15 0.21 0.04 0.06 0.06 Total 99.80 99.29 99.30 100.70 100.83 100.36 100.81 100.63 100.96 99.70 99.30 99.06

Mg# 0.28 0.34 0.31 0.86 0.88 0.87 Cr# 0.62 0.59 0.59
Fo 82.92 83.21 83.49 An 68.29 72.91 68.38

42
Table 4.1 (continued)
Plagioclase harzburgite Spinel harzburgite
Orthopyroxene Plagioclase Spinel Olivine
Sample PALJ-01 PALJ-01 PALJ-01 PALJ-01 PALJ-01 PALJ-01 PALB-05 PALB-09 PALG-01 PALB-05 PALB-09 PALG-01 C5-7 C6-4 C7-1
--
C11-3 C5-4 C6-6 C7-04 C1-6 C4-5 C8-04 C1-5 C1-3 SiO 2 55.02 55.26 55.47 49.86 49.12 49.60 0.01 40.15 41.34 40.53 TiO2 0.15 0.15 0.13 0.09
0.28 0.03 28.25 23.06 31.03 41.00
0.03 0.03 0.01 - - - Al2O3 1.55 1.48 1.61 31.71 31.66 31.49 19.55 0.01 0.01 - Cr2O3 0.23 0.21 0.20 0.02 - - 47.43 -
0.03 - FeO 10.17 10.34 10.53 0.21 0.17 0.13 30.32 25.74 22.72 13.54 9.85 9.33 MnO 0.24 0.21 0.25 - - 0.01 0.30 0.34 0.33 0.19 0.11 0.12 MgO
O
30.54 30.77 30.91 0.02 0.02 0.03 10.24 10.10 10.61 46.08 48.91 49.63 CaO 2.08 1.48 1.48 14.81 14.99 14.94 - - - 0.01 0.01 - Na 2 0.03 0.02 0.03
0.01 0.03 O - 0.01
3.12 3.08 3.03 0.02 - 0.01 0.01 K2 - - 0.02 0.03 0.01 - - - - - NiO 0.03 0.05 0.08 - - 0.04 0.21 0.11 0.05 0.28 0.35 0.37 Total 100.04
99.97 100.71 99.86 99.07 99.31 100.64 100.41 100.73 100.26 100.61 100.00

Mg# 0.84 0.84 0.84 0.46 0.47 0.50

Cr# 0.42 0.54 0.62
Fo 85.85 89.85 90.46 An 72.28 72.85 73.13

43
Table 4.1 (continued)
Spinel harzburgite Dunite
Sample Clinopyroxene Orthopyroxene Spinel Olivine PALB-05 PALB-09 PALB-05 PALB-09 PALG-01 PALG-04 PALG-04 PALG-02 PALG-04
53.87 55.87 56.86 40.59 40.67
PALG-04 PALG-02 C15-08 C1-4 C6-01 C1-1 C14-2 C4-5 C7-1 C5-1 C9-3 C10-2 C6-3 SiO 2 54.59 57.31 0.01 - 0.02
0.04 0.02 - -- 1.66 1.79 1.55 -- 0.66 0.48 0.52
40.89 TiO2 0.03 - 0.01 - - 0.01 Al2O3 1.48 0.83 19.55 20.91 20.24 0.02 Cr2O3 0.46 0.34 47.43 46.77
- 0.01
47.23 - FeO 3.53 2.36 8.73 5.97 6.50 22.72 21.16 19.20 10.03 10.19 7.68 MnO 0.10 0.09 0.20 0.17 0.10 0.33 0.32 0.32 0.14 0.13 0.14 MgO
O 0.35 0.02 0.01
16.43 17.48 31.76 33.34 34.56 10.61 11.35 11.89 49.65 49.41 50.53 CaO 22.78 23.83 1.11 1.73 0.60 - - - - - - Na 2 0.21 0.02 0.02
0.03 - O - - 0.01 - 0.01
0.01 0.02 0.02 K2 - 0.03 - 0.01 0.03 - NiO 0.08 0.05 0.08 0.10 0.11 0.05 0.10 0.09 0.45 0.43 0.05 Total 99.49 100.59 100.06
100.27 100.39 100.73 100.63 99.03 100.89 100.84 99.34

Mg# 0.89 0.93 0.87 0.91 0.90 0.50 0.53 0.56

Cr# 0.62 0.60 0.61
Fo 89.82 89.63 92.14

44
Figure 4.6. (a) Olivine forsterite against spinel Cr# for the spinel harzburgites and plagioclase peridotites from the southern

Palawan Ophiolite. The spinel harzburgites dominantly plot within the olivine spinel mantle array (OSMA). Trends for

fractionation, metasomatism, partial melting and OSMA are from Arai (1994). (b) Cr# versus Mg# of chromian spinels in the

spinel harzburgites and plagioclase peridotites from the southern Palawan Ophiolite. (c) TiO 2 vs Cr# in spinel of the southern

Palawan Ophiolite peridotites. Mantle-melt reaction trends for boninites and MORB are after Choi et al. (2008). (d) Ternary

diagram showing the Cr-Al-Fe3+ content in the spinel harzburgites and plagioclase peridotites. The chromian spinels plot

within and near the forearc peridotite field. Field of abyssal peridotites (light green from Dick and Bullen, 1984) and forearc

peridotites (solid line from Ishii et al., 1992). Also shown are the background data of spinel abyssal peridotites from Hamlyn

and Bonatti (1980); impregnated plagioclase peridotites from Dick et al. (2010), and Loocke et al. (2013); recrystallized

plagioclase peridotites from Pirnia et al. (2018); back-arc basin peridotites from Ohara et al. (2003), respectively. Forearc

peridotite data from Ishii et al. (1992). The error bars denote the compositional variation of the respective minerals.

45
 abyssal peridotites which underwent melt-rock interaction (Ohara et al., 2002; 2003; Sato and

Ishii, 2011; Loocke et al., 2013).

4.3.3 Clinopyroxene

Clinopyroxenes in spinel harzburgites are mostly identified as diopside (En47-50, Wo47-

49 , and Fs3-6) while in plagioclase peridotites and gabbros they are idetntified as augites (Figs.

4.7a-b; Morimoto et al., 1988). Clinopyroxenes in the spinel harzburgites are highly

magnesian (Mg# = 0.93-0.95) with low Na2O (<0.28 wt. %), Al2O3 (Fig. 4.8c) and TiO2

content (Fig. 4.8d). They are consistent with forearc peridotites formed after high degrees of

partial melting. On the other hand, clinopyroxene in plagioclase peridotites and PALB-05 are

Fe-rich (Mg# = 0.87-0.90) and contain more Na 2O (0.37-0.47 wt. %), Al2O3 (Fig. 4.8c) and

TiO2 than the spinel harzburgites (Fig. 4.8d). Such signatures are similar to clinopyroxenes in

the troctolite (PALB-02) and olivine gabbro (PALB-03 and PALF-04) containing much lower

Mg#, higher Al2O3 and TiO2 (Figs. 4.8c-d). The olivine gabbro dike sample (PALF 04),

however, contains much lower TiO2 content than the troctolite dike (PALB-02) and olivine

gabbro pod (PALB-03) albeit having similar Mg#. Clinopyroxenes in the gabbros particularly

in the troctolite dike (PALB-02) and olivine gabbro pods (PALB-03) have higher TiO 2

contents at a given Mg# compared to some of the gabbros and plagioclase peridotites (Figs.

4.8d; 4.9a). These samples have similar characteristics with the plagioclase peridotites and

show comparable signatures to the MOR and back-arc related gabbros (Fig. 4.9a). Some of

the gabbros including the troctolite dike (PALB-02) and olivine gabbro pod and dikes

(PALB-03 and PALF-04) apparently show increasing Al2O3 with decreasing Mg#

characteristic of primitive arc gabbros (Fig 4.9b).

46
Table 4.2 Representative microprobe analysis of olivine, clinopyroxene, orthopyroxene and plagioclase in the olivine gabbros and troctolites from
southern Palawan Ophiolite. Total iron as FeO*. (-) means below detection limit.
Olivine gabbro
Olivine Clinopyroxene Orthopyroxene Plagioclase Sample PALB-03 PALB-12 PALF-04 PALB-03 PALB-12 PALF-04 PALB-03 PALB-12 PALF-
39.29 39.82 40.11 52.90
04 PALB-03 PALB-12 PALF-04 C3-2 C4-2 C3-2 C5-1 C11-5 C4-4 C4-3 C3-2 C1-6 C12-5 C1-5 C3-8 SiO 2 52.49 53.58
55.16 48.27 0.05 - - 0.31 0.19 - - - - 2.95 1.48 32.73
55.46 56.37 46.19 50.01 TiO2 0.12 0.08 0.01 0.03 - 0.03 Al2O3 2.77 3.19 1.29 1.69 34.24 30.19
 - - - 0.85 0.28 0.05
Cr2O3 0.33 0.08 0.30 - - - FeO 18.33 14.38 20.44 5.20 4.26 5.03 12.05 10.16 11.85 0.20 0.24 0.22 MnO 0.24 0.21 0.34 0.15 0.11
0.14 0.31 0.22 0.32 - - 0.01 MgO 42.11 45.74 39.87 15.94 16.57 13.88 30.42 31.91 29.81 0.03 0.02 0.09 CaO - 0.01 - 21.29 23.18 23.15 0.56 0.74
O 0.01 0.01 0.05 0.36 0.01 2.11 O - 0.01 0.01 - - 0.01
0.59 15.88 17.87 16.80 Na2 0.32 0.52 0.02 0.05 1.48 3.10 K2 0.01 - - 0.02 0.02 0.02 NiO 0.26
0.21 - 0.04 0.03 0.02 0.08 0.04 - 0.01 - 0.05 Total 100.30 100.39 100.82 99.98 100.18 99.66 100.52 100.15 100.72 99.29 100.06 100.51

Mg# 0.85 0.87 0.83 0.82 0.85 0.79

Fo 80.37 85.00 77.66
An 80.61 77.06 74.88

47
Table 4.2 (continued)
Troctolite
Olivine Clinopyroxene Orthopyroxene Sample PALB-02 PALB-02 PALB-02 PALB-02 PALB-02 PALB-02 PALB-02 C7-4 C7-1 C7-3 C1-1 C5-4
C6-3 C3-1 SiO2 39.06 39.75 38.33 53.09 52.89 52.72 52.96 TiO2 - - - 0.91 0.95 0.98 0.34 Al2O3 - - - 2.75 2.79 2.93 1.46 Cr2O3 - - - 0.63 0.78 0.74
0.25 FeO 17.21 17.51 17.03 5.06 4.69 5.11 11.73 MnO 0.21 0.23 0.26 0.13 0.11 0.16 0.29 MgO 43.25 43.51 42.65 16.36 15.67 15.83 30.35 CaO
0.02 - 0.01 21.12 21.64 21.21 0.63 Na2O 0.05 0.01 0.01 0.43 0.54 0.45 0.01 K2O - - - - - 0.01 0.01 NiO 0.19 0.24 0.25 0.03 0.02 0.06 0.06 Total
99.99 101.27 98.54 100.52 100.07 100.19 98.08

Mg# 0.85 0.86 0.85 0.82 Fo 81.75 81.57 81.69

An

48
Figure 4.7. (a-b) Pyroxene ternary diagram of Morimoto et al. (1988) showing orthopyroxene and clinopyroxene compositions
of the (a) peridotites and (b) gabbros from the southern Palawan Ophiolite.

49
 Figure

4.8. (a-b) Mg# versus Al2O3 and Al2O3 versus Cr2O3 of orthopyroxenes from the southern Palawan peridotites. Plots

for orthopyroxene Al2O3 versus Cr2O3in spinel harzburgites show lower Al 2O3 and show similar signatures with the forearc

peridotites. (c-d) Clinopyroxene Mg# versus Al 2O3 and TiO2from the southern Palawan peridotites and gabbros. Data source

used for the abyssal spinel peridotites are after Hamlyn and Bonatti (1980); impregnated plagioclase peridotites from Dick

and Bullen (1984), Takazawa et al. (1996), Takahashi (2001), and Dick et al. (2010); recrystallized plagioclase peridotites

from Pirnia et al. (2018); back-arc basin peridotites from Ohara et al. (2003). Data for forearc peridotites from Ishii et al.

(1992) and Parkinson and Pearce (1998), respectively.

50
4.3.4 Plagioclase

Plagioclase in the gabbroic rocks (An80-87) (Ca/[Ca + Na] = 80-87) are generally more

calcic than the plagioclase peridotites (An71-76) with a more sodic character. The plagioclase

in the plagioclase peridotites plot in the MOR field while those in the gabbros fall in the

MOR and arc gabbro fields. (Figs. 4.9c, d). It is also worth noting that line analyses of
plagioclase grains in the plagioclase peridotites revealed that they are compositionally

homogenous and unzoned (Appendix A). Intragrain compositional variations are also low as

signified by the error bars in the mineral chemistry plots (Figs. 4.6; 4.8; 4.9).

4.4 Trace element concentration

Trace element data have been widely used to model and interpret different

petrological processes operating beneath oceanic basins (e.g. Bizimis et al., 2000; Aldanmaz,

2009). The relative distribution of trace elements among major rock-forming minerals has

potentially provided useful and important information into various mantle petrogenetic

processes such as nature and degree of melting, fluid phase enrichment and reaction

refertilization processes (Hellebrand et al., 2005). Clinopyroxene, in particular, is identified

to be extremely refractory in nature and has preserved its high temperature chemical signature

(Bizimis et al., 2000). In addition, clinopyroxene is known to have high affinity for

incompatible elements which could significantly host REEs and other incompatible trace

elements (e.g., Johnson et al., 1990; Hellebrand et al., 2005). Hence, the trace element

abundances in clinopyroxene from peridotites and associated rocks have been extensively

used to infer melting processes in the upper mantle and have provided information for

interpreting mantle melting and conditions of melt formation and melt migration (Hellebrand

et al., 2005). In order to constrain the different mantle processes involved in the

51
Figure 4.9. (a) TiO2 vs Mg# in clinopyroxenes from the ultramafic (triangle) and mafic rocks (circles)

from southern Palawan. (b) Trend of increasing Al 2O3 vs decreasing Mg# in clinopyroxene. (c)

Olivine Fo content plotted against plagioclase An content. (d) Mg# of coexisting clinopyroxene and

plagioclase An content of the plagioclase peridotites and gabbroic rocks. Data for arc gabbros from

Niu et al. (2002); MOR gabbros from Elthon (1987) and Niu et al. (2002); BAB gabbros from Ohara

et al. (1996; 2002).

52
formation of the peridotites and gabbros from southern Palawan Ophiolite, trace element

concentrations are obtained from clinopyroxene and coexisting orthopyroxene. Trace element

compositions of clinopyroxene and orthopyroxene are reported in Table 3. Accuracy and

precision of the concentrations are within 12% and 13%, respectively, for all elements

(Appendix B). The trace element patterns of clinopyroxenes in the plagioclase peridotites,

spinel harzburgites (PALB-05) and gabbroic intrusions (PALB-03 and PALF-04) are parallel

to each other further indicating their genetic relation. They are characterized by depletion in

light rare earth elements (REEs) and relatively flat middle to heavy REE (Fig. 4.10a). They

also exhibit strong negative Sr, Zr and Ti anomalies and weak negative Eu anomaly (Eu/Eu*

= 0.85-1.15) that is more distinct in the gabbros (Fig. 4.10a). Peridotites have higher

concentrations of middle to heavy REE compared to the gabbros. These trace element

patterns have generally resembled present-day oceanic peridotites (e.g. Johnson et al., 1990;

Johnson and Dick, 1992; Dick and Natland, 1996; Hellebrand et al., 2002). In contrast, the

clinopyroxenes in the spinel harzburgites have a flat trace element pattern with significantly

lower MREE-HREE concentrations compared to the plagioclase peridotites (Fig. 4.10a).

They are also marked by depletion in Zr and Ti and enrichment in Sr and Eu (Eu/Eu* = 1.04-

1.60). Orthopyroxenes in spinel harzburgites are more depleted than those in plagioclase

peridotites in middle to heavy REE concentrations (Fig. 4.10b). Those in the plagioclase

peridotites also contain higher concentrations of middle to heavy REEs compared to the

gabbros. Orthopyroxene in spinel harzburgite meanwhile is significantly enriched in light

REEs.
 53
Table 4.3 Representative trace element composition of clinopyroxene and orthopyroxene in the plagioclase peridotites, spinel harzburgites and
olivine gabbro from southern Palawan Ophiolite. (-) means below detection limit.
Plagioclase lherzolite Plagioclase wehrlite Spinel harzburgite Clinopyroxene Orthopyroxene Clinopyroxene Clinopyroxene Sample PALB-01
PALB-01 PALB-01 PALB-01 PALB-04 PALB-04 PALB-04 PALB-09 PALB-09 102 103 101 111 201 202 203 301 302 Ti 2193 2468.04 987.86
1188.09 1831.30 1638.86 1784.97 102.49 105.08 Sr 5.30 4.89 0.44 0.10 5.36 3.72 4.69 17.65 15.72 Y 14.55 16.98 1.21 1.89 11.80 12.48 12.22 0.95
0.86 Zr 5.01 5.45 0.23 0.46 3.34 3.58 3.38 0.22 0.19 La 0.064 0.090 - - 0.063 0.062 0.067 0.04 0.05 Ce 0.54 0.76 - - 0.52 0.52 0.47 0.22 0.26 Pr 0.14
0.20 - - 0.13 0.14 0.12 0.04 0.05 Nd 1.02 1.65 - - 1.06 1.10 1.02 0.21 0.22 Sm 0.59 0.95 - - 0.65 0.65 0.60 0.06 0.06 Eu 0.31 0.42 - - 0.28 0.27 0.27
0.04 0.04 Gd 1.17 1.88 - - 1.11 1.27 1.11 0.08 0.08 Tb 0.28 0.38 - - 0.24 0.26 0.22 0.02 0.02 Dy 2.42 2.98 0.12 0.22 1.94 2.18 1.91 0.14 0.14 Ho 0.57
0.65 0.04 0.07 0.46 0.48 0.47 0.03 0.04 Er 1.87 2.10 0.20 0.28 1.46 1.52 1.52 0.12 0.11 Tm 0.29 0.33 0.05 0.06 0.22 0.23 0.24 0.02 0.02 Yb 2.02
2.29 0.47 0.55 1.65 1.59 1.84 0.16 0.17 Lu 0.29 0.33 0.09 0.10 0.23 0.24 0.26 0.03 0.03

54
Table 4.3 (continued)
Spinel
harzburgite Olivine gabbro
Clinopyroxene Orthopyroxene Clinopyroxene Orthopyroxene Sample PALB-05 PALB-05 PALB-09 PALB-05 PALB-05 PALJ-03 PALJ-03 PALJ-
03 PALB-03 PALB-03 101 104 311 112 113 401 402 403 601 611 Ti 217.23 264.29 51.39 191.03 199.34 1407.22 1397.49 1186.15 1755.04 886.12
Sr 34.35 20.96 0.69 1.20 1.10 3.07 2.98 2.98 4.21 0.84 Y 9.02 9.64 0.08 0.96 0.98 6.91 7.02 6.89 10.55 1.15 Zr 7.86 8.48 0.03 0.96 1.10 6.48 5.57
5.39 3.82 0.30 La 0.27 0.33 - - - 0.10 0.09 0.11 0.06 - Ce 1.62 1.98 - - - 0.70 0.65 0.74 0.50 - Pr 0.35 0.43 - - - 0.15 0.15 0.17 0.14 - Nd 2.14 2.66 - -
- 1.06 1.02 1.09 1.10 - Sm 0.87 1.063 - - - 0.48 0.49 0.48 0.67 - Eu 0.35 0.42 - - - 0.19 0.18 0.22 0.27 - Gd 1.23 1.45 - - - 0.83 0.91 0.83 1.29 - Tb
0.22 0.26 - - - 0.19 0.16 0.17 0.24 - Dy 1.63 1.92 0.01 0.11 0.13 1.24 1.23 1.27 1.92 0.14 Ho 0.34 0.39 - 0.03 0.03 0.27 0.29 0.26 0.43 0.04 Er 0.99
1.15 0.02 0.13 0.14 0.78 0.79 0.81 1.26 0.17 Tm 0.15 0.16 - 0.03 0.03 0.11 0.12 0.13 0.19 0.03 Yb 0.95 1.04 0.04 0.25 0.26 0.76 0.80 0.86 1.23
0.29 Lu 0.12 0.15 0.01 0.05 0.05 0.12 0.11 0.12 0.17 0.05

55
 (a) (b) Figure 4.10. (a) Chondrite-normalized trace element compositions of (a) clinopyroxenes and (b)
orthopyroxenes in the spinel harzburgite, plagioclase peridotites and olivine gabbros from southern Palawan Ophiolite.
Plagioclase peridotite and gabbros have distinct signature showing strong depletion in LREE and relatively flat MREEs-HREEs
and Sr and Eu negative anomalies. Chondrite normalization values are from Sun and McDonough (1989). Data for the abyssal
peridotites are from Johnson et al. (1990), Johnson and Dick (1992), Dick and Natland (1996) and Hellebrand et al. (2002);
BAB peridotites are from Ohara et al. (2002; 2003). Fields for SSZ peridotites are after Ishii et al. (1992) and Parkinson et al.
(1992).

56
4.5 Geothermometry and oxygen fugacity

The coexistence of high-Ca pyroxene (clinopyroxene) and low-Ca pyroxene has long

been recognized to potentially yield thermometric information for a wide variety of rocks

(Lindsley, 1983; Hellebrand et al., 2005). This is due to the solubility between the high- and

low-Ca pyroxenes as temperature decreases. In particular, the Ca content of high-Ca

pyroxene has decreased with increasing temperature, while consequently increased to that of

the low-Ca phase (Lindsley, 1983; Hellebrand et al., 2005). Ca partitioning of two pyroxenes

is also accompanied by the distribution of Fe and Mg between the high- and low-Ca

pyroxenes (Kretz, 1982). Experimental studies have shown that a transfer-exchange reaction

may have taken place between Ca-Mg-Fe2+ ratio of two pyroxene minerals resulting from a

changed in temperature (Kretz, 1982). For these reasons, the Ca-Mg-Fe pyroxene relationship

has been widely employed as a geothermometer for obtaining temperature conditions during
which the rocks have crystallized and formed. Equilibration temperature in spinel peridotites,

dunites and plagioclase peridotites was estimated using the two pyroxene geothermometer of

Putirka (2008). Orthopyroxenes are identified to be significantly less common in the gabbros

and only an initial estimate of their equilibration temperature can be provided. The formula

employed is based on Brey and Köhler (1990) which used the mutual solubility of Ca and Mg

and Fe/Mg partitioning between coexisting clinopyroxene and orthopyroxene. New global

regression data was used to calibrate and increase the precision of the Brey and Köhler (1990)

thermometer. Pressure estimates are not included in this study as most pyroxenes exhibited

exsolution lamellae indicative of subsolidus reequilibration at lower pressure conditions.

o
The calculated temperature for the plagioclase lherzolite (=957 ± 48 C) and

plagioclase harzburgite (= 949 ± 24 oC) although slightly higher than the spinel harzburgites

(= 888 ± 48 oC) are still within the range of the latter. These equilibration temperature values

57
are noted to be comparable to other suprasubduction zone ophiolites, IBM forearc (921 oC;

Okamura et al., 2006) and mantle wedge-derived xenoliths (Arai and Ishimaru, 2008) and are

considered to be lower than abyssal peridotites (1139 oC; Dick, 1989). The equilibration

temperature for the troctolite (933 oC) and olivine gabbros (= 961 ± 23 oC) are also known to

be within the range of typical high temperature cumulates formed from primitive magmas

(e.g. Niu et al., 2002; Alonso-Perez et al., 2009).

The oxygen fugacity (fO2) of the mantle is considered an important parameter for

determining the oxidation state of a system, which is thought to vary due to partial melting

and post-metasomatic processes (Parkinson and Arculus, 1999). Notably, samples of

exhumed mantle xenoliths and mantle peridotites recovered from lavas and pyroclastic rocks

in island arcs are mostly oxidized relative to other tectonic settings (e.g., Arai and Ishimaru,

2008; Payot et al., 2018; Valera et al., 2019). This in part reflects the tectonic environment in

which the ophiolitic rocks of the southern Palawan Ophiolite may have formed. The oxygen

fugacity (fO2) of the dunite, spinel harzburgites and plagioclase peridotites of the southern

Palawan Ophiolite is calculated using the olivine-orthopyroxene-spinel oxygen barometer of

Ballhaus and others (1990). The calculation of fO2 depends on the pressure and temperature

of equilibrium of the samples. A pressure of 1.5 GPa was used based on the stability of spinel
in mantle peridotites (Green and Ringwood, 1967). Assuming 1.5 GPa, the calculated fO2 for

the plagioclase peridotites falls within a narrow range of Δlog(fO2)FMQ = +1.3 to +2.0 where

Δlog is a log unit difference in oxygen fugacity from the fayalite-magnetite-quartz (FMQ)

buffer. The dunites and spinel harzburgites exhibit a wider spread of oxygen fugacities

[Δlog(fO2)FMQ = -1.75 to +2.2] but are indistinguishable from the plagioclase peridotites (Fig.

4.11). Such values are considered high and broadly consistent with arc peridotites

[Δlog(fO2)FMQ = -0.2 to +1.9 (Parkinson and Arculus, 1999)] and to mantle wedge-derived

xenoliths exhumed throughout the western Pacific island arcs (e.g. Arai and Ishimaru, 2008).

58

Figure

4.11. Histograms of the calculated oxygen fugacity (fO2) of the spinel harzburgites, dunites

and plagioclase peridotites from the southern Palawan Ophiolite. Oxygen barometry of Ballhaus et al.

(1991) was used for calculation.

 59

Chapter 5
Mantle depletion and
melt-rock interaction

60
CHAPTER 5

MANTLE DEPLETION AND MELT-ROCK INTERACTION

5.1 Petrogenesis of spinel harzburgites and dunites

Peridotites formed either in mid-oceanic ridges and subduction zone settings have
provided fundamental information on the different tectono-magmatic processes involved in

their formation (e.g. Choi et al., 2008; Uysal et al., 2014; Rizeli et al., 2016). Studies on

abyssal peridotites have shown that they represent solid residues of fractional melt extraction

as a result of adiabatic decompression forming and producing mid ocean ridge basalt

(MORB) (e.g. Johnson et al., 1990; Dick and Bullen, 1984). Peridotites in arc settings,

however, are formed by hydrous melting of the oceanic upper mantle above a subducting slab

coupled with the enrichment components originating from either the sediments and/or the

basaltic crust of the subducting slab (Pearce et al., 1984; Bizimis et al., 2000; Bonev and

Stampfli, 2008). However, isotopic variations in the peridotites have demonstrated the

compositional heterogeneity in the mantle which indicated that peridotites were not simply

the residues of fractional melting (e.g. Johnson and Dick, 1992; Hellebrand et al., 2002;

Warren and Shirey, 2012). Instead their composition is often altered by fluid phase

enrichment and mantle-melt interaction processes subsequent to melt extraction (e.g.

Kelemen et al., 1992; Bizimis et al., 2000; Warren, 2016). Hence, the occurrence of

refractory peridotites as well as crustal materials (i.e., gabbros and basalts) is considered as a

significant source of information to gain insights about the composition and melting

processes in the Earth’s upper mantle. For instance, SSZ peridotite samples have provided the

best indication on the composition of the mantle wedge above subduction zones (Choi et al.,

2008). These peridotites are characterized by spinels with significantly higher Cr#s (38-80)

61
than abyssal peridotites. Spinel Cr#, in particular, was an important petrogenetic indicator of

the degree of partial melting a peridotite has undergone (e.g. Arai, 1994; Choi et al., 2008;

Guotana et al., 2017). Moreover, the strong correlation between high spinel Cr# with

decreasing Mg# indicated re-equilibration of spinel and olivine to low temperatures which is

considered to be distinguishable to SSZ peridotites (Dick and Bullen, 1984). The association

of these characteristics with high degrees of partial melting is also confirmed by the

chemistry of pyroxenes that are characterized by extremely low minor elements (Al, Na, Ti)

and enrichment in LILEs (such as Cs, Rb, Ba, Th, K, Sr and Pb) (Pearce et al., 1984; Choi et

al., 2008).

The dunite and spinel harzburgite, except PALB-05, of the southern Palawan
Ophiolite typify residual mantle peridotites formed above a subduction zone. The slightly

deformed textures and the refractory mineral composition of the spinel harzburgites and

dunite indicate that these are residues of mantle melting. They exhibit protogranular to

porphyroclastic texture and are composed of magnesian olivine and high Cr#-low Mg# spinel

with low concentration of TiO2 in spinel (Figs. 4.6a,b). Estimates of their degree of partial

melting using spinel Cr# put them at approximately ~30-40% (Fig. 4.6a). These highly

refractory peridotites are identified as characteristic of mantle wedge materials typically

preserved in suprasubduction zone ophiolites (Rizeli et al., 2016; Guotana et al., 2017) or arc

xenoliths (Arai and Ishimaru, 2008). This is also evidenced by the low concentration of TiO 2

and Al2O3 in the pyroxenes (Figs. 4.8a-d). Unlike other spinel harzburgites, sample PALB 05,

however, records contrasting signatures indicating secondary processes involved in its

formation. This sample is characterized by its peculiar texture as shown by the embayed

contact between olivine and orthopyroxene grains (Fig. 4.3c). Also, they exhibit

characteristics similar to plagioclase peridotites rather than spinel harzburgites (Figs. 4.6b-d).

62
The depletions in Zr, Ti, and middle to heavy REEs in the clinopyroxenes of spinel

harzburgites as well as the low REE concentrations of both in clinopyroxene and

orthopyroxene also suggest that they underwent high degrees of partial melting (Figs.

4.10a,b). Unlike typical residual peridotites, however, their elevated LREE patterns and

positive Sr anomalies in clinopyroxene suggest enrichment of these components by the

subsequent modification of the harzburgites. This modification is likely by subduction

components (e.g. slab-derived fluids) similar to the IBM forearc (Ishii et al., 1992; Parkinson

et al., 1992). The slight positive Eu anomaly in the clinopyroxene in the spinel harzburgites is

noted to be remarkable since Eu behaved incompatibly during mantle melting (Sun and

Liang, 2012). Experimental studies have shown that the partitioning of Eu in mantle minerals

is affected by oxygen fugacity conditions (e.g. Sun et al., 1974). The high oxygen fugacity

[Δlog(fO2)FMQ = -0.2 to +1.9] of the spinel harzburgites suggests that these harzburgites were

generated by partial melting under oxidizing conditions above a suprasubduction zone (Fig.

4.11). Lastly, the clinopyroxene Ti vs. Dy diagram (Fig. 5.1) shows the spinel harzburgite
located near the clinopyroxene-out end of the melting curve consistent with at least 25%

partial melting.

5.2 Petrogenesis of plagioclase peridotites

The formation of plagioclase peridotites is noted to be more complex than that of

spinel harzburgites. Earlier works on the origin of plagioclase peridotites established two

petrogenetic models for their origin: (1) metamorphic recrystallization during subsolidus

decompression of mantle peridotites from pre-existing spinel facies to plagioclase facies

assemblage through reaction involving orthopyroxene + clinopyroxene + Al-spinel = olivine

+ plagioclase (Hamlyn and Bonatti, 1980; Rampone et al., 1993; Borghini et al., 2010) or (2)

interaction-reaction between a residual peridotite and percolating melts through reaction of

63
melt + Al-spinel = plagioclase + Cr-spinel (e.g. Dick and Bullen, 1984; Rampone et al., 1997;

Bodinier et al., 2008).

Figure 5.1.

Clinopyroxene Ti vs Dy composition. Trend for partial melting shows residual

clinopyroxene compositions during anhydrous melting. Numbers along the line represent percent

melting. Partial melting trend after Hellebrand et al. (2001). Background data from Bizimis et al.

(2000) and Ohara et al. (2002; 2003).

The subsolidus reequilibration model resulted from the cold tectonic exhumation of

lithospheric mantle during thinning of the overlying crust-mantle material. Peridotites formed
through this process are commonly found in rift zones such as in mid-oceanic ridges

(Borghini et al., 2010; Pirnia et al., 2018). Plagioclase in these peridotites is noted to occur

either as symplectites around spinel grains or as exsolution in clinopyroxene together with

orthopyroxene (e.g. Pirnia et al., 2018). Plagioclases are formed as retrograde breakdown

reaction products of clinopyroxene, orthopyroxene and spinel in the peridotites (e.g.

Takahashi, 1996; Ohara et al., 2003). Plagioclase and pyroxene created through this process

64
show prominent compositional zonation (Rampone et al., 1993; Borghini et al., 2010; Pirnia

et al., 2018). On the other hand, peridotites produced by melt-rock interaction are typically

formed during migration, entrapment and crystallization of basaltic melts in porous peridotite

material (e.g. dunites) usually close to the mantle-crust boundary (Kelemen et al., 1992;

Piccardo, 2007; Müntener et al., 2010). This type of plagioclase peridotite is more commonly

found in abyssal peridotites (e.g. Dick, 1989; Barth et al., 2003; Loocke et al., 2013) although

also documented in back-arc-basin peridotites (e.g. Ohara et al., 2002; 2003; Sato and Ishii,

2011; Sanfilippo et al., 2013). Plagioclase formed through this process is typically known to

occur as blebs or interstitial patches confined within grain boundaries of preexisting minerals

(Rampone et al., 1997; Piccardo et al., 2007). Other microtextures that are associated with

melt-rock interaction include the presence of interstitial clinopyroxene and/or orthopyroxene

around plagioclase grains (Rampone et al., 1997).

Plagioclase peridotites of the southern Palawan Ophiolite show textural and

geochemical evidence consistent with a melt-rock interaction origin. The textural features of

the plagioclase peridotites are characterized by: (1) the intergrowth of subhedral bleb-like

plagioclase (± spinel) and interstitial clinopyroxene (Fig. 4.3e); and (2) the lobate or irregular

outlines of the surrounding orthopyroxene and olivine (Fig. 4.3f). These petrographic

characteristics are noted to be similar to ophiolitic mantle rocks with plagioclase and other

melt relicts (e.g. Menzies, 1973; Barth et al., 2003). The occurrence of gabbroic dikes cutting

the plagioclase peridotites indicates that subsequent melts have intruded and reacted with the

residual peridotites. Similar to plagioclase peridotites, sample PALB-05 that is locally cut by

a gabbroic dike (PALF-04), generally preserved dissolution textures as recorded by the

involvement of migrating melts with the residual peridotites.

The chemistry of the minerals comprising the peridotites is also consistent with a

melt-rock interaction origin. The plagioclase peridotites, spinel harzburgites and dunite are

65
composed of the same high Cr# spinel suggesting that these peridotites experienced the same

high degrees of partial melting. However, olivine in the plagioclase peridotites and in PALB

05 is less magnesian. Consequently, these plot away from the partial melting trend and

outside the olivine-spinel mantle array (Fig. 4.6a) (Arai, 1994). This signature is noted to

suggest late-stage processes affecting plagioclase peridotites and PALB-05 such as chemical

refertilization of lithospheric mantle material to equilibrate with impregnating melts

(Rampone et al., 1997; Barth et al., 2003; Piccardo et al., 2007; Dygert et al., 2016).

Furthermore, spinel composition has recorded incomplete chemical equilibration of these

peridotites with the impregnating melt. Equilibration with Fe-rich silicate melts has shifted

spinel compositions toward lower Mg# as seen in the plagioclase peridotites (Fig. 4.6b) (Dick

and Bullen, 1984; Cannat et al., 1990). This interpretation is supported by the elevated TiO 2 in

spinel grains of these peridotites compared to the spinel harzburgites which suggested

secondary addition by significant volumes of impregnating melt (Fig. 4.6c) (Cannat et al.,

1990). The Fe-Ti trend seen in plagioclase peridotites (Figs. 4.6c-d) is noted to indicate a

purely low-pressure fractionation trend similar to the Fe-Ti enrichment in harzburgites

observed from Garrett Deep and Hess Deep which are affected by melt-rock interaction

processes (e.g. Cannat et al., 1990; Arai and Matsukage, 1996). Clinopyroxenes in

plagioclase peridotites and in PALB-05 are also chemically distinct, with higher TiO2, Na2O

and Al2O3 contents compared to clinopyroxenes in spinel harzburgites and dunite (Figs.

4.8c,d). Plagioclase in these lithologies is also chemically unzoned (Appendix A). These

signatures are considered to be comparable to abyssal plagioclase peridotites (e.g. East

Pacific Rise, Kane Megamullion, and Godzilla Megamullion Oceanic Core Complexes) (Arai

and Matsukage, 1996; Dick et al., 2010, Loocke et al., 2013) and back-arc plagioclase

peridotites and gabbros (e.g. Parece Vela Basin and Mariana Trough) (Ohara et al., 2003;

Ohara, 2006; Sato and Ishii, 2011; Sanfilippo et al., 2013). These are believed to be products
 66
of refertilization of residual peridotites with migrating liquids at shallow pressures (Ohara et

al., 2003; Sato and Ishii, 2011).

5.3. Petrogenetic model and the nature of the impregnating melts

The high degree of partial melting recorded in spinel harzburgites suggests that they

represent mantle material beneath either the forearc or the main arc region. This was

eventually emplaced as the Palawan Ophiolite. Petrogenetic indicators (e.g. high spinel Cr#-

low Mg#, high TiO2 contents) further suggest that the plagioclase peridotites were originally

derived from the same highly depleted spinel harzburgites which reacted with migrating

melts. We therefore suggest a multistage reaction process which formed the plagioclase

peridotites, PALB-05 and gabbros (Figs. 5.2a-d).

The distinct geochemical signatures of the plagioclase peridotites, PALB-05, and the

associated gabbroic rocks (PALB-03, PALB-02 and PALF-04) suggest that they were formed

by a complex process that involved both fractional crystallization from a basaltic melt

migrating through the upper mantle and its reaction with the surrounding peridotite wall rock.

The proposed interaction is considered to be similar to the combined concept of partial

melting and crystal fractionation which concentrated incompatible elements (K, Ti, REE,

etc.) in the melt during reaction with the peridotite wall rock (e.g. Quick, 1981; Arai et al.,

1997). The process that is involved in the formation of the plagioclase peridotites, PALB-05,

and the associated gabbroic rocks (PALB-03, PALB-02 and PALF-04) included the

crystallization of a basaltic melt and the dissolution of orthopyroxene in an originally

depleted spinel harzburgites to form dunitic pods (e.g. Arai and Matsukage, 1996; Dick and

Natland, 1996) (Figs. 5.2a-d). This is given by the following reaction:

orthopyroxene + melt1 🡪 olivine + clinopyroxene + plagioclase + melt2

67
Figure 5.2. (a) Schematic diagram showing the petrogenetic processes involved in the formation of spinel harzburgites, dunites

and plagioclase peridotites. The box in A shows the location where these processes take place. (b) Spinel harzburgites represent

residual peridotites after high degrees of partial melting above a subduction zone. (c) Addition of olivine-saturated melt

promotes incongruent melting of orthopyroxene and crystallization of olivine at the expense of orthopyroxene. (d) Intrusion of

gabbroic dikes with MORB-like composition allows reaction with the host dunites which leads to the formation of plagioclase

peridotites. Sketch of the textural evolution of peridotites is modified after Basch et al. (2018) and Rospabé et al. (2018).

68
Spinel harzburgites represent original residual mantle peridotites subsequently affected by

melt-rock interaction (Fig. 5.2b). As the melt (melt 1) ascends through the upper mantle,

olivine is fractionated from the melt due to the incongruent breakdown of orthopyroxene

which eventually formed dunite (Fig. 5.2c). Incongruent melting of mantle orthopyroxene in

residual spinel harzburgites is known to promote the crystallization of olivine by dissolving

pyroxene from the mantle as it migrated upwards because the high-pressure melt was

undersaturated with pyroxene components and oversaturated with olivine at low pressures
(e.g. Kushiro, 1968; Basch et al., 2018; Rospabé et al., 2018). Some of these spinel

harzburgites, however, still preserved their orthopyroxenes. The dunite formed through

incongruent melting and subsequent fractionation may have acted as preferential pathways

for migrating melts and the melt (melt2) produced by this interaction gradually became

pyroxene-saturated owing to the dissolution of mantle pyroxenes at lower pressures (Fig.

5.2d) (e.g. Rampone et al., 1997; Sanfilippo et al., 2013). However, direct crystallization of

interstitial minerals from the melt may have caused progressive clogging of the pathways and

forced the migrating melts to intrude along cracks and fractures (Piccardo, 2003). These

cracks and fractures then provided a high permeability pathway for melt to rise through the

shallow mantle toward the crust (Dick and Natland, 1996). As the melt (melt 2) continues to

migrate, the secondary melt (melt2) formed through this process will become enriched with

some incompatible elements (such as Ti) and Cr to precipitate chromian spinel,

clinopyroxene and plagioclase into the porous dunite-forming plagioclase peridotites (Fig.

5.2d). The Cr# of the melt thus would remain constant due to the counteraction between the

crystallization of chromian spinel and the dissolution of orthopyroxene which is high in Cr

supply (e.g. Arai and Matsukage, 1996). The Ti enrichment observed in spinel and

clinopyroxene is caused by the condensation of incompatible elements in these peridotites.

This may have occurred due to crystal accumulation during interaction of the most evolved

69
melt (melt2) in the peripheral region of the surrounding peridotite (e.g. Arai and Matsukage,

1996; Fig. 5.2d). This process is likely considered to occur within a closed system or within

melt-stagnant conduits because the melt could evolve through interaction with the wall rock

peridotite concentrating more incompatible elements in the melt (e.g. Arai and Matsukage,

1996; Arai et al., 1997). This is noted to be comparable to the formation of the ultramafic

mafic plutonic rock suites in East Pacific Rise and Mid-Cayman Trough which were products

of melt-rock interaction process (e.g. Arai and Matsukage, 1996; Dick and Natland, 1996;

Arai et al., 1997). The final products of this multi-stage reaction process are now preserved as

plagioclase harzburgites, plagioclase lherzolites, plagioclase wehrlites and the gabbroic

intrusions that cut those plagioclase peridotites. Common field occurrences associated with

plagioclase peridotites grade from residual harzburgites to gabbroic rocks through

intermediate dunites. This rock suite is characterized by ragged or gradational contacts within

the boundaries of various lithologies formed from this process as seen in peridotites from

Hess Deep (Arai and Matsukage, 1996). In this study, gradational contact between

plagioclase peridotite and gabbroic intrusions are not observed. Instead these peridotites are

cut by tabular gabbroic dikes showing sharp planar contacts. This is similar to the Alpine

Apennine peridotites where gabbroic veins and dikes intruding the impregnated peridotites

show sharp contacts and chilled margins (e.g. Müntener and Piccardo, 2003; Piccardo, 2003).

Some of the spinel harzburgites intruded by several gabbroic dikes only experienced cryptic

metasomatism. This would explain the peculiar signature of PALB-05. Sample PALB-05 is

characterized by low contents of forsterite (Fig. 4.6a) and NiO in olivines, high spinel TiO 2

(Fig. 4.6c), and high Al2O3, TiO2 concentration in the low Mg# pyroxenes similar to

plagioclase peridotites (Figs. 4.8a-d). This is also supported by the occurrence of tabular

gabbroic dike (PALF-04) cutting through PALB-05. This gabbro is characterized by anhedral

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clinopyroxenes that are generally replaced by amphibole further suggesting post-metasomatic

processes involved after its formation.

The reaction-refertilization model also explains the enriched trace element (i.e. middle

to heavy REE) concentration of clinopyroxenes and orthopyroxenes in the plagioclase

peridotites with respect to their precursor spinel harzburgites and their overlapping

concentrations with those in the olivine gabbro (PALB-03 and PALF-04) (Figs. 4.10a,b). The

model also resolves the apparent contrast in the degree of partial melting recorded in the

spinel (~30%) and those estimated from the clinopyroxenes (<10%; Fig. 5.1). Their similar

equilibration temperatures and oxygen fugacities with those calculated for the spinel

harzburgites further supports the model.

The nature of these impregnating melts is constrained by looking at the characteristics

both of the plagioclase peridotites and the troctolite (PALB-02) and olivine gabbros (PALB

03 and PALF-04). Both the gabbroic dikes (PALB-02) and gabbroic pod (PALB-03) are

characterized by ragged and irregular textures (Figs. 4.5d-f). These observations are
commonly interpreted as reaction between melts and crystals where disequilibrium may have

resulted to dissolution and embayed habits of co-existing minerals (Lissenberg et al., 2016).

These reaction textures are noted to be similar to the gabbroic rocks found in the Hess Deep

and Kane Megamullion Oceanic Complexes, which contained evidence for melt-rock

interaction (e.g. Dick et al., 2010; Lissenberg et al., 2016). In addition, the interstitial

occurrence of clinopyroxene and subhedral shape of plagioclase in the plagioclase peridotites

suggest crystallization of plagioclase ahead of clinopyroxene. The same crystallization order

is preserved in the troctolite and olivine gabbros where olivine fractionation likely occurred

along with plagioclase. This order of crystallization is characteristic of anhydrous MOR

derived melts. Fractional crystallization of MORB at low pressure has crystallized

clinopyroxene after olivine and plagioclase (Burns, 1985). As a result, the Mg# of

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