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Authors’ contributions
This work was carried out in collaboration between all authors. Author JAO designed the study, wrote
the protocol, and wrote the first draft of the manuscript. Authors KSA, HBH and NBB managed the
analyses of the study performed and also improved the results. All authors read and approved the
final manuscript.
Article Information
DOI: 10.9734/JGEESI/2015/19622
Editor(s):
(1) Ioannis K. Oikonomopoulos, Core Laboratories LP., Petroleum Services Division, Houston Texas, USA.
Reviewers:
(1) Anonymous, Wrocław University of Technology, Poland.
(2) Anonymous, Phranakhon Rajabhat University, Thailand.
(3) Abdel Monem Soltan, Geology Department, Ain Shams University, Egypt.
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ABSTRACT
The mineralogical characteristics of metacarbonate from the Obajana area were determined with
combine petrographic and X-ray diffraction methods. These methods revealed that the marble
samples contains major proportion of calcite with minor quartz, dolomite, graphite, pyrite, olivine
and phlogopite as accessory minerals. Also, analytical data from inductive coupled mass plasma
spectrometry (ICPMS) showed an average SiO2 of 2.39%, high CaO content of 54.89%, with low
MgO content of 1.1% and iron oxide content of 0.33%. Trace element composition, indicated that
the metacarbonate is rich in Ni, Rb, Sr and Ba compared to Co, Ga and Nb in the metacarbonate.
These characteristics make the metacarbonate suitable for major industrial use especially the
production of high grade precipitated calcium carbonate (PCC).
_____________________________________________________________________________________________________
Metacarbonate rocks in the study area are 3.1 The Field Relations and Mode of
utilized for the production of cement, fertilizer and Occurrences Characteristics of the
tiles by local industries. Hence, the purpose of Mable
the study is to investigate the petrographic and
geochemical characteristics of metacarbonate
The Obajana marble deposit lies 13km west of
found in the north central Nigeria towards its
Obajana town and is located between latitude N
applications in the production of PCC. 070 54’ to N 080 00’ and longitude E 0060 25’ to E
0
006 30’. Notable occurrences of metacarbonate
The combination of X-ray Diffraction (XRD), rock in lensoid form can be found around the
inductively coupled plasma mass spectrometry
northern to southern area of Obajana. These
analysis (ICPMS), the petrographic and physical
metacarbonate rocks are interbanded with meta-
techniques were used to reveal qualitatively, the
igneous rocks such as phyllite and quartz mica
contents of the metacarbonate rock for the
schist (Fig. 1). The major rock types in Obajana
production of high quality precipitated calcium area are gneisses, schists, banded iron
carbonate (PCC).
formation, quartzite and marble. Rocks in this
area generally have a North-South trend and dip
2. METHODOLOGY in a western direction.
Representative samples of the metacarbonate
rock were collected along the trend of the marble The marble bodies are exposed along river
band extending from the Southern area (Fig. 1) channels. However, the contacts with the schist
of the deposit towards the Northern part (N 07° rocks are not exposed. They are two textural
54’ to N 08° 00’ and longitude E 006° 25’ to E varieties of the metacarbonate rock which are
006° 30’). Optical microscopy and X-Ray fine-grained variety which sometimes has a
Diffractrometery (XRD) obtained with Philip 1140 mixed band of white and grey colour. The second
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Onimisi et al.; JGEESI, 3(3): 1-10, 2015; Article no.JGEESI.19622
is the medium to coarse-grained variety which is homogeneous; for instance; pyrite is enriched in
mostly bright white to pale white in colour. In the marble samples located around the northern
addition to the carbonate minerals abundant in part of the deposit while the green olivine is
the marble samples, graphite, quartz, phlogopite, enriched in samples from southern areas. The
iron oxides, olivine and pyrite were also present marble samples further display calcite with twin
as accessory mineral constituents. However, the lamellae and rhombohedral cleavages.
distribution of these accessory minerals are not
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Onimisi et al.; JGEESI, 3(3): 1-10, 2015; Article no.JGEESI.19622
Fig. 2. Photomicrograph of the marble in transmitted light showing: Quartz, calcite, and
phlogopite
Petrographic study of the metacarbonate rock reveals the metasomatism of the parent mineral assemblage.
Alteration assemblage were possibly composed of Tremolite ± Phlogopite ± Calcite ± Quartz
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Onimisi et al.; JGEESI, 3(3): 1-10, 2015; Article no.JGEESI.19622
Fig. 3. X-ray diffractogram for Obajana marble sample showing calcite (abundant) and
dolomite (minor)
60
50 Loc 1
Loc2
Composition in wt%
40 Loc3
Loc 4
Loc 5
30
Loc 6
Loc 7
20
Loc 8
10
0
SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5
Loc 1 7.99 0.12 2.31 0.88 0.02 2.37 46.9 0.33 0.47 0.09
Loc2 3.12 0.04 0.81 0.35 0 0.85 52.9 0.15 0.21 0.06
Loc3 0.58 0 0.08 0.06 0 0.18 57.97 0.07 0.02 0.03
Loc 4 1.99 0.03 0.43 0.24 0 2.89 51.66 0.12 0.04 0.05
Loc 5 1.56 0.02 0.34 0.19 0 0.73 54.28 0.1 0.06 0.05
Loc 6 0.67 0 0.1 0.09 0 0.31 58.54 0.07 0.01 0.08
Loc 7 2.54 0.03 0.52 0.25 0 1.06 53.43 0.11 0.09 0.05
Loc 8 0.67 0 0.11 0.08 0.03 0.41 55.51 0.07 0.02 0.12
Components
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Onimisi et al.; JGEESI, 3(3): 1-10, 2015; Article no.JGEESI.19622
High content of silica of about 7.99% in loc1 of very suitable in pcc production. The elemental
the sample may indicate a fluid inclusions which Cu concentration in the samples ranges from 1.0
could be evidences for syn to post metamorphic ppm – 6.3 ppm with an average value of 2.58
hydrothermal interactions with the ppm, higher values were encountered in samples
metacarbonate and the host rocks. Most of the where marbles formed intercalation with quartz
samples in Table 1 shows low values of L.O.I, mica schist. These values of Cu are acceptable
this indicate the calcitic nature of the deposit, in for the production of pcc using British standard
addition to having a very low amount of Al2O3, as show in Table 3. Lead concentrations in the
MnO, K2O, TiO2 and Na2O. sample ranges from 0.3 – 1.8 ppm with an
average value of 1.3 ppm. However, zinc
Trace elements content shown in Table 2 reveals concentration range from 1.0 ppm – 10 ppm with
that the marble has high Strontium values that an average of 2.63 ppm. Lead and zinc occur
ranges from 1577 ppm – 3673 ppm with the generally in close association. Most lead and
lowest values detected in some impure samples zinc occurrence are confined to marble,
close to the contact with the host rock. Average limestone, dolomite and other calc-magnesium
value for the Strontium is 2853.5 ppm. Of all the rich rocks. In Obajana, they occurred as
trace element Strontium is the highest which associated element in the marble deposit [11].
confirms its association with high calcium These values are within range for the production
content. The presence of high strontium makes it of high grade precipitated calcium carbonate.
Table 2. Geochemical analytical results of the trace elements found in Obajana marble
samples
4000
3500
Trace element concentration (ppm)
3000 Loc 1
Loc2
2500
Loc3
2000 Loc 4
Loc 5
1500 Loc 6
Loc 7
1000 Loc 8
500
0
Ba Co Cu Pb Zn Rb Sn Sr Ta Th Zr Ag Au Hg Ti
Loc 1 157 1.5 6.3 4 10 21.6 37 3186 44.2 2.5 28.6 0.1 0.5 0.01 0.1
Loc2 100 0.6 1.3 1.5 3 7.8 0 3058 0.3 0.7 8.7 0.1 0.5 0.01 0.1
Loc3 57 0 1.7 0.5 0 0.8 16 3678 16.2 0.3 2.2 0.1 0.5 0.01 0.1
Loc 4 24 0.5 3.2 1.3 1 2 5 1577 5.4 0.4 7.7 0.1 0.9 0.01 0.1
Loc 5 64 0 2.3 0.7 2 2.9 15 2318 11.5 0.5 5.9 0.1 0.5 0.01 0.1
Loc 6 36 0.4 1.8 0.3 0 0.2 9 2586 7.7 0.2 1.9 0.1 0.5 0.01 0.4
Loc 7 83 0.4 2.8 1.8 2 4.1 5 3156 4.2 0.5 5.4 0.1 0.8 0.01 0.1
Loc 8 50 0 1 0.9 1 1.1 0 3269 0.3 0.3 3.4 0.2 1.6 0.02 0.1
Trace Elements
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Onimisi et al.; JGEESI, 3(3): 1-10, 2015; Article no.JGEESI.19622
Table 3. Typical chemical specifications of a geochemical results from ICPMS confirm that it is
PCC product [12] calcitic rather than dolomitic.
3.3 Physical Characteristics Table 3 shows the product specifications for high
quality PCC product, however the desired
Physical property determinations in Table 4 properties of PCC generally varies according to
showed that there is no marked difference in its field of application. In paper industries, high
apparent porosity values for the raw marble quality PCCs enhances the smoothness,
samples (0.66%), due to these low porosity brightness, and opacity of paper. It also
values the marble deposit aside the production of increases receptivity of the ink. In paint, CaCO3
pcc can also be use by the constructions is used as the primary extender compound to
industries. The bulk density value (2.54 g/cm3) reduce consumption of higher cost pigments, like
and specific gravity value (2.72) for the samples TiO3. Fine sized and narrowly ranged PCC
are within the ranges for Precambrian marble grains provide gaps among TiO2 particles and
generally [13]. These values are comparable to improves their binding power. By this extension,
Indiana marble [13] and Cheetor marble [14]. the opacity is improved. The usual product
However, these values are slightly higher specifications for PCC is purity of more than
compared to those for Sharpfell marble [15], 99%, density of 2.7 g/cm, particle size for filler
Muro marble [16] and British whitening [16]. pigments of 70% < 2 µm, and the specific
Compressive strength (93.77 Mpa), and Shear surface area of about 10 m2/g. The particle size
strength (13.81 Mpa) are within the range of has a significant effect on smoothness, gloss and
values for marbles [13] and meets specification printing characteristics of the paper [18].
for use as road bases, construction stone and Characteristics of printing are also in relation to
ornamental stones. PH value of 8.3 for the the particle size range and particle shape of
studied marble is comparable to Igbetti marble PCC, which also directly affects the consumption
[17] and Cheetor marble [14]. This simply means of chemical additives in papermaking. The
that the powdered marble sample can be used to brightness of the PCC filler pigments should be
reduce soil acidity level, thereby optimizing higher than 93%, and the pH of 1 mol of PCC in
maximum plants growth in agriculture. Most 1 L solution should be 9. Average particle size of
tropical soil is acidic due to high precipitation, PCCs as coating pigment should be in 0.4 to 2
acid rain and depletion of basic nutrients by µm size range, refraction index of 1.49 – 1.67
crops and application of nitrogen fertilizers [2]. and a specific surface area of 4 – 11 m2/g.
Studies by [14] revealed that aluminum ion is the Narrower particle size ranges and higher
prominent cation in the majority of soils with pH 5 refraction indexes of PCCs improves light
or less. Above all, these figures are comparable scattering of the sheets. The ISO standards for
to international standards for PCC production. brightness of PCCs as a coating pigment is 95%,
which necessitates a CaCO3 source with a high
Furthermore, a plot of the ternary diagram in purity in order to be used as a raw material [19]
Fig. 4 for the studied marble samples using For PCC manufacturing industry, raw material
7
Onimisi et al.; JGEESI, 3(3): 1-10, 2015; Article no.JGEESI.19622
SiO20 1
0.2 0.8
0.4 0.6
YA
xis
ZA
xi s
0.6 0.4
0.8 0.2
1 0
should contain low manganese and iron as importation of the PCC from Asia and Europe for
mineral impurities because these elements have use in most developing nations like Nigeria
detrimental effects on the brightness of the prevails. The PCC, an value added product (in
product [19]. high demand) from the marble rock following its
characteristic compositions has received wide
Study by [4] reveals that marble with less than applications in paper, paint, textile and
0.50% of MgCO3 is calcitic, those with greater detergents, among others [20-23]. Industrially,
than 40% of MgCO3 are dolomitic and those that PCC is synthesized from limestones [24] and
falls in-between 5% and 40% of MgCO3 are from high purity calcium carbonate resources.
referred to as magnesia marble. Based on this, The availability of the active ingredients CaO
the Obajana marble is calcitic and therefore can (46.9 – 58.54 wt%) in high percentage makes the
be applied in a variety of precipitated calcium deposit a natural raw material for the production
carbonate industries. of PCC. Similarly, [25] reported the industrial
PCC manufacturing process from naturally
Obajana marble deposit has a considerable high
available carbonate rocks following three
content of calcium carbonate that makes it
successive steps: (1) calcination process where
suitable in several industrial applications such as
quicklime (calcium oxide, CaO) is produced by
fertilizer, cement production, production of lime
heating limestone ore, (2) conversion of CaO into
for both steel industries and water treatment.
slaked lime (calcium hydroxide, Ca (OH)2
Although, the Obajana marble is being utilized for
through the hydration process and (3) synthesis
some of the mention applications. However, the
of PCC by bubbling CO or adding aqueous
production of high grade precipitated calcium
solutions of carbonate salts such as sodium
carbonate (PCC) is being neglected due to
carbonate through Ca(OH)2.
inadequate information. Therefore, the
8
Onimisi et al.; JGEESI, 3(3): 1-10, 2015; Article no.JGEESI.19622
Consequently, the compositions of the marble 4. Elueze AA. Rift system for Proterozoic
rock samples stand to justify the economic schist belt in Nigeria. Tectonophysics.
potential of the marble rock deposit in the study 1992;209:167–169.
area as suitable source for high quality PCC 5. Elueze AA, Okunlola OA. Petrochemical
production. and petrogenetic characteristics of meta
sedimentary rocks of Lokoja-Jakura Schist
4. CONCLUSION belt, Central Nigeria. Journal of Mining and
Geology. 2003;39:21–27.
The metacarbonate deposits of Obajana occur in 6. Harrison DJ, Hudson JM, Cannel B.
beds intercalated by schist, phyllite, and granite Appraisal of high purity limestone in
gneiss. The mineralogy and the petrography of England and Wales. Part 1. Resources.
the metacarbonate samples have been Technical report British Geological Survey
examined. Calcite is found to be the major WF/90/10; 1990.
mineral in the marbles. Quartz appears as the 7. Mathers SJ, Harrison DJ, Alvarado R. An
minor mineral in almost all varieties of Obajana assessment of the potential of Barra
marbles. Other minerals present are graphite, Honda limestone, Guanacaste Province,
olivene, pyrite and very low content of dolomite. Costa Rica. Technical Report British
In term of texture, the recognized field samples Geological Survey WC/90/37; 1990.
are of two varieties termed fine-grained that 8. Emofurieta WO, Ekuajemi VO. Lime
sometimes has a mixed bands of white and grey products and economic aspects of Igbetti
colour. The second is the medium to coarsed- Ososo and Jakura marble deposits in
grained veriety which is mostly bright white to Southwest Nigeria. Journal of Mining and
pale white in colour. Results from XRD analyses Geology. 1995;1:89-97.
and petrographic investigation suggests that the 9. Bathurst RGC. Carbonate sediments and
appearance of quartz depends on the availability their diagenesis. Developments in
of silica in the limestone precursor prior to Sedimentology, Amsterdam. 1975;620.
regional metamorphism. The geochemical 10. Brown T. Setting the standard in the
analysis of pulverized the marble sample shows natural stone industry. Marble Institute of
that CaO content varies from 46.90 to 58.54%. America 2007;278.
Other impurities includes: Fe2O3, Al2O3, MgO and 11. Abdullateef JO, Elueze AA, Ahmed II JB.
SiO2. Only the latter two have an average Geochemistry and economic potential of
content higher than 1%. All these characteristics marble from Obajana, north central,
makes the deposit highly suitable for most Nigeria. Advances in Applied Science
industrial use especially precipitated calcium Research. 2014;5:146–151.
carbonate production (PCC). 12. Yamuna Pvt, Ltd. Specification Grade for
Calcium Carbonate Paper Industry.
COMPETING INTERESTS Available:http://www.yamunacalcium.in/ht
ml/calciumcarbonate-paper-industry.html
Authors have declared that no competing th
(May, 4 2015)
interests exist. 13. Boynton S. Chemistry and technology of
limestone. John Wiley and Sons Inc, New
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Onimisi et al.; JGEESI, 3(3): 1-10, 2015; Article no.JGEESI.19622
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