PERSIDANGAN JMG 2012 LISAN

Mineralogy and Chemistry of Wulfenite Deposit in Sg. Pong

Pengkalan Hulu
Mohd Zaidi Mohd Hassan1 & A.Kamarudin2,
Technical Services Division, Department of Mineral and Geosciences Malaysia
mzaidi@jmg.gov.my1, akma@jmg.gov.my2

Abstrak Wulfenite atau dengan sebutan kimianya plumbum molibdat (PbMoO4)

merupakan sejenis mineral yang amat jarang ditemui. Selain dari kewujudannya yang seringkali
digunakan dalam memberi penerangan yang lengkap berkaitan aktiviti pemineralan, mineral ini
merupakan bahan penting dalam pembuatan pelbagai jenis pencerap partikel kriogenik yang
banyak digunakan dalam industri aeroangkasa. Kewujudan wulfenite telah dikenalpasti berlaku di
Sg. Pong Pengkalan Hulu, terutama dibeberapa kawasan yang dipercayai amat aktif dengan
kegiatan hidroterma. Pengkristalan mineral ini dipercayai berlaku hasil dari sumbangan logam
plumbum yang ketara dari syal berkarbonat yang ditemui wujud antara zon pertembungan granit
dan batu kapur. Sementara unsur molibdenum dipercayai berasal dari pemekatan dari sumber syal
berkarbonat dan batuan ‘igneous’. Kajian susulan berkaitan sebaran dan kewujudan mineral
wulfenite ini wajar diteruskan memandangkan ia merupakan satu indikasi penting dalam
menemukan mineral-mineral berharga seperi mottramida, vanadinit, kasiterit, tullerida dan logam
berharga seperti emas.Selain dari kepentingannya dalam kajian mineral mineral ini juga semakin
penting terutama dalam bidang elektronik, dan industri petrokimia.

Abstract Wulfenite is a rare and delicate lead molybdate (PbMoO4) mineral that is
occurring in highly oxidized zone. Despite of using wulfenite as an indicator for predicting
mineralization process, it is also has been use as a main ingredient for fabricating most of the
cryogenic particle detector in aerospace technology. Recently wulfenite crystal was found in a
hydrothermal active area of Sg. Pong Pengkalan Hulu. The occurrence and formation of the
wulfenite crystal is due to the highly concentration of the lead minerals in the carbonaceous like
shale in the middle of granitic to limestone contact. The source of molybdenum is believed to be
originated from both the carbonaceous shale and igneous rock that concentrate in late hypogene
solution. As indication of an active base metal precipitation a significant amount of vanadium
content is monitored and observed from the XRF analysis in the range of 0.5 – 1.0 percent. A detail
study on the existence of wulfenite and its gauge will be useful in predicting the behavior of the
existence of many other valuable minerals such as, mottramite,vanadinite, cassiterite, tellurite and
gold. Despite of the importance of wulfenite in mineral exploration the demand starts to increase as
it is use in electronics and petrochemical industries.

1. Introduction

Lead has been one of earliest metal that has been exploited for industrial purpose. It has been a
metal of choice for ammunitions due to its favorable physical characteristics such as low melting
point (327.4ºC), low malleability but with high density (11.34g cm-3), high resistance of corrosion
and having the highest atomic number among the most stable element making it is the best choice
for radiation shielding.
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Naturally occur as metallic and ore, the most common lead deposit is in the form of Galena.
Wulfenite on the other hand is one of the most rarely found lead bearing mineral that occur
associated with other lead minerals such as galena, cerrusite, mimetite, anglesite, and vanadinite.
Wulfenite crystal is hard to be indicated using naked eyes. Most of the wulfenite is in microstructure
size distributed between 0.1mm to 20mm of diameter. The only prominent indicator of wulfenite
despite of chemical or mineralogical analysis is a slightly heavier and dense than normal concentrate
minerals.
There is no concrete explanation on the source of molybdenum and the formation of lead
molybdate in oxidized and highly mineralization area. In Sg, Pong for example, the molybdenum
present in small quantity relatively in igneous rocks, residual soils and hypogene ore primary
cassiterite, iron ore, and even pyrites that is found in the area. It is possible if the main source of
molybdenum come from the hypogene solution an extensive study could reveal an interesting fact
behind the mineralization of the area. It is very seldom for the molybdenum minerals to be found in
a huge extractable quantity.
The oxidized ores of lead carrying molybdenum chiefly as the mineral wulfenite usually
contain some tungsten, chromium, vanadium, copper and calcium. This is due the nature of
wulfenite that is widely distributed in varying but generally small amount in lead ores that is
subjected to prolonged oxidation. Because of this, wulfenite is generally not present in any
considerable amount where it is economic for it to be extract. Somehow there are still some
workable wulfenite mines such as the Wheatley Mines in Pennsylvania, Collins Mines in Schultz
Arizona where 1 – 2% of wulfenite is extracted from their oxidized ore bodies and Questa near
Cutter, New Maxico that is operated by Chevron is extracting 0.05 – 0.3% of molybdenum from
their ferromolybdite and 0.5 – 1.0% of low grade wulfenite and vanadinite. The high demand and
expensive price for natural plumbum molydate (PbMoO4) and molybdenum itself has created
possibilities for effective extraction technique.
Wulfenite is one of the main sources of molybdenum besides Molybdenite (MoS2). After
the first world war global demand of molybdenum increase mainly in the ferroalloy industries. The
replacement of ferromanganese and ferrotungten with ferromolydenum in the fabrication of military
equipment were due the properties of alloy itself. Ferromolydenum were found lighter, greater
maneuverability, and more resistive to oxidation and corrosion formation. (Gupta, 1992).
Lead molybdate (PbMoO4) is well known as a superior medium for acousto-optic devices
and in the construction of effective cryogenic detector that is in use in major aerospace, electronics,
and medical equipment. Magnetic resonance imaging (MRI) is one of equipment that rely natural
and synthetic PbMoO4 for the fabrication of its cryogenic detector that could withstand a running
temperature of -269°C. Agamalyan [ ] discovered unique photoelectric properties of natural and
artificial lead molybdate. The mineral exhibit an important differential negative resistance that is
similar to several important semiconducting materials such as gallium arsenide (GaAs) and Indium
Phosphide (InP). Both GeAS and InP is somehow found to be unstable. The stability of wulfenite
has made it is an important choice in semiconductor technology mainly in electronic industries.

2. General Geology and Depositional Description

The location of the study is situated 10 km North-West of Kampung Pong, Gerik, Perak. The area is
accessible through a 8 km timber track from kawasan rehat Sg. Rui on the Grik-Kupang new
highway. The area of deposition is believe to be a highly active mineralization area that located
between the intrusive vein from the Bintang Hill on the west and partly compose of the Main Range

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formation on the east. Clear occurrences of interbedded tuff, limestone, carbonaceous shale that host
clastic sedimentary products such as limestone, manganese oxides and iron oxides.

Blok 5 Blok 8

Blok 7

Figure 1.0 Location of wulfenite sampling area in sungai Pong.

3. Mineralogical and Chemical Analysis

Thirty samples were collected for analysis. We categories the sample into four types that is rock
fragment, river concentrate, soil and shale. All the samples were collected at block seven of Sg.
Pong. A systematic panning was done along sungai Pong with 10 stream concentrate sample was
collected every 100 meters. Concentrate sample was panned and later lights that comprise of quartz
and some clay materials were washed, separate using bromoform and dried at 60ºC for 3 hours to
remove traces of bromoform.
Initial magnetic and microscopic separations were done at Mineralogy and Petrology Unit
of Technical Services Division (BPT) in Ipoh. Stages magnetic separation is conducted to remove
metallic minerals. Microscopic separation was conducted to separate mineral base on visual
interpretation/reference. Mineralogical phase spectral analyses were conducted using Bruker D8
Advance X-Rray Diffraction (XRD) at Mineral Research Centre (PPM) in Ipoh. The finely ground
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and separated heavy minerals were then prepared in standard PMMA sample holders with the cavity
diameter of 25mm and 1mm depth. The milled powders were pressed with a palletizer to flatten the
surface. In this determination a Cu Kα radiation was in use with measurement time constant 0.5 s,
limit of measurement 10 impulses per second with a step size of 0.02º. The recorded XRD spectra
were used to identify the existence of minerals in each collected samples.
Bruker S4 Pioneer wavelength dispersive x-ray fluorescence spectrometry were use to
determine chemical composition of all the minerals. Samples were fused into glass bead and were
analyze quantitative and qualitatively.

4. Result and Discussion

4.1 Mineralization

During the field investigation there is no of indication of massive galena ore in the area. An
excessive amount of lead fluid is observed in almost all natural occurring aggregates and soil.
Galena and lead bearing minerals are prominent to changes and it is quite significant with the area
that is hydrothermal active with pH in the range of 5.5 – 6.5.

4.1.1 Pyrite and the Occurrence of Secondary Lead Minerals

The presence of pyrite in the region at a very high quantity (from as low as 120ppm to 10%) might
give high influences on the low pH reading as observed. Pyrite will form a galvanic couple with lead
compounds and galena due to the large difference in the rest potentials. Galena will act as anode and
pyrite will reduce oxygen as it is a highly cathodic material.

Anode
Oxidation : Pb → Pb2+ + 2e-
Formation of Sulphur : PbS → Pb 2+ + S + 2e-

In anode dissolution of galena or primary Lead compound is occurring

Cathode
Reduction : Fe → Fe2+ - 2e-
FeS → Fe2+ + S + - 2e-
Reduction of Oxygen : 2e- + ½O2 + H2O ↔ 2OH- (aq)

Where the electron is supply for the oxygen reduction

The full reaction

PbS + ½O2 + H2O ↔ Pb 2+ + S + 2OH-

Pb will form a secondary lead mineral with the releasing of Sulphur

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Lead form intermediate product (To form PbO/Litharge or PbCO3/Cerrusite) and finally secondary
product that in the case of Sg. Pong wulfenite

Pb 2+ + O2- → PbO or PbO + CO2 → PbCO3

Secondary product, wulfenite is form with the introduction of molybdite (MO3)

Pb 2+ + CO2- + O- MO3 → PbMO4 + CO2

This results in accelerated oxidation of lead particularly as the pyrite content in the soil and
aggregates is increased. The observed mineral association and sequence of mineralization in the
oxidized zone at Sg Pong should be clearly outlined and understood to provide background
information against which the activity of electron and hydrogen ion relation (Eh-pH) and their
control over the distribution of Pb-Mo in the area.
The most obvious effect of the galvanic oxidation of lead by pyrite is the release into the
system of oxidation products, providing an ample supply of lead ions available to activate gauge
mineral, most notably in the area of which is lead/molybdenum to form wulfenite, lead/carbon
forming cerrusite, lead/arsenic forming pyromophite and lead/phosphate that the main source of
mimetite formation.
Observation on the mineral and chemical quality on the soft carbonaceous shale, soil and
panned concentrate shows that there might be a close relation between the oxidation of galena to
form these secondary minerals (Table 1.1). A similar process is also observed on the oxidation of
pyritic tin such as stannous ferrous pyrite that is found in Bukit Paku, Pengkalan Hulu. The
oxidation and weathering of pyrite induced the concentration of cassiterite in the river concentrate
near Bukit Paku.

4.2 Mineralogy and Chemical Analysis

The carbonaceous shale and river concentrate exist together with manganite ilmenite, tourmaline,
iron oxides, stannite and other lead secondary mineral such wulfenite, galena, sphalerite, plattnerite,
cerrusite and mimetite, that formed due to natural weathering and floatation of lead by oxidation that
is induced by pyrite. X-ray diffraction (XRD) pattern and XRF spectra of Sg. Pong non magnetic
concentrate, confirm the presence of these secondary lead minerals in all the lithological categories
sample.
The presence of lead and molybdenum in soft shale, concentrate, and soils in most of the
area are quite significant. The source of molybdenum is believe to be originated from of the
surrounding rock such as granite and quartz (Table 1).
Apparently the wulfenite has a close appearance and physical properties with the mineral
mimetite. Exist in a very small quantity, it is almost invisible in the XRD pattern and XRF spectrum
only indicate a small amount of arsenic and chloride in most of the sample collected. it is quite
difficult to separate both the mineral as it has similarity in size and colour. The XRD spectra of a
wulfenite that is separated during quantitative mineral examination (QME) show an indication that
the mimetite is still exist with the remaining wulfenite minerals (Figure 1)
Ten samples of each shale, river concentrate, and soil sample from block seven are collected and
qualitatively analyze. All of the sample contain a significant amount of lead, molybdenum,
vanadium, and chlorine. The highest percentage detected express as oxides are listed in table

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Table 1 Chemical Composition of shale, river concentrate and soil from Sg. Pong. (S1, SL1,
RF1 collected from block 5 and S2, RC1, RF2 from block 7, SL2 from block 8)

Shale River Concetrate

Analyte
S1 S2 RC1
Raw Panned Clean Raw Panned Clean Panned Clean
PbO 0.48 50.8 57.8 3.08 37.5 48.0 0.80 20.6
MoO3 0.21 21.7 25.0 0.64 17.2 20.2 0.42 11.5
V2O5 0.08 1.32 3.02 0.39 2.08 4.77 0.02 0.01
Fe2O3 5.33 1.55 0.06 2.10 1.22 0.03 6.82 0.45
TiO2 0.15 0.23 0.01 0.22 0.36 0.01 9.22 0.05
S 0.29 0.01 <0.01 0.05 0.01 <0.01 3.22 0.02
MnO 0.05 2.78 0.03 8.11 18.7 6.25 7.22 0.09
ZnO 0.02 0.02 0.01 0.03 0.11 0.07 0.01 0.02
SiO2 65.3 7.83 2.55 67.8 10.7 0.97 80.5 0.23
Al 2O3 17.4 5.91 0.05 16.9 4.66 0.02 0.15 0.04
Cr2O3 0.02 0.04 0.16 0.05 0.22 0.76 0.03 1.01
SnO2* 18 120 118 21 140 625 233 1380
Cl* 26 1200 3520 45 920 7400 2.0 22
As* 42 3.3 1.5 33 282 320 332 12.5

Soil Rock
SL1 SL2 RF1 RF2 RF2
Granite Indurated Quartz
Shale
Raw Panned Clean Raw Panned Raw Raw Raw
PbO 6.68 12.7 20.3 7.42 22.5 0.23 2.11 <0.01
MoO3 0.64 6.00 10.1 2.12 8.55 0.81 0.85 0.02
V2O5 0.39 0.92 0.45 0.33 0.77 0.07 0.21 <0.01
Fe2O3 3.41 7.65 0.12 2.02 5.35 3.87 3.15 0.16
TiO2 0.76 1.72 0.02 1.22 0.30 2.88 0.02
S 0.81 0.01 0.01 0.02 0.42 0.89 <0.01
MnO 18.7 40.8 22.2 8.21 3.33 2.56 0.52
ZnO 0.11 0.21 0.42 0.22 0.03 0.02 <0.01
SiO2 50.7 11.2 0.38 47.5 66.8 61.5 97.5
Al2O3 8.72 0.42 0.02 20.5 17.6 16.1 0.95
Cr2O3 0.04 0.38 2.22 0.15 0.02 0.11 <0.01
SnO2 10.5 37.2 162 46.7 21.2 2.2 <1.0
Cl 65 201 550 162 102 232 <1.0
As 3.3 7.1 19.2 2 126 118 21.2

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21000

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Fig 1 XRD phase analysis of non magnetic separation of concentrate containing ( X ) galena, ( )
cerrusite, ( ) wulfenite , sphalerite ( ), plattnerite ( ),

28000
712
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Fig 1.0 XRD phase analysis of ( ) wulfenite and ( ) mimetite after QME analysis from collected
concentrate sample marked 712

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Ten samples of each shale, river concentrate, and soil sample from block seven are collected and
qualitatively analyze. All of the sample contain a significant amount of lead, molybdenum,
vanadium, and chlorine. The highest percentage detected express as oxides are listed in table

4.3 Microscopic Study

In Sg. Pong, under magnification the tiny patch of wulfenite are orange, orange-red, orange-yellow
and colourless crystals. It has similarity in colour with mimetite and vanadinite that occur
associating with the mineral. Superficially wulfenite crystal looks like cubes or hexagonal crystal,
but close magnification there is a significant different that separate wulfenite from other lead
minerals and gauge. The obvious and almost transparent tetragonal symmetry with squarish cross
section outline confirm its existence. Mimetite and vanadinite that are associating wulfenite on the
other hand is hexagonal.
In term of hardness Sg. Pong wulfenite is fragile and the most softest lead crystal after
anglesite. The hardness is in the range of 3.7 – 4.0 mohs and hardly exceeds 4.0 of the mohs scale.
Even though the crystals are brittle where it could be easily crunch into whitish powder, Sg, Pong
wulfenite is very well formed and show no obvious signs of corrosion. This is due to the stability of
lead molybdate (PbMO4) structure of wulfenite that could withstand robust temperature and pH
condition.
Most of the wufenite in block 5,7, and 8 were found in carbonaceous shale and indurated
shale and it exist associating with some manganese oxides minerals such as manganite and
hydromanganite. This manganese oxide mineral is easily leached and dissolved from its host rock.
The deposition of manganese oxides and hydromanganese oxides could be observe on most of the
surface of the Wulfenite.
And apparently it make microscopic study and QME analysis tougher where visual
interpretation to separate the minerals might leads to a misleading information.. The thick deposition
of ferrous manganese oxides mixture on the wulfenite surface gives a good superficial magnetic
conductivity, which most of the ferrous manganese coated wulfenite is collected by the magnetic
separator.
Even though there is a significant deposition of manganese oxides on the surface of the
wulfenite, no penetration or seeping of this manganese fluid to form dentrital manganese we
observed. Replacement of molybdenum by manganese to form coronadite (PbMn8O16) is not
detected from all the XRD spectra. This shows a good chemical stability of Tetragonal
Diphyramidal structure of PbMO4.

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A B

C D

Figure 2 (A) Collected mineral after a clean panning

(B) Wulfenite that is collected after magnetic separation where most of the lead minerals is non magnetic
(C) A close up of the wulfenite coated by manganite and hydromanganite
(D) Tetragonal dipyramidal structure of sungai Pong wulfenite

5. Conclusion

Wulfenite mineralization in sungai Pong occur in a highly mineralization zone that is located
between intrusive vein from the Bintang Hill on the west and partly compose of the Main Range.
The low pH with the presence of pyrite in the region form a galvanic couple with lead minerals
(galena) due to large difference in their rest potentials and accelerate the oxidation of primary lead
to form secondary products such as wulfenite, mimetite and cerrusite. It is suggested that in future
the formation of secondary minerals in sg pong is study in detail.

6. Acknowledgements

The author wishes to thanks Sand and Mineral Processing Sdn. Bhd. the concession holder for their
kind cooperation while this works was being conducted. The author would also like to express their
sincere gratitude to mineralogy and petrology staffs and Puan Siti Maizatul Azwa and Dr. Samsul
from mineral research centre for assisting us during the XRD and SEM analysis. This paper is
personally dedicated to the author’s family for understanding their interest and passion.

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7. Reference

ASM International, 1987, Glosarry of term in Ninth Edition of the Metal Handbook, Volude 13,
Corrosion, pp 1- 4 (American Society of Metal International: Metals Park)

C.J. Greet, 2005, The Influence of Pyrite on Galena Oxidation and Subsequent Flotation, Journal of
Centenary of Flotation Symposium, pp 959 – 966.

J.W Micheal ( 2009) Solubility controls for molybdenum in neutral rock drainage, Journal of
Geochemistry : Exploration, Environment, Analysis, pp 21 – 32.

T. Dean (1960) A galena – Wulfenite – Uraniferous – Asphaltite Horizon in the Magnesian

Limestone of Nottinghamshire, Journal of Mineral Society, pp 705 – 710

Mithell et. al., (1947) Geology of the Country around Barnsley. Mem. Geology Survey.

H.P Frederick (2010) A Field Guide to Rocks and Minerals, Houghton Mifflin Publisher, pp 44 – 50

A.A. Kaminskf (2006 ) Achievements in the Field of Physics and Spectroscopy of Activated Laser
Crystals, phys. Stat. sol pp11 – 57

S.L Erik et. al., (1981) Retrival of Wulfenite fron the Cryolite Deposit, Ivigtut, South Greenland ,
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F. L. Hess (1924) Molybdenum Deposit, A Short Review, United State Geological Survey

C.K. Gupta (1992) Extractive Metallurgy of Molybdenum CRC Press

A.K Suri (1997) Production of Ferromolybdenum from Indian Resources, NML pp 71 – 82

N.R. Aghamalyan (2006) Photoelectric and Spectal Properties, Romanian conference on Advance
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