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Coexistence of high-Al and high-Cr chromite orebodies in the Acoje block of

the Zambales ophiolite, Philippines: Evidence for subduction initiation

Peng-Fei Zhang, Mei-Fu Zhou, Graciano P. Yumul Jr.

PII: S0169-1368(20)30353-X
DOI: https://doi.org/10.1016/j.oregeorev.2020.103739
Reference: OREGEO 103739

To appear in: Ore Geology Reviews

Received Date: 9 April 2020

Revised Date: 15 August 2020
Accepted Date: 23 August 2020

Please cite this article as: P-F. Zhang, M-F. Zhou, G.P. Yumul Jr., Coexistence of high-Al and high-Cr chromite
orebodies in the Acoje block of the Zambales ophiolite, Philippines: Evidence for subduction initiation, Ore
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Coexistence of high-Al and high-Cr chromite orebodies in the Acoje block

of the Zambales ophiolite, Philippines: Evidence for subduction initiation

Peng-Fei Zhanga, Mei-Fu Zhoub, a*, Graciano P.Yumul Jr.c

a. School of Earth Resources, China University of Geosciences, Wuhan, China

b. Department of Earth Sciences, The University of Hong Kong, Hong Kong, China

c. Cordillera Exploration Company, Inc., NAC Tower, BGC, Taguig City, Philippines

* Corresponding author: Mei-Fu Zhou

E-mail: mfzhou@hku.hk
Abstract

The Acoje block of the Eocene Zambales ophiolite (NW, Philippines) is a fragment of

forearc lithosphere in the Western Pacific and hosts a world-class chromite deposit.

The compositions of chromitites, dunites and harzburgites in the block are used to

explore origin of ophiolitic chromite deposits during subduction initiation. Chromite

grains in these rocks have a large range of Cr# [100×Cr/(Cr+Al)]. Those in the

cpx-rich harzburgites have the lowest Cr# range (15-35). Those in the chromitites

have a bimodal Cr# distribution, ~ 45-48 and 73-76, confirming presence of both

high-Al and high-Cr chromitites in the block. Those in the cpx-poor harzburgites and

dunites have similar Cr#s, ranging from ~ 35 to 85. The TiO2 contents of chromite

grains are generally < 0.25 wt.% and increase from the cpx-rich harzburgites to

cpx-poor harzburgites, dunite and chromitites. Olivine grains in all the rocks have

forsteritic compositions (Fo, 90-93) and δ18O values consistent with that of the upper

mantle (+5.18±0.20). The oxygen fugacities (fO2) of the harzburgites, dunites and

chromitites range from ~ -0.5 log unit below the fayalite-magnetite-quartz (FMQ)

buffer to ~ 1.5 log unit above the buffer, generally comparable to or slightly higher

than the range of abyssal peridotites. The dataset reveals that parental magmas of the

high-Cr chromitites have boninitic affinities, whereas those of the high-Al chromitites

have compositions intermediate between MORB and boninitic lavas. Both types of
chromitites originated from mantle sources that may have moderately refractory

compositions equivalent to residues after ~ 10% melting of fertile MORB mantle,

accounting for the low TiO2 contents of chromite in the chromitites. The Acoje mantle

wedge was infiltrated by small amounts of slab-derived fluids, which were

insufficient to elevate the fO2 values of peridotites but notably facilitated partial

melting in mantle sources of the chromitites. The Acoje mantle sequence was

modified by parental magmas of both the high-Al and high-Cr chromitites, causing

two different chemical variation trends of peridotites. Peridotites and chromitites in

the Acoje mantle sequence record evolving magmatism changing from early

MORB-like to later boninitic features, comparable to those developed in the infant

IBM arc system, and relevant information can be used for reconstructing the

geodynamic evolution of subduction initiation.

Keywords: Acoje block, chromite deposit, slab components, melt-peridotite reaction,

subduction initiation.

1. Introduction

Subduction plays an important role in driving global plate tectonics (e.g.,

Bercovici, 2003; Stadler et al., 2010), and its initiation is thought to be caused by

spontaneous or induced subsidence of denser oceanic lithosphere into underlying

asthenosphere, accompanied by a variety of processes including asthenospheric

upwelling and slab dehydration (Hall et al., 2003; Stern and Bloomer, 1992; Ueda et

al., 2008). Studies of the Eocene Izu-Bonin-Mariana (IBM) arc system have revealed

that volcanic rocks formed during subduction initiation evolve from early MORB-like

to later boninitic compositions (Reagan et al., 2010, 2019; Ishizuka et al., 2020),

comparable to the volcanic sequences of several well-preserved fore-arc ophiolites

(Fig. 1A; Whattam and Stern, 2011; Stern et al., 2012). Although such volcanic

sequences are thought to reflect the change of magma sources from lherzolitic to

harzburgitic mantle and an intensified slab input with time during subduction

initiation (Reagan et al., 2010, 2019; Whattam and Stern, 2011; Stern et al., 2012),

fore-arc ophiolites often have no well-kept crustal sequences because of tectonic

fragmentation, and it is impossible to testify their subduction initiation origin by using

lavas. Moreover, the subduction initiation-related processes have not been well

investigated from the mantle perspective, and it still remains unclear how nascent

mantle wedges respond to the changing magmatism during subduction initiation.

Supra-subduction zone (SSZ) ophiolites, especially forearc ones, are increasingly

thought to be generated during subduction initiation, and their mantle sequences can

be considered as the remnants of nascent mantle wedges in newly-initiated subduction

zones (Casey and Dewey, 1984; Wallin and Metcalf, 1998; Stern, 2004; Whattam and

Stern, 2011; Stern et al., 2012). Chromite deposits are the main economically valuable
resources of ophiolites and are commonly distributed along the petrological Moho

boundaries of SSZ ophiolites (Dickey, 1974; Stowe, 1994; Zhou and Robinson,

1997). These deposits can be further divided into high-Al and high-Cr varieties, in

which chromite grains have Cr#s higher and lower than 60, respectively (Thayer,

1964; Leblanc and Violette, 1983; Zhou et al., 1994; Arai and Miura, 2015). Origin of

ophiolitic chromite deposits have usually been attributed to melt-peridotite reactions

at the uppermost mantle (Zhou et al., 1996, 1998; Arai, 1997; Ahmed and Arai. 2002;

Ahmed and Habtoor, 2015; Uysal et al., 2009, 2015, 2018), and the parental magmas

of high-Al and high-Cr chromitites are thought to have MORB-like and boninitic

compositions, respectively (Zhou et al., 1996, 1998; Uysal et al., 2009). Accordingly,

formation of high-Al and high-Cr chromite deposits theoretically involves reactions

between mantle peridotites and melts with MORB-like to boninitic compositions,

sharing similar magmatic features to the lava sequence of the IBM arc system. Thus,

chromitites and peridotites in ophiolitic mantle sequences possibly record melt events

that are related to subduction initiation, and investigating the origin of ophiolitic

chromite deposits and relevant melt histories would potentially help to testify if the

mantle sequences of SSZ ophiolites record as effective messages of subduction

initiation as in the crustal sequences.

The Zambales ophiolite in the NW Luzon island of Philippines is a lithospheric

fragment of the West Pacific Ocean (Fig. 1A). The Acoje block in this ophiolite

shows forearc affinity and hosts a world-class chromite deposit (Fig. 1B; Hawkins and

Evans, 1983; Leblanc and Violette, 1983; Hock and Friedrich, 1985; Yumul and

Balce, 1994), and has a well-preserved profile from the mantle to crustal sequences

(Hawkins and Evans, 1983; Rossman et al., 1989). With these features, the Acoje

block is ideal for studying the chromitite mineralization during subduction initiation.

In this study, we present a new dataset of major element and oxygen isotopic

compositions for minerals in chromitites and peridotites from the block. The dataset is

used to investigate the origins of parental magmas of chromitites and effects of those

parental magmas on peridotites in the block. These messages are further used for

exploring subduction initiation-related magmatic evolution recorded in the mantle

sequence of the block.

2. Geological background

The Zambales ophiolite is a large allocthonous terrane along the western margin

of the Luzon Island, Philippines (Fig. 1A-B). It extends ~ 130 km long from the

Lingayen Gulf in the north to the Subic Bay in the south and covers an overall area of

~ 4500 square km (Hawkins and Evans, 1983; Abrajano et al., 1989; Yumul et al.,

1998). Divided by graben structures, three distinct massifs have been recognized in

the ophiolite and are named Masinloc massif, Cabangan massif, and San Antonio
massif from north to south, respectively (Fig. 1B). The Masinloc massif can be further

divided into the Acoje block in the north and Coto block in the south (Fig. 1B;

Leblanc and Violette, 1983; Hock and Friedrich, 1985; Abrajano et al., 1989). The

Acoje block has been considered to be formed at ~ 44-43 Ma in a forearc setting

(Hawkins and Evans 1983; Geary et al., 1989; Yumul et al. 1998; Encarnaciȏn et al.,

1999), and it hosts a world-class high-Cr chromite deposit with a reserve up to ~ 25

Mt (Yumul and Dimalanta, 1997; Xiong et al., 2013). This block can be classified

stratigraphically into four sequences from the west to east: an upper mantle sequence,

a Moho transition zone (MTZ), an ultramafic-mafic cumulate sequence and a

hypabyssal-volcanic sequence (Fig. 1C; Hawkins and Evans 1983; Leblanc and

Violette 1983; Yumul, 2001; Abrajano et al., 1989).

The upper mantle sequence is ~ 10 km thick and mainly made of harzburgites.

These harzburgites include both cpx-rich and cpx-poor varieties and have undergone

varying degrees of serpentinization (Fig. 2A, B). According to Leblanc and Violette

(1983), there is a decreasing trend of pyroxene modal% from the bottom to top of the

mantle sequence (Fig. 1C). Cpx-rich harzburgites are mainly distributed at the lower

stratigraphic level of the mantle sequence, ~ 4 to 10 km below the petrological Moho

according to Evans and Hawkins (1983), whereas cpx-poor harzburgites are mainly

found at the upper stratigraphic level of the mantle sequence. Cpx-poor harzburgites
at the topmost mantle sequence also contain cpx-rich harzburgite lenses (e.g., Stop 6#

in Fig. 1C) and abundant dunite bodies. Chromitite pods are locally found enveloped

by dunites in harzburgite hosts (Fig. 2B-D; Leblanc and Violette 1983; Bacuta et al.

1990). The MTZ, ~ 500 m thick, is mainly made of dunites and locally contains

chromitite layers and websterite bodies (Fig. 2E; Leblanc and Violette 1983; Bacuta et

al. 1990). Overall, chromite orebodies are distributed near the petrological Moho

either in the uppermost mantle sequence or in the lower MTZ, and chromitites in the

orebodies mostly belong to the high-Cr variety. However, high-Cr and high-Al

chromitites can be found occasionally together in same mining areas (e.g., Stop 6# in

Fig. 1C). Because of intensive weathering, high-Al chromitites can only be found as

fragment in the soils (Fig. 2C). The MTZ dunites are bounded by foliated gabbros in

the east, which are overlain by undeformed gabbros that are equivalent to the crustal

level (Fig. 2F; Leblanc and Violette 1983; Abrajano et al., 1989). The volcanic

sequence consists of a lower basaltic andesite-andesite unit and an upper boninite unit

(Perez et al., 2018). Such a lava sequence is comparable with those developed in the

IBM system, confirming the subduction initiation origin of the Acoje block.

3. Petrography

Cpx-rich harzburgites contain ~ 20-30 modal% orthopyroxene, ~ 3-5 modal%

clinopyroxene and < 2 modal% chromite (Fig. 3A; Leblanc and Violette, 1983).
Petrographically, these cpx-rich harzburgites are similar to lherzolites. The cpx-poor

harzburgites are more or less impoverished in orthopyroxene than the cpx-rich variety

and have few or even no clinopyroxene (Fig. 3B). Olivine and clinopyroxene grains in

the harzburgites have been variably serpentinized, but clinopyroxene and chromite are

usually well preserved (Fig. 3A-B). Dunites in the mantle sequence and MTZ have

been serpentinized to different degrees with olivine relicts dispersed in the serpentine

matrix (Fig. 3C). Moreover, accessory chromite grains (~ 1-3 modal%) can be

observed in the dunites. Chromitites vary from disseminated (chr ~ 20-60 modal%) to

massive (chr > 80 modal%) varieties. Olivine grains in the massive chromitites have

been totally serpentinized, those in the disseminated ones partly preserved due to

slight-moderate degrees of serpentinization (Fig. 3D). More detailed petrographic

description can be found in Leblanc and Violette (1983) and Evans and Hawkins

(1989).

4. Sampling and analytical methods

Representative samples of cpx-rich harzburgites, cpx-poor harzburgites, dunites

and chromitites were selected from the block for in-situ compositional analyses (Fig.

1C). These include the major element compositions of olivine and chromite and the

in-situ oxygen isotopic compositions of olivine grains in the dunites and chromitites.

The major element compositions of olivine and chromite will be used for restoring
melt events in the Acoje mantle sequence and calculating the fO2 values of peridotites

and chromitites. The oxygen isotopic compositions of olivine grains will be used for

evaluating the contributions of slab components in mantle sources of the chromitites.

The major oxide compositions of olivine and chromite were obtained with a

JEOL JXA-8230 electron probe microanalyzer (EPMA) with a WDS/EDS combined

micro-analyzer in the Department of Earth Sciences, University of Hong Kong. The

measurements were done with 15 kV accelerating voltage, 20 nA beam current and 1

μm spot diameter. The counting durations varied from 10 to 30 s for different

elements and specially 120 s for Ti. Natural and synthetic oxides were used as

standards. The data were calibrated with the PAP matrix correction and ZAF

procedure-based program. The Fe3+/ΣFe ratios of chromite were calibrated based on

the ideal stoichiometry of spinel. The BSE images were obtained with the same

EMPA.

In-situ oxygen isotopic compositions of olivine grains in peridotites and

disseminated chromitites were acquired by using a Cameca IMS-1280 SIMS at the

Guangzhou Institute of Geochemistry. Small pieces of thin sections were put adjacent

to the reference material San Carlos olivine in mounts and polished to obtain flat and

smooth surfaces. During each analysis, the primary Cs+ beam was accelerated under

conditions of 10 kV and ~ 2 nA intensity. The size of each analytical spot was ~ 20

μm in diameter (10 μm beam diameter + 10 μm raster). An electron gun was

meanwhile used to compensate for sample charging during the analysis. Secondary

ions were extracted with a −10 kV potential. Oxygen isotopes were measured in

multi-collector mode with two off-axis Faraday cups. The oxygen isotopic

compositions of olivine are expressed in the form of δ18O (1000 ×

[(18O/16O)sample/(18O/16O)V-SMOW − 1]). The δ18O value of San Carlos olivine (+5.25;

Eiler et al., 1995) was used as the reference materials for calibrating the instrumental

mass fractionation. The external reproducibility of the standard was better than 0.5

(2SD) for δ18O. The matrix effect on the oxygen isotopic analysis is non-negligible

when the Fo values of olivine are higher than 70 (Bindeman et al., 2008; Gurenko et

al., 2010).

5. Results

5.1 Olivine

Olivine grains in the harzburgites, dunites and chromitites are all forsterite

(90-93; Table-1 and S-1; Fig. 4A), and have overlapping Fo values among different

lithologies. These olivine grains have oxygen isotopic compositions generally

consistent with that of upper mantle (+5.18±0.20) (Table-1 and S-1), and no

correlation is observed between the δ18O (with 2σ) and Fo values (Fig. 4B).

5.2 Chromite
 Chromite grains in the peridotites and chromitites have large variations of Mg#

[100×Mg2+/(Mg2++Fe2+)] and Cr# [100×Cr/(Cr+Al)], ranging from 35 to 80 and from

15 to 85, respectively (Table-2 and S-2; Fig. 5A, B). Those in the cpx-rich

harzburgites have the lowest Cr#s (~ 15-40), falling in the range of abyssal

peridotites. Those in the chromitites have a bimodal Cr# distribution, ~ 45-48 and

73-76, respectively (Fig. 5A). Chromite grains in the cpx-poor harzburgites and

dunites have overlapping Cr#s, ranging from ~ 38 to 85, mainly falling in the range of

forearc peridotites (Fig. 5A). Such compositional features are comparable to those of

chromite reported for peridotites in the San Antonio block, which is located in the

southernmost part of the Zambales ophiolite and also show forearc affinity (Yumul

and Dimalanta, 1997). In the diagram of Cr# vs. TiO2 (Fig. 5B), the chromite grains in

the cpx-rich harzburgites plot along the partial melting trend, whereas those in the

dunites and cpx-poor harzburgites plot along two reaction trends towards to the areas

defined by high-Al and high-Cr chromitites, respectively.

6. Discussions

6.1 Melt-harzburgite reactions in the mantle sequence

Reaction between the Mg-rich melts and peridotites could dissolve pyroxene and

precipitate olivine and chromite in peridotites, resulting in refractory peridotites and

dunites under conditions of varying melt/rock ratios (Arai and Yurimoto, 1994; Zhou
et al., 1994; Kelemen et al., 1995; Kelemen and Dick, 1995; Uysal et al., 2017). In

topmost part of the mantle sequence of the Acoje block, spatially associated cpx-poor

harzburgites and dunites are observed, and cpx-rich harzburgitic bodies can also be

locally found to be enclosed in cpx-poor harzburgites (Fig. 1C). Such a lithological

variation can be explained by the postulation that peridotites in the Acoje mantle

sequence had reacted with Mg-rich melts, which almost used out clinopyroxene grains

in the cpx-rich harzburgites and generated cpx-poor harzburgites and dunites under

conditions of increasing melt/rock ratios. According to our observation, both anhedral

and euhedral chromite grains can be found in the harzburgites (Fig. 3A-B). Irregular

(e.g., wormy) chromite grains are commonly seen in upper mantle harzburgites and

traditionally thought to result from partial melting (Mercier and Nicolas, 1975;

Nicolas et al., 1980; Ohara and Ishi, 1998; Hellebrand et al., 2002), whereas the

euhedral chromite grains in the harzburgites can be best explained as the result of

crystallization from infiltrating rather than partial melting, just as if how the euhedral

chromite grains were formed in replacive dunites (Arai and Yurimoto, 1994; Kelemen

et al., 1995; Zhou et al., 1996, 2005). Therefore, harzburgites in the Acoje block are

not simply residues of partial melting but also underwent later melt infiltration,

accounting for the coexisting euhedral and anhedral chromite grains. However, the

euhedral and anhedral chromite grains in an individual sample overall have identical
compositions. Such results imply that the anhedral relicts have been compositionally

transformed by infiltrating melts even though their outlines are still well preserved.

From the cpx-poor harzburgites to dunites, the compositions of chromite grains

show two different variation trends (Fig. 5B), and such features can be particularly

exemplified by the compositions of chromite grains in the two composite samples

A-115 (R-I) and A-125 (R-II), both being composed of associated harzburgite and

dunite parts (Fig. 5B and 6). Generally, larger melt/rock ratios during melt-peridotite

reactions would result in higher TiO2 contents and Cr#s of chromite grains in

peridotites (Arai and Yurimoto, 1994; Zhou et al., 1996; Pearce et al., 2000). Because

chromite grains in the harzburgite part of sample A-125 have higher TiO2 contents

and Cr#s than those in the dunite part of sample A-115 (Fig. 6A, B), the dunite parts

in samples A-115 and A-125 must have been caused by reactions with different melts

rather than with similar melts under increasing melt/rock ratios. Moreover, the two

variation trends finally overlap the compositional ranges of chromite grains in the

high-Al and high-Cr chromitites, respectively (Fig. 5B). Chromitites in ophiolitic

mantle sequences have been commonly thought to be formed by reactions between

Mg-rich magmas and harzburgites. Such reactions could consume pyroxenes

(including both opx and cpx) in the harzburgites and transfer the magma compositions

from the stability field of olivine to that of chromite during crystallization, finally
causing precipitation of chromite before olivine and formation of chromitites (Arai

and Yurimoto, 1994; Zhou et al., 1994; Uysal et al., 2009). Given that chromitites

themselves are formed via melt-rock reactions (Zhou et al., 1996, 2005, Uysal et al.,

2009, 2015, 2018), it is reasonable to claim that the reactant melts that accounted for

the two compositional variation trends of chromite have similar compositions to the

parental magmas of high-Al chromitites and high-Cr chromitites in the Acoje block,

respectively.

6.2 Parental magmas of the high-Al and high-Cr chromitites

Ophiolitic chromitites have been thought to be formed either by melt-peridotite

reaction under high melt/rock ratios or by magma accumulation in magma chambers

(Lago et al., 1982; Duke, 1983; Arai and Yurimoto, 1994; Zhou et al., 1994; Zhang et

al., 2017). In both cases, the compositions of chromite grains in chromitites are highly

controlled by their parental magmas. The Cr#s of chromite grains in the chromitites

display a bimodal distribution, (Fig. 5A, B), indicative of different compositions of

their parental magmas. Chromite grains in chromitites form at the earliest stage of

magma crystallization (Roeder and Reynolds, 1991; Kamenetsky et al., 2001), and

their TiO2 contents can be used effectively for evaluating the compositions of their

parental magmas. Using the equations of Rollinson (2008), the parental magmas of

the high-Cr chromitites are calculated to have TiO2 contents ~ 0.3 wt.% on average,
those of the high-Al chromitites ~ 0.5 wt.% on average (Fig. 7). Compared with lavas

produced in the IBM arc system, the parental magmas of the high-Cr chromitites have

TiO2 contents similar to boninitic lavas, whereas those of the high-Al chromitites have

TiO2 contents comparable to lavas with compositions transitional from MORB-like

forearc basalts to boninites (named transitional lavas hereinafter) (Fig. 7).

Although the calculated results support that the parental magmas of the high-Cr

chromitites have boninitic affinity, those of the high-Al chromitites have TiO2 content

obviously lower than typical MORB, inconsistent with traditional viewpoints that

high-Al chromitites were generated from MORB-like melts (Zhou et al., 1996, 1998;

Arai, 1997; Uysal et al., 2009). To better understand why the chromitites have low

TiO2 contents, we carried out quantitative compositional evaluation for their mantle

source using batch and fractional partial melting models. Details can be found in the

Supplementary materials. The calculated results show that up to 30% partial melting

is required in order to generate melts that have TiO2 contents as low as 0.5 wt.%

directly from fertile MORB mantle (FMM) (Fig. 8A, B). According to Kushiro

(2001), such assumed melts must reach picritic compositions and are suitable for

generating high-Cr chromitites rather than high-Al ones. This implies that the parental

magmas of the high-Al chromitites could not directly originate from FMM but from

mantle sources that had been depleted before. It has been commonly thought that the
parental magmas of ophiolitic high-Al chromitites were produced by low to moderate

degrees of partial melting in mantle sources under sulfur saturated conditions (Zhou et

al., 1996, 1998; Rollinson, 2008; Uysal et al., 2009; González-Jiménez et al., 2011).

Given our calculated results, the mantle sources of the high-Al chromitites had

composition equivalent to peridotites that probably underwent ~ 10% melt extraction

from FMM, and a second stage of 5-10% partial melting was required to generate

their parental magmas (Fig. 8A, B). Likewise, the parental magmas of the high-Cr

chromitites could be produced via a second stage of 10-20% partial melting in similar

mantle sources to those of the high-Al chromitites.

6.3 Slab contribution in mantle sources of the chromitites

Previous studies proposed that the fO2 values of peridotites in subarc mantle are

overall higher than those of abyssal peridotites due to the modification of slab-derived

materials (Parkinson and Arculus, 1999; Malaspina et al., 2009; Brounce et al., 2015).

The mantle sequence of the Acoje block is equivalent to the uppermost part of a

nascent mantle wedge. Therefore, peridotites in the Acoje block had probably been

modified by slab-derived materials and also show different redox states from abyssal

ones. Using the compositions of paired chromite and olivine grains (Ballhaus et al.,

1991), the fO2 values of most peridotites in the Acoje mantle sequence range from ~

-0.5 log unit below the FMQ to 1.5 log unit above the buffer (Table-2; Fig. 9A). In the
diagram ΔlogfO2(FMQ) vs. Cr# of chromite, the data of peridotites fall in the mantle

regimes across different tectonic settings . In particular, dunites and chromitites have

obviously higher fO2 values than harzburgites and fall in the subarc mantle regime

(Fig. 9A, B), implying that parental magmas of the chromitites and dunites were more

oxidized than typical MORB and had SSZ affinity. Such results reveal involvement of

small amounts of high-fO2 materials in the Acoje mantle sequence, consistent with the

forearc affinity of the block.

Although contribution of slab materials exists in the peridotites, especially in

mantle sources of the dunites and chromitites, the oxygen isotopic compositions of

olivine in the peridotites do not deviate from the upper mantle range (+5.18±0.20; Fig.

4B; Chazot et al., 1997; Eiler, 2001; Mattey et al., 1994). Although crustal materials

are usually thought to have heavier oxygen isotopic compositions than the upper

mantle, e,g., reported δ18O values of +13 for some slab-derived melts (Eiler et al.

1998; Liu et al., 2014), fluids and melts in the nature usually have similar O contents

to peridotites, making it difficult to change the oxygen isotopic compositions of

peridotites during limited degrees of fluid/melt modifications. Supposing the δ18O

value of slab-derived fluids ranges from 10 to 20, addition of even 3-5 mol% such

fluids cannot elevate the δ18O values of peridotites beyond that of the upper mantle

range according to Zhang et al. (2019). Further given that the fO2 values of the
peridotites are merely slightly higher than those of abyssal peridotites, we suggest that

the mantle sequence of the Acoje block was modified by small amounts of

slab-derived fluids.

6.4 Geodynamic implication

Mantle fertility usually increases with depth as the result of either decreasing

degrees of partial melting or increasing degrees of melt refertilization (Zhou et al.,

2005; Batanova and Sobolev, 2000; Bodinier and Godard, 2003; Godard et al., 2000;

Xiong et al., 2017). The parental magmas of both the high-Al and high-Cr chromitites

were generated from greater depths than the lowermost mantle sequence of the Acoje

block, which is occupied by cpx-rich harzburgites according to our field observation.

Therefore, the mantle sources of the chromitites probably had at least similar fertility

to cpx-rich harzburgites. As is indicated by the low TiO2 contents of chromite grains

in the chromitites, the mantle sources of the chromitites had compositions equivalent

to peridotites that had undergo ~ 10% partial melting from FMM in order to achieve a

first stage of Ti depletion. With such degree of melting, peridotites in the FMM would

have become cpx-poor lherzolites according to the evaluation of Kostopoulos (1990).

Combined both the geological and petrological observation, the mantle sources of the

chromitites, especially of the high-Al ones, were likely made of cpx-rich harzburgites

or cpx-poor lherzolites.
 Although moderately refractory peridotites (e.g., cpx-rich harzburgites) cannot

be easily melted under anhydrous conditions, the mantle sequence of the Acoje block

and mantle sources of the chromitites were modified by small amounts of slab-derived

fluids, which could remarkably affect the melting behavior of peridotites. Based on

experimental studies, a small amount of fluids (< 1 mol%) is able to notably decrease

the solidus temperatures of peridotites, e.g., down to 1150 ºC (Hirose and Kawamoto,

1995; Ulmer, 2001). Slab rollback is a prominent feature of subduction initiation and

may induce asthenospheric upwelling below spreading proto-forearc regions (Reagan

et al., 2010, 2019; Whattam and Stern, 2011; Stern et al., 2012). Given that

asthenospheric upwelling can effectively elevate the geothermal gradient (Hall et al.,

2003; Ueda et al., 2008), the lowered solidus temperatures could be easily satisfied in

nascent mantle wedges via geothermal disturbance during asthenospheric upwelling.

Thus, infiltration of slab-derived fluids should have largely facilitated development of

magmatism in the Acoje mantle wedge, even though the amounts of added fluids were

probably too small to elevate the fO2 values of peridotites in the mantle wedge.

Presence of cpx-rich harzburgites in the uppermost mantle sequence of the Acoje

block supports that the whole mantle sequence was possibly once occupied by

cpx-rich harzburgites, which were transformed to cpx-poor harzburgites, dunites and

chromitites after reacting with Mg-rich melts under conditions of increasing melt/rock
ratios. Cpx-rich harzburgites have usually been considered either as residual products

after extraction of MORB-like melts or as refertilization products of MORB-like

melts (Bodinier and Godard, 2003; Godard et al., 2000). In either case, formation of

cpx-rich harzburgites is genetically related to MORB-like magmatism. Based on the

compositional variation of chromite in the peridotites and chromitites, the cpx-rich

harzburgites reacted with at least two types of melts, which have transitional lava-like

and boninitic affinities, respectively. As a result, coexistence of cpx-rich harzburgites,

cpx-poor harzburgites, dunites, high-Al chromitites and high-Cr chromitites in the

Acoje mantle sequence reflects combined effects of MORB-like, transitional lava-like

and boninitic magmatism, well comparable to those developed during subduction

initiation recorded in the IBM arc system and Neo-Tethyan ophiolites (Reagan et al.,

2010; Whattam and Stern, 2011; Stern et al., 2012). As a result, chromitites and their

associated peridotites in the Acoje block demonstrate that mantle sequences of forearc

ophiolites preserve as useful information as in lava sequences for reconstructing the

geodynamic evolution of subduction initiation.

7. Conclusions

The main conclusions of this study can be drawn as below:

1. The Acoje block contains both high-Al and high-Cr chromitites. Their parental

magmas have compositions similar to the IBM transitional and boninitic lavas,
 respectively, and originated from moderately refractory mantle sources.

2. Peridotites in the Acoje block have been modified by two types of melts sharing

similar compositions to parental magmas of the high-Al and high-Cr chromitites,

accounting for two compositional variation trends of chromite in the peridotites.

3. The Acoje mantle wedge was infiltrated by small amounts of slab-derived fluids,

which largely decreased the solidus temperatures of harzburgites and facilitated

generating Mg-rich parental magmas of the chromitites.

4. The magmatic events recorded in the Acoje mantle sequence is overall consistent

with those developed in the IBM system and can be effectively used for restoring

the geodynamic evolution of nascent mantle wedge during subduction initiation.

Acknowledgments

This study was supported by the Research Grant Council of Hong Kong (Grant

17306018) and National Natural Science Foundation of China (Grant 41473038 and

41772087). We thank Nikko Pacle and Americus Perez for their assistance during the

field excursion, Ms. Xiao Fu for the EMPA analysis, and Mr. Yan-Qiang Zhang for

the oxygen isotopic analyses. All the data used in this study can be found from the

Mendeley database. This paper benefited from important suggestions and helps from

Dr. Ben-Xun Su, Dr. Yan Xiao and Dr. Dong-Yang Lian. The constructive comments

and suggestions from Prof. Ibrahim Uysal and Prof. Ahmed Hassan Ahmed are also
highly appreciated.

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 Figure Captions

Fig.1 Location and geological maps of the Zambales ophiolite and the Acoje block.

Distribution of high-Cr and high-Al chromite deposits in the Zambales ophiolite and 8

sampling locations (yellow stars with sample names) in the Acoje block are shown in

the diagrams B and C, respectively. The diagrams A and B are modified from Hock et

al. (1986), diagram C modified from Yumul (2001).

Fig.2 Outcrop photos of rocks in different stratigraphic sequences of the Acoje block.

(A) Harzburgites with pyroxene relicts on weathered surfaces. (B) Associated dunite

and harzburgites at the topmost mantle sequence. (C) High-Al chromitites (ore rocks)

and alluvial high-Al chromite grains. It is noted that these high-Al chromitites were

only found as dispersed fragments in red soils probably as the result of high degrees

of weathering. These ore fragments and alluvial chromite grains were once used for

exploration. (D) Irregular high-Cr chromitite in dunite host at the topmost mantle

sequence. (E) Interlayered chromitites and dunites in the lower MTZ. (F) Plagioclase-

and pyroxene-rich layers at the topmost MTZ.

Fig.3 Petrological photos of rocks in the Acoje block. (A-B): Cpx-rich harzburgite

and cpx-poor harzburgite with irregular clinopyroxene and euhedral chromite grains.

(C): Dunite with large olivine and euhedral chromite grains. (D) Highly serpentinized

disseminated chromitites with small olivine and anhedral chromite grains.

Fig.4 Compositions of olivine in the peridotites and chromitites. (A) Plot of NiO vs.

Fo. (B) Oxygen isotopic compositions of olivine. The shaded area represents the

oxygen isotopic compositions of normal upper mantle that were not modified by

slab-derived components (δ18O, +5.18±0.20).

Fig.5 Plots of Cr# vs. Mg# and Cr# vs. TiO2 of chromite in the harzburgites, dunites

and chromitites. The diagram A is modified after Dubois-Côté et al. (2005), diagram

B after Pearce et al. (2000). The IBM and FMM represent Izu-Bonin-Mariana and

fertile MORB mantle, respectively. The subscripts b, i and m are short for boninite,

island arc tholeiite and MORB, respectively. The insert diagram in the diagram B

show two reaction trends (R-I and R-II) defined by the composite samples A-115 and

A-125.

Fig.6 Plots of Cr# vs. Mg# and TiO2 vs. Cr# of chromite in the composite samples

A-115-01~02 and A-125-01~03. Detailed dataset can be found in the Table-S2.

Fig.7 Calculated TiO2 contents in the parental magmas of the high-Cr and high-Al

chromitites. The empirical formula are from Rollinson (2008). The TiO2 ranges of the

IBM fore-arc basalts, transitional lavas and boninites are from Reagan et al. (2010).

Fig.8 TiO2 contents of melts generated via batch and fractional melting models. The

data of grey, green, blue and red diamonds were calculated by assuming the mantle

sources had compositions equivalent to FMM, 5% melting residue (MR) from FMM,
10% melting residue from FMM and 15% melting residue from FMM, respectively.

The compositions of MR used in the diagrams A and B were also calculated based on

batch and fractional melting models, respectively. The dash green and red lines mark

the averaged TiO2 contents in the parental magmas of the high-Al and high-Cr

chromitites, respectively. The equations and initial parameters used in the modeling

can be found in the Supplementary materials.

Fig.9 Oxygen fugacity variation among the peridotites and chromitites (A) and from

the cpx-poor harzburgite to dunite parts in each of the two composite samples A-115

and A-125 (B). The fO2 values are calculated using the oxygen barometer of Ballhaus

et al. (1991) under 1Gpa. The averaged compositions of chromite and olivine in each

sample are used for calculation in the diagram A, the composition of individual

chromite grains and averaged composition of olivine in each part of the composite

samples are used for calculation in the diagram B.

Declaration of interests

☐ The authors declare that they have no known competing financial interests or

personal relationships that could have appeared to influence the work reported in this

paper.

☐ The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests:
 Dear Editor,

We confirm that we have no financial interests or personal relationships to declare for

this work. We would highly appreciate if this paper can be considered for publication in

Ore Geology Reviews. Thank you very much.

Best regards

Table-1 Major element and oxygen isotopic compositions of olivine grains.

Sample MnO NiO CaO FeO SiO2 MgO Total Fo δ18O 2SE
Cpx-rich harzburgite
A-01 0.15 0.34 0.02 9.33 41.2 48.8 99.8 90.4
A-02 0.12 0.35 bdl. 9.57 40.9 48.1 99.0 90.1
A-04 0.10 0.34 0.01 8.88 41.4 49.4 100.2 90.9
A-05 0.14 0.36 0.02 9.06 41.1 48.6 99.3 90.6
A-78 0.13 0.35 0.01 9.22 41.3 49.0 100.0 90.5
A-79 0.13 0.37 0.01 8.99 41.1 48.6 99.2 90.7
A-82 0.13 0.36 0.02 9.09 41.2 49.2 100.0 90.7
A-114 0.14 0.33 0.02 9.04 41.2 49.0 99.7 90.7
A-154 0.11 0.36 0.01 8.74 41.4 49.3 99.9 91.0
A-156 0.12 0.34 0.01 9.05 41.2 49.1 99.8 90.7
A-158 0.13 0.38 0.02 9.21 41.6 49.2 100.5 90.6 5.59 0.05

Cpx-poor harzburgite
A115-01 0.13 0.37 0.02 9.30 41.7 49.4 100.9 90.5 5.29 0.06
A-119 0.12 0.31 0.02 9.17 41.5 49.7 100.9 90.7
A-120 0.11 0.34 0.03 8.76 41.7 49.9 100.8 91.1
A-124 0.13 0.36 0.03 8.85 41.7 48.8 99.9 90.8 5.40 0.06
A125-01 0.13 0.35 0.02 9.26 41.7 49.6 101.1 90.6 5.37 0.05

Dunite
A-20 0.14 0.22 0.02 9.46 41.7 49.4 100.9 90.4 5.36 0.04
A-22 0.14 0.25 0.04 9.11 41.4 49.3 100.3 90.7 5.18 0.07
A-23 0.15 0.22 0.05 9.15 41.9 49.6 101.1 90.7 5.12 0.06
A115-02 0.14 0.37 0.02 9.31 41.7 49.2 100.7 90.5 5.24 0.06
A125-02 0.13 0.34 0.05 9.26 41.2 49.4 100.4 90.6 5.22 0.05
 A125-03 0.14 0.34 0.06 9.26 41.4 49.1 100.3 90.5 5.21 0.05
A-128 0.13 0.36 0.14 8.59 41.5 49.5 100.2 91.2 5.30 0.06
A-131 0.14 0.26 0.11 9.43 40.8 48.7 99.4 90.3
A-133 0.13 0.32 0.13 8.86 41.8 49.6 100.8 91.0 5.29 0.05
A-136 0.10 0.33 0.10 8.49 42.0 49.9 100.9 91.4
A-139 0.12 0.34 0.11 8.98 41.3 49.2 100.1 90.8 5.58 0.05

Disseminated chromitite
A-17 0.14 0.16 0.08 9.53 41.6 49.1 100.7 90.3 5.28 0.07
A-19 0.15 0.16 0.10 9.46 41.5 48.4 99.8 90.2 5.39 0.04
A-39 0.11 0.34 0.06 7.22 42.1 50.5 100.4 92.6 5.07 0.06
Note: (1) Fo = 100×Mg2+/(Mg2++Fe2+); (2) Only disseminated chromitites have olivine relicts;
(3) the “bld” is short for below detection limit. (4) Detailed dataset can be found in the
supplementary material Table-S1.

Table-2 Major element compositions of chromite grains and ƒO2 values of peridotites and chromitites.
Sample SiO2 TiO2 Al2O3 V2O3 Cr2O3 FeO MnO MgO ZnO NiO Total Cr# Mg# Fe3+/∑Fe Δlog(ƒO2)
Cpx-rich harzburgite
A-01 bdl. 0.041 53.2 0.08 14.4 12.2 0.13 20.4 0.13 0.27 100.9 15.3 80.1 0.26 0.74
A-02 0.03 0.070 51.9 0.09 15.4 12.3 0.12 19.5 0.13 0.30 99.9 16.6 77.8 0.20 -0.13
A-04 bdl. 0.062 33.6 0.18 32.7 18.4 0.21 14.5 0.21 0.10 100.0 39.5 63.7 0.20 0.60
A-05 0.01 0.042 46.1 0.17 20.3 15.1 0.15 17.3 0.21 0.19 99.6 22.8 71.4 0.19 0.41
A-78 0.01 0.028 43.1 0.13 23.7 14.7 0.15 17.3 0.17 0.19 99.5 26.9 72.5 0.20 0.23
A-79 bdl. 0.022 39.8 0.20 26.8 15.7 0.18 16.1 0.28 0.15 99.2 31.1 68.9 0.18 0.18
A-82 0.01 0.028 37.3 0.18 29.9 15.9 0.18 15.7 0.18 0.12 99.5 35.0 67.8 0.16 -0.04
A-114 0.02 0.099 27.1 0.21 39.7 19.6 0.25 12.7 0.17 0.08 100.0 49.6 57.9 0.16 0.20
A-154 0.02 0.067 25.9 0.20 41.4 18.4 0.24 13.4 0.16 0.11 99.9 51.7 61.1 0.17 0.15
A-156 0.01 0.031 42.5 0.13 25.2 14.7 0.16 17.1 0.17 0.18 100.2 28.5 71.5 0.17 -0.01

Cpx-poor harzburgite
A-119 0.02 0.140 18.6 0.19 48.8 20.8 0.30 11.4 0.17 0.10 100.6 63.8 54.0 0.17 0.22
A-120 bdl. 0.044 30.5 0.18 36.3 19.3 0.23 13.2 0.31 0.08 100.2 44.4 59.4 0.16 0.40
A115-01 0.01 0.062 34.5 0.19 31.9 17.6 0.21 14.8 0.25 0.13 99.6 38.3 64.7 0.19 0.32
A125-01 0.02 0.132 21.8 0.22 44.8 19.4 0.28 11.5 0.23 0.06 98.4 58.0 54.4 0.12 -0.41

Dunite
A-13 0.01 0.177 16.1 0.19 47.7 23.7 0.36 8.81 0.17 0.02 97.3 66.5 44.1 0.16
A-22 bdl. 0.206 12.4 0.22 54.1 22.5 0.33 8.94 0.15 0.02 98.8 74.5 44.6 0.12 -0.11
A-126 0.01 0.145 6.70 0.13 53.0 29.9 0.44 7.13 0.16 0.05 97.6 84.2 37.6 0.29
A-131 0.01 0.187 9.20 0.20 53.3 27.5 0.43 7.57 0.11 0.03 98.6 79.5 38.9 0.23 1.31
A133 0.01 0.207 11.4 0.22 51.2 25.4 0.35 9.07 0.14 0.06 98.1 75.1 45.8 0.24 1.37
A-136 0.02 0.195 12.8 0.18 50.3 25.0 0.34 9.34 0.13 0.06 98.4 72.5 46.6 0.24 1.36
 A-138 0.01 0.219 13.1 0.17 49.5 25.4 0.32 8.82 0.14 0.07 97.8 71.7 44.4 0.23 1.50
A115-02 0.01 0.071 31.3 0.20 33.0 20.0 0.23 13.7 0.26 0.13 98.9 41.6 61.5 0.23 1.43
A125-02 0.02 0.151 20.1 0.23 46.3 20.5 0.31 10.9 0.26 0.06 98.9 60.7 52.2 0.13 -0.12
A125-03 0.02 0.183 18.9 0.25 45.3 22.1 0.30 10.9 0.23 0.07 98.3 61.6 52.5 0.21 0.75

Chromitite
A-19 0.01 0.211 11.3 0.23 52.6 25.7 0.37 8.21 0.12 0.03 98.8 75.7 41.4 0.19 0.87
A-39 0.01 0.193 12.2 0.18 54.0 20.7 0.29 11.3 0.05 0.08 99.0 74.8 55.3 0.21 1.03
A-42 0.03 0.150 29.5 0.12 38.7 13.2 0.16 16.5 0.05 0.17 98.5 46.8 73.2 0.18
A-45 0.05 0.154 29.9 0.12 38.7 13.7 0.14 15.3 0.05 0.21 98.3 46.5 68.2 0.08
A-46 0.03 0.152 29.9 0.11 38.3 13.9 0.15 15.9 0.04 0.21 98.6 46.2 70.5 0.15
A-57 0.02 0.190 13.4 0.17 54.5 16.8 0.22 13.3 0.06 0.09 98.8 73.2 64.2 0.21
Note: (1) The counting duration for Ti during EPMA analysis was specially set to be 120s in order to
ensure the data accuracy; (2) Mg# = 100×Mg2+/(Mg2++Fe2+); (3) Cr# = 100×Cr3+/(Cr3++Al3+); (4) The
Δlog(ƒO2) values are calculated using the averaged compositions of chromite and olivine grains in each sample
based on the oxygen-barometer of Ballhaus et al. (1991) relative to FMQ buffer. (5) Detailed dataset can be
found in the supplementary material Table-S2.

Highlights

 Parental magmas of all Acoje chromitites originated from harzburgitic sources.

 The Acoje peridotites had reacted with parental magmas of different chromitites.

 The Acoje mantle wedge was infiltrated by tiny amounts of slab-derived fluids.

 Coexistence of high-Al and high-Cr chromitites evidences subduction

initiation.