RARE EARTH ELEMENTS POTENTIAL OF ALKALINE IGNEOUS

ROCKS OF THE PESHAWAR PLAIN ALKALINE IGNEOUS

PROVINCE, PAKISTAN

INTRODUCTION

1.1. General Statement

The term "Rare Earth Elements (REE)" refers to a group of 17 chemically similar elements,
including the 15 lanthanides (having atomic number 57-71), scandium and yttrium. Scandium
and yttrium are also placed in this group due to their similar chemical and physical properties
(Kogel et al., 2006).

REEs have considerable concentration in the earth's crust having an overall abundance of 9.3
ppm (Rudnick and Gao, 2003). Cerium is the most abundant REE with concentration of 43
ppm and thulium is the rarest having abundance of 0.28 ppm (Taylor and McLennan, 1985;
Rudnick and Gao, 2003). The REEs do not occur as native elements but are hosted by more
than 200 minerals including carbonates, phosphate, halides and silicates. Although a variety of
minerals can host REEs but the significant and economical concentrations can be associated
with bastnasite, monazite and xenotime (Y, Dy, Er, Yb, and Ho) (Eckstrand et al., 1995;
Chakhmouradian and Zaitsev, 2012). Recently, the demand of REEs has increased
considerably due to development of innovative technologies across the globe, which include
lighter flints, glass polishing, phosphorus, lasers, magnets, batteries, magnetic refrigeration,
light bulbs, high definition televisions and electronics, and in many small telecommunication
gadgets, we rely ondaily basis (Haxel et al., 2002).

The alkaline and peralkaline igneous rocks have been considered as the major source of REES
(Verplanck and Hitzman, 2016). Several REEs deposits in similar rocks have been discovered
in different parts of the world, e.g. the Llimaussaq alkali complex in the Greenland and Khibina
and Lovozero alkali complex in Russia (Orris and Grauch, 2002). The REEs deposits of
alkaline igneous rocks are primarily enriched in heavy rare earth elements (HREEs) and Y, but
they can also contain other economic minerals hosting high field strength elements (HFSEs)
e.g. titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb) as well as uranium (U) and
thorium (Th), however, low in grade compared to light rare earth elements (LREEs) (Kogel et
al., 2006). Alkaline rocks hosting REEs mainly include nepheline syenites, peralkaline granites
(including pegmatites) and sometimes peralkaline felsic volcanic rocks (Dostal, 2017). The
source for these host rocks is derived by partial melting of lithospheric mantle which is
metasomatically enriched in REEs, HFSEs, U and Th content (Pilet et al., 2008). The REES-
bearing minerals in peralkaline granites and felsic volcanic rocks usually occur in disseminated
form derived during the fractional crystallization of magma processes, particularly the late
stage fractionation (Dostal, 2017). The REEs and trace elements in a lithological unit can
describe the geochemical signatures of a rock body and can help interpret the tectonic setting
in which it is evolved. In addition, the different anomalies displayed by the REEs can be used
to infer the parental magma composition and its evolutionary history (Marshall, 1996).

Alkalline complexes are present in the North Pakistan as well as in the Nagar Parkar, Sindh.
However, no detail studies have been carried out yet to investigate the petrogenesis and REES
significance of these alkaline rocks. One of the important exposures of the alkaline complexes
in Pakistan is the Peshawar Plain Alkaline Igneous Province (PPAIP). The PPAIP is a 150-200
km long magmatic body exposed along the north and northwestern margin of Peshawar plain

(Fig.1.1; Kempe and Jan 1970). It extends from the Loe Shliman carbonatite in the West
through Warsak alkaline pluton, Sillai Patti carbonatite complex, Malakand pluton, Shewa
Shahbazgarhi Porphyries, Ambela granitic complex to the Tarbela alkaline complex in the East
(Kempe and Jan, 1980; Jan and Karim, 1990). The PPAIP has crystallized in two stages in a
rift related tectonic environment;

1) Permo-Carboniferous (Zeitler, 1988; Smith et al., 1994) and

2) Tertiary (Oligocene) (Khattak et al., 2012). The rocks in PPAIP are mildly to strongly
alkaline and include alkali granites, microgranites, syenites, albitites and carbonatites (Kempe
and Jan, 1980).

The Warsak alkaline pluton, Shewa Shahbazgarhi porphyries of the PPAIP and the Malakand
pluton are the focus of the present study to provide detail understandings of their petrogenesis,
tectonic setting and REE profile. Earlier Researches encompassing petrogenetic and tectonic
evolution of these rocks include e.g. Kempe and Jan, 1980; Jan et al., 1981d; Rafiq and Jan,
1989; Tahirkheli et al., 1990; Khattak et al., 2001; Ahmad et al., 2013; Sajid et al., 2014.

Moreover, various REEs hosting phases e.g. sphene, zircon, monazite, xenotime, and apatite
have been identified in these bodies. However, little efforts have been made to better evaluate
their REE potential and the petrogenesis using the trace and REEs data. It is, therefore, critical
to analyse different mineral phases in these plutonic bodies for the REEs and other trace
elements concentrations.

1.2. Aims and Objectives

The Main objectives of the present study are outlined below:

➢ To target mineralogical characterization of alkaline plutonic rocks of PPAIP with

major emphasis on Warsak pluton, Malakand pluton and Shewa Shahbazgarhi
porphyritic pluton.
➢ To carry out detail geochemical investigation of the above-mentioned plutons to
estimate major, trace and REE elements concentrations.
➢ To investigate the origin of mineralization in the alkaline plutonic bodies using
geochemical modeling.

1.3. Location and accessibility of the study area

The Warsak, Malakand and Shewa Shahbazgari porphyritic plutons are well exposed along the
East-West extension of the PPAIP. The overall climate of the region is semi arid with extreme
hot summers and cool winters. The average precipitation is about 400mm in a year. These
alkaline bodies are bounded to the North and South by the MMT and MBT respectively, to the
West by Afghanistan and to the East by the Hazara division (Fig. 1.1).

The outcrop exposure of the Warsak pluton is present in the Mulagori village (34° 07' 39.8"N,
71° 24' 50" E) of the Warsak area along the southern side of the Warsak dam. It can be accessed
through the Peshawar-Regi road. Shewa Shahbazgari is an isolated igneous body of the acidic
and basic rocks that intruded into the metasedimentry rocks of the Swabi-Chamla group of
Martin et al. (1962); (Fig 2.3). It is located about 29 km north-west of Swabi city (34° 13' 49"N,
72° 10' 18"E) and can be accessed through the Peshawar-Swabi GT road.

Malakand pluton, a leucocratic body has an oval shape, covering an area of 40 km², is exposed
along the Mardan-Swat road near the Tor Morh Rest House (34° 34' 09"N, 71° 55' 48"E).
1.4. Methodology

1.4.1. Field work

A comprehensive field work in the proposed study areas of Warsak, Shewa Shahbazgari of the

PPAIP and Malakand was undertaken. 60 representative samples were collected from all the

alkaline plutonic complexes at intervals, where lithological variation is visible. GPS point data

was recorded for each sample. All the macro and micro field features were recorded for the
detail investigation and to understand field relationship of these plutonic bodies.

1.4.2. Laboratory work

Thin sections will be prepared from selected samples for detail petrographic analysis to classify
various rock units and identify different rare earth bearing phases.

For major elements concentration (in weight %) specimens will be analyzed using X-ray
Fluorescence (XRF). The XRF samples (Pressed Pellet) will be prepared by crushing the rock.
samples using jaw crusher which were then powdered using agate mill. Pressed pallets will be
formed from the powdered sample by mixing 12g of sample with 3g of cellulose binder. The
sample and cellulose mixture was then placed in a cylindrical disc and pressed with the help of
press machine which exerted a load of 300kN on the cylindrical disk. The pellets were then run
on XRF for the determination of major oxides present in a rock sample.

For trace and rare earth elements concentration, samples will be analyzed through Inductively
Coupled Plasma-Mass Spectrometer (ICP-MS). Four acids (HCI, HNO3, HC104 and HF)
digestion method will be used for the sample preparation. In this method 250mg powdered
sample was taken in a Teflon beaker. 4ml concentrated HF and 4ml of aqua regia was added
to the powdered sample and heated on the heating plate for 20-30mins. After heating, the
samples were allowed to cool. Then 1 ml of HCLO4 and 1ml HNO3 was added to the Teflon
beaker containing the sample and heated to dry. After cooling the sample, 1ml concentrated
HNO3 and 5ml distilled water was added to the dried sample and again heated for 10-15mins
at 100°C. Finally, the sample will be diluted with 50ml distilled water and analyzed on the ICP-
MS.