Environ Earth Sci (2016) 75:1115
DOI 10.1007/s12665-016-5916-7
ORIGINAL ARTICLE
Assessment of barite of Lasbela, Balochistan, Pakistan, as drilling
mud and environmental impact of associated Pb, As, Hg, Cd
and Sr
Bushra Shahab1 • Erum Bashir1 • Maria Kaleem1 • Shahid Naseem1
Tahir Rafique2
Received: 15 January 2016 / Accepted: 19 July 2016 / Published online: 25 July 2016
Ó Springer-Verlag Berlin Heidelberg 2016
Abstract Barite deposits of the Lasbela District,
Balochistan, hosted in the Ferozabad Group (FG) of
Jurassic are relatively pure and have BaO value ranging
from 40.18 to 60.91 % with minor amounts of Sr, Fe and
Ca. The measured average density of the studied samples
(4.21 g/cm3) is compatible with the API-13A specification.
The quantity of water-soluble alkaline earth metals found is
very low (av. 50.76 mg/kg) and safe to be used in the
drilling mud. The scanning electron microscope study of
some of the selected samples revealed nearly 10 % parti-
cles are fine (\6 lm) and have equant, subrounded to
rounded shape; however, larger particles ([10 lm) are
tabular and low in quantity. The average content of Pb
(3418 mg/kg) in the barite samples is relatively high as
designated by the API specification (1000 mg/kg), while
Hg, As and Cd contents are very low, except in a few
samples. The average content of Sr is 1.19 %, indicating
hydrothermal origin of the barite deposits of the study area
and to some extent it is toxic in biological functions. Some
of the samples have elevated amount of SiO2
(1.83–8.88 %) which may cause risk of silicosis in the
persons either involved in milling industry or at well site.
The positive loadings of first factor of principal component
analysis for Ba and S, and density revealed genetic alliance
with MVT/SEDEX mineralization, and negative loadings
of Ca, Mg and Fe demonstrate hydrothermal alteration of
host rock.
& Bushra Shahab
bushra_shahab@ymail.com
1
Department of Geology, University of Karachi,
Karachi 75470, Pakistan
2
Applied Chemistry Research Centre, PCSIR Laboratories
Complex, Karachi 75280, Pakistan
•
Keywords Barite
Drilling mud
Trace elements

Environmental impacts
Lasbela
Introduction
Barite (BaSO4) is known for its heavy specific gravity and
used primarily as a weighting agent for drilling fluids; in
addition, it has application as radiation-shielding material
(Fugaru et al. 2015; Godwin 2012) and heavy weight
aggregate (Naseem et al. 2011). Nearly 85 % of the
worldwide barite production is consumed in drilling of oil
and gas wells (Scott et al. 2010). In exploration, drilling
mud plays a vital role and is used as weighting agent. It is
normally powder of some heavy minerals, viz. ilmenite,
haematite, galena and barite (Julius et al. 2015), and bal-
ances high subsurface formation pressure during oil and
gas well drilling. Among these, barite is widely used in the
mud because of easy availability, low price, high specific
gravity, low hardness and brittle nature. The production of
barite powder requires certain specification to meet the
requirement of petroleum industry. The specification of
barite for drilling mud is established by API-13A (2010)
(Table 1).
In Pakistan, barite is mainly obtained from the districts
of Lasbela (Fig. 1) and Khuzdar (Ahsan and Mallick 1999).
Other deposits are located in Hazara District (Ali et al.
2011). During the last few decades, the production of barite
in Pakistan was poor, but recently production of barite
increased to 75,000 metric tons; this promotes Pakistan
from 12th to 8th rank in the world as producer of barite
(Jewell and Kimball 2015). Pakistan’s barite has a good
demand in the international market. Persons involved in
mining and processing of barite are often affected from the
toxicity of barium and allied hazardous elements (OGP
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Table 1 Physical and chemical
Parameters
specifications of drilling barite
(after, API Specification 13A,
2010)
Density
Water-soluble alkaline earth metals, as Ca
Residue greater than 75 lm
Particles less than 6 lm
Maximum mercury
Maximum cadmium
NE Not estimated due to higher isolated patchy values
2009); furthermore, prolong exposure to fine quartz (SiO2)
particles (\10 lm) poses a health hazard and may cause
silicosis (Salisu et al. 2015). In the barite mineralized area,
groundwater quality is also contaminated (Suresh et al.
2007). Hydrocarbon exploration companies face the prob-
lem of disposing drilling waste that have the potential to
impact the environment too (Onwukwe and Nwakaudu
2012). Barite is often associated with minerals of Pb
(galena), Hg (cinnabar) and As (orpiment, realgar, niccol-
ite, etc.), which are proved hazardous materials not only for
human life, but also for other biota (Neff 2005). A hypo-
thetical model is presented to elaborate the phenomenon of
contamination from barite and associated hazardous ele-
ments, from mining, processing and drilling areas (Fig. 2).
In this study, the distribution of major and trace ele-
ments within a suit of selected samples has been used. The
distribution and variations of chemical elements mainly
determined and related to the physical and chemical
properties of the host minerals (Perri et al. 2014) and
assessment of environmental impact of associated toxic
elements with barite. Furthermore, the principal component
analysis (PCA) has been used to better understand the
distribution of and relationships among major and trace
elements; PCA is a technique to combine numerous vari-
ables into several latent variables that underlie the multi-
variate data (Perri and Ohta 2014; Perri et al. 2014, 2015).
The environmental problem related to barite used in the
drilling mud is demonstrated diagrammatically to make
public aware of concern to opt for proper mitigation pro-
gram (Fig. 2).
Methodology
Thirty-three barite samples were collected from seventeen
different locations (Fig. 1). Large (15 cm) pieces of barite
were excavated from open-cast mine are first crushed in a
jaw crusher to 10–15 mm size and pulverized in a hammer
mill. Further beneficiation was done with the help of
classifier (Fig. 2). After proper coning and quartering,
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Environ Earth Sci (2016) 75:1115
Specification Current study
Min. Max. Mean
4.10 g/cm3, minimum 3.85 4.42 4.21
250 mg/kg, maximum 16.35 185.60 50.76
Maximum allowed, 30 % 0.67 1.03 0.78
Maximum allowed, 30 % 9.78 12.13 11.03
1.0 mg/kg 22.4 148.6 NE
3.0 mg/kg 0.50 30.90 NE
about 1 kg sample is selected for physical, chemical and
grain size analysis.
The geochemical analyses were performed by XRF,
following the method of Salisu et al. (2015) using Thermo
Fisher Scientific Niton XRF Analyzer (XL3 Analyzer
version 7.0.1) and calibration with certified reference
materials from National Institute of Standards and Tech-
nology (NIST, USA). Alternately, for chemical analysis of
BaSO4, pulverized barite samples were digested by car-
bonate fusion method and wet acid treatment and estimated
gravimetrically (API 2010). Water-soluble alkaline earth
metals (as Ca) were determined by using EDTA complex
titration method. The density of the pulverized barite
samples was determined by Le Chatelier specific gravity
bottle, using good-quality kerosene oil at controlled tem-
perature. For grain size analysis, a 200-mesh sieve is used
and the grains with size designated as [75 lm are retained.
The surface morphology and size of micronized grains of
barite sample was examined by using JEOL JSM 5910
SEM in the Faculty of Science Laboratory, University of
Karachi, Pakistan. Analytical data of barite were statisti-
cally analyzed, and component plot on rotated space dia-
gram was prepared by IBM SPSS software (version 22).
General geology and mineralization
In the Lower Indus Basin (LIB), Wulgai Formation is
probably the earliest Triassic sedimentary rock, poorly
exposed in the Zhob, Kalat and Khuzdar areas (Kazmi and
Jan 1997). The upper contact of the Wulgai Formation is
transitional with the Early Jurassic sequence and shows
facies change in the sedimentation, from shale of Wulgai
Formation to thin-bedded limestone and intercalated shale
of Jurassic rock. The Lower Jurassic consists of clastic
sediments, dominantly continental origin, that grade up
into the marine carbonates and subordinate amount of
argillaceous rocks, and finally at the end of Middle Juras-
sic, regressive phase is evident (Asim et al. 2014). Seismic
interpretation and well data indicate Jurassic rocks as a part
Environ Earth Sci (2016) 75:1115 Page 3 of 10 1115

Fig. 1 Geological map of Lasbela area showing sample sites of barite; Top left, map of Pakistan, showing study area

of platform cover in major areas of the LIB. In the Kirthar
and Sulaiman provinces, the Jurassic rocks are found in the
anticlinal core; however, in the Western Fold Belt (WFB),
Jurassic rocks are widely distributed and form extensive
thrust blocks and sheets. The WFB represents the foreland
fold and thrust belt along the western margin of the Indian
Plate. During the obduction of Bela ophiolite, the Jurassic
rock of the study area bifurcated in two parts, the eastern
main Mor Range, a broad belt about 300 km striking north
south, while the western part is known as Piaro Ridge, a

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Fig. 2 Schematic model showing environmental impact of Lasbela barite during mining, milling and drilling process and possibilities of
silicosis and health hazards of Hg, Cd, Sr, As, Pb and Ba in the mine workers, labors and inhabitants of drilling site (without scale)
small, narrow wedge-shaped belt (Fig. 1). Small- to med-
ium-size barite deposits are widespread in both belts. The
Mor Range is located in the southern part of the WFB and
mainly consists of rocks of FG (Jurassic) in association
with Bela ophiolite of Cretaceous age (Naseem et al. 2016).
The Kharrari, Malikhore and Anjira formations constitute
the FG.
The Kharrari Formation (Early Jurassic) consists of
flaggy, gray micritic limestone, followed by calcareous
sandstone and quartzose sandstone; it is deposited in a
shore face to inner shelf environment (Hasany et al. 2007).
The clastic fraction of the formation contains Pb–Zn–barite
mineralization (Ahsan and Mallick 1999). Malikhore For-
mation occupies the middle part of the FG and mainly
consists of hard, compact, thick-bedded micritic limestone
deposited in platform conditions (Sheikh et al. 2006). The
sulfide-hosted (SEDEX/MVT) Pb–Zn–barite–fluorite min-
eralization within the formation is common (Husain et al.
2002). The youngest formation of FG is Anjira of Upper
Toarcian to Middle Bajocian age and is differentiated into
lower black carbonaceous shale, siltstone and mudstone
unit and an upper thin interbedded limestone in association
with shale (Shah 2009). Ahsan and Mallick (1999) reported
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Environ Earth Sci (2016) 75:1115
the presence of large barite deposits (Gunga, Surmai and
Duddar) in association with Zn–Pb in the Anjira
Formation.
The FG was deposited on the shelf flank of a rift system
resulting from the breakup of Gondwanaland and the sep-
aration of the India from Madagascar (Gnos et al. 1997).
The listric faulting during the rifting causes ascent of
hydrothermal solutions, rich in Ba, Zn, Pb, which was
deposited in the lower Kharrari and Malikhore formations
similar to the Mississippi Valley type (MVT) as indicated
by Bradley and Leach (2003), while stratiform (SEDEX)
mineralization is common in top most Anjira Formation
(Ahsan and Mallick 1999).
Results and discussion
Physical and chemical parameters
Barium sulfate and density
Ideally barite has 65.70 % BaO and 34.30 % SO3, whereas
in the presence of impurities the content of BaO and SO3
Environ Earth Sci (2016) 75:1115 Page 5 of 10 1115

Table 2 Density, water-soluble alkaline earth metals (WSAEM), major and trace element composition of Lasbela Barite
Sample SiO2 Fe2O3 Al2O3 BaO CaO MgO MnO SO3 CO2 Sr Pb Cd As Hg Density WSAEM

GM1 2.48 0.27 0.27 57.89 3.02 0.08 BDL 30.22 0.41 1.08 95 17.1 14.3 54.7 4.31 135.67
GM3 2.01 0.79 0.79 59.12 2.99 0.12 BDL 30.86 1.03 1.08 59 1.5 BDL 107.5 4.34 119.09
GM7 2.45 0.24 0.24 60.91 3.01 0.11 BDL 31.79 0.53 1.09 66 3.7 25.9 147.21 4.39 32.70
PL3 6.00 0.46 0.46 52.55 2.41 0.05 BDL 27.43 1.84 1.38 2857 30.9 165.7 92.8 4.13 40.87
PL5 8.44 1.17 1.17 51.02 3.69 0.07 0.19 26.63 1.76 1.21 1865 BDL 76.6 148.6 4.11 33.47
RN2 2.58 0.06 0.06 58.03 1.34 0.01 BDL 30.29 0.19 2.25 84 BDL 39.6 139.1 4.29 40.76
RS1 4.95 0.51 0.51 53.85 3.79 0.02 BDL 28.12 2.52 1.42 74 1.3 48.6 111.6 4.17 39.22
GL1 3.94 0.39 0.40 51.84 5.75 0.21 BDL 27.06 3.68 1.43 231 BDL BDL 104.9 4.14 29.38
HM1 4.40 0.73 0.73 45.63 10.31 0.01 0.19 23.82 6.30 1.16 173 0.6 23.58 139.3 3.95 37.56
HM3 4.79 0.30 0.30 49.64 5.26 0.01 BDL 25.91 2.28 2.55 14108 1.2 27.13 BDL 4.21 40.87
CL2 2.98 0.15 0.15 54.97 2.61 0.12 0.55 28.69 1.52 2.05 117 0.5 44.5 32.4 4.24 57.22
CL4 4.64 0.14 0.14 55.98 0.59 0.01 BDL 29.22 0.4 2.84 136 1.6 48.6 23.7 4.25 49.05
JR3 8.21 2.65 2.65 40.18 10.08 2.03 0.21 20.97 1.4 0.53 787 1.4 21.0 43.0 3.85 32.70
JR4 7.58 1.10 1.10 51.68 6.312 0.02 0.2 26.97 1.5 1.01 515 1.4 BDL BDL 4.13 35.13
KD1 8.88 1.25 1.25 49.94 4.81 0.01 BDL 26.06 4.5 1.33 119 BDL 34.1 BDL 4.08 40.87
KD2 4.56 0.61 0.61 55.87 2.811 BDL BDL 29.16 3.11 2.14 74 0.6 24.1 BDL 4.25 40.87
AD4 8.63 0.55 0.55 49.96 5.00 BDL BDL 26.07 0.46 0.70 19474 0.9 21.0 31.7 4.11 40.87
AD7 5.01 1.48 1.48 51.24 6.71 0.02 BDL 26.74 0.89 0.81 2907 BDL BDL BDL 4.12 57.22
LN2 6.16 1.03 1.03 57.12 1.86 0.01 0.31 29.81 0.89 1.45 560 1.0 14.4 BDL 4.27 51.48
LN7 5.36 0.24 0.24 57.21 0.97 0.02 0.23 29.86 0.57 1.45 823 1.4 18.2 23.0 4.42 40.87
AR4 1.83 0.22 0.22 59.35 2.30 BDL BDL 30.98 1.64 0.50 64 1.3 56.1 BDL 4.37 106.06
ZK2 2.92 0.36 0.36 60.37 0.55 0.02 0.42 31.51 1.47 1.51 159 BDL 13.9 BDL 4.34 40.87
ZK7 2.56 0.508 0.50 59.96 1.13 0.03 0.35 31.30 2.21 1.13 3226 1.3 11.6 BDL 4.31 61.31
ZK9 5.05 0.89 0.89 55.31 0.88 0.02 BDL 28.87 1.09 0.94 761 0.6 11.3 24.7 4.21 24.52
KH1 3.59 0.19 0.19 53.87 5.82 BDL BDL 28.12 0.54 0.59 9992 0.5 16.0 22.4 4.19 32.70
KH4 4.40 0.31 0.31 56.04 4.86 0.12 0.32 29.25 0.56 0.50 6125 1.1 37.9 BDL 4.25 37.56
KH5 4.08 0.24 0.24 55.62 6.55 0.01 BDL 29.03 1.83 0.52 45675 BDL 527.5 27.4 4.22 185.60
BN2 5.54 0.38 0.38 58.74 0.65 0.02 BDL 30.66 0.36 1.08 319 BDL BDL BDL 4.33 36.79
BN3 4.01 0.33 0.33 59.02 1.018 BDL 0.23 30.81 0.21 0.79 524 BDL 59.7 34.8 4.28 16.35
KN1 6.01 1.31 1.30 52.17 5.03 0.01 BDL 27.23 0.98 1.03 473 1.0 BDL 27.1 4.11 32.70
KN3 4.51 0.23 0.23 56.67 5.21 0.01 0.33 29.58 0.25 1.37 176 1.1 7.2 24.0 4.28 26.95
GH9 2.88 0.39 0.39 48.68 10.91 BDL BDL 25.41 10.57 0.39 82 BDL 9.0 34.0 4.15 40.87
GH10 4.70 0.34 0.34 48.97 9.21 0.02 0.42 25.56 1.87 0.54 97 1.4 BDL 28.5 4.16 36.79
Min 1.83 0.06 0.06 40.18 0.55 0.01 0.19 20.97 0.19 0.39 59.0 0.5 7.2 22.4 3.85 16.35
Max 8.88 2.65 2.65 60.91 10.91 2.03 0.55 31.79 10.57 2.84 45675 30.9 527.5 148.6 4.42 185.60
Av 4.73 0.60 0.60 54.22 4.16 0.12 0.30 28.30 1.79 1.19 3418 NE NE NE 4.21 50.76
3
Units: All major oxides including Sr are in %, trace elements and WSAEM are in mg/kg and density in g/cm
NE Not estimated due to higher isolated patchy values

decreases. Important impurities diluting the quality of
barite are SiO2, Al2O3, Fe2O3, CaO, MgO, SrO, CO2 and
several trace elements (Pb, Cu, Cd, As, Hg). The range of
BaO in the studied samples is from 40.18 to 60.91 % with a
mean of 54.22 % (Table 2). Despite the nonmetallic min-
eral, barite has exceptionally high density, mainly due to
the presence of barium (Ba) whose atomic weight is high
(137.327). The binary plot between BaO and density is
positive (Fig. 3a), which is also supported by the strong
correlation matrix 0.941. The amount of SiO2 ranges from
1.83 to 8.88 %, and it is high in the samples of barite
hosted in sandstone beds of Kharrari Formation, and such
samples are slight harder. Total iron (Fe2O3) varies from
0.06 to 2.65 % with a mean of 0.60 %. Iron is beneficial in
mud because the density of iron-bearing minerals is high.
The average contents of CaO and CO2 in barite samples are
4.16 and 1.79 %, respectively, most probably high amount
is the reflection of associated limestone of Malikhore
Formation. In the samples, Mg is extremely low except in
sample JR3 (1.22 %). The contrast difference in the ionic

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Fig. 4 Physical, chemical and trace elements of studied barite on

rotated space diagram (PCA)

Table 3 Factor loading values and variance %

Variables Factors
1 2 3 4

Fe -.803 -.167 .357 .197

Ba .954 -.115 .202 .128
Ca -.891 -.068 -.072 -.108
Mg -.723 -.036 .385 .114
S .954 -.115 .202 .128
Sr .387 .172 -.264 -.652
Pb -.199 -.103 -.873 .208
Fig. 3 a Plots of density (g/cm3) versus BaO (%) of studied samples; Cd .079 .815 -.005 .447
b water-soluble alkaline earth metals (WSAEM) versus Ca (%) of
barite samples of Lasbela area As .061 .914 -.091 .115
Hg -.095 .525 .329 -.491
Density .940 -.169 .086 .112
size of Mg (0.66 Å) and Ba (1.32 Å) is probably respon-
sible to hinder the uptake of Mg in the barite. The PCA Variance % 38.48 16.62 11.27 8.62
(Fig. 4) demarcated source apportionment of elements by Cumulate % 38.99 55.10 66.37 74.99
means of factor loading (Table 3). The positive and neg-
ative loadings of first factor is related to major chemical
composition of barite in consequence of either MVT or and \4.10 g/cm3 in 57, 33 and 10 % samples, respectively
SEDEX mineralization and subsequent hydrothermal (Table 2). The low-grade barite is also utilized in the
alteration, which substitute Ca, Mg and Fe of host rocks of industry, probably to mix it with high-grade barite to obtain
the study area. desirable grade. According to Scott et al. (2010), low-grade
The high density of barite is one of the important factors barite may have deleterious impurities and significantly
that make it permissible to use as a drilling fluid. Due to increase the quantity of drilling fluid required to drill a
high density of the mineral, drilling fluid produces a well, which in turn increases the quantity of disposal waste.
pressure that balances the formation pressure and prevents
the blowout of the well. Due to low production of high- Water-soluble alkaline earth metals (WSAEM)
grade barite in the market, the API 13A (2010) recom-
mended density of high-quality barite (4.21 g/cm3) may be The solubility product constant of barium sulfate is high
replaced by marginally low density (4.11 g/cm3). Analyt- 1.08 9 10-10 and pure barite is highly insoluble in water,
ical results have indicated density [4.21, 4.19–4.10 but in the presence of certain accessory minerals, some of

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Fig. 5 Scanning electron images of barite samples: a GM7, b ZK2
the elements become soluble. One of the most significant
minerals is gypsum CaSO4
2H2O, which is slightly soluble
in water (2.6 g/l) and releases Ca2? ions, and similarly
carbonate minerals (calcite, dolomite, ankerite and side-
rite), though not soluble in water but can release their
cations (Ca2? and Mg2?) in the presence of hydroxyl ions
(API 1993). Total water-soluble material in barite used in
the drilling should be less than 1000 mg/l, while soluble
alkaline earth metals (Ca) are allowed up to 250 mg/kg
(API 2010). This may react with other components in
drilling fluids and cause adverse changes in the drilling
fluid properties and different types of logging.
In the studied samples of barite, the WSAEM ranges
from 16.35 to 185.6 with a mean of 50.76 mg/kg (Tables 1,
2); however, samples collected from Khinyar Dhora,
Ghormas and Arara (Fig. 1) have indicated relatively high
WSAEM, but well within the prescribed limits of API 13A
(2010) protocol. The scatter plot between WSAEM and
total Ca content of barite samples displays that at
50.76 mg/kg value with variable concentrations of Ca from
0.39 to 7.79 %, it has little impact on the water-soluble
alkaline earth metals (Fig. 3b). Six samples (KH5, GM1,
Page 7 of 10 1115
GM2, AR4, ZK7 and CL4) show positive relation with
increasing Ca content, possibly due to the presence of
gypsum.
Grain size and shape
The control of particle size of barite powder significantly
affects the way in which the mud interacts with the
lithology being drilled. Particle size plays an important role
in the rheological behavior of drilling mud and helps the
formation of a filter cake that prevents the loss of circu-
lating fluids. The grain size mainly depends upon the
milling method and time of grinding (Zhou et al. 2015).
Shape of the grinded particles is also important; the fine-
size (\6 lm) particles have equivalent spherical diameter
(API 2010). The scanning electron microscope (SEM)
studies of some selected samples revealed equant, sub-
rounded to rounded particles; however, larger particles
([10 lm) are tabular (Fig. 5). In general, shape analysis is
crucial in the preparation of good drilling mud. Rounded-
shape particles have more wettability properties, and it will
increase floatability of barite particles in the drilling mud
(Ulusoy and Yekeler 2007).
Trace elements and health hazards
The concentration of trace elements in the minerals largely
depends on the composition of mother fluid and physico-
chemical parameters, which actually is the reflection of
genetic process (Dill 2010). The environment of natural
mineral forming processes is not ideal and uniform in
character, but in general shows intermingling. The PCA is
valuable to elucidate the distribution of trace elements in
barite and to identify the mineral formation process (Edet
et al. 2014; Engle and Rowan 2014).
Mercury
Trace quantities of Hg are often associated with the barite
deposits of hydrothermal origin as cinnabar (Jurković et al.
2011). In general, Hg concentration in barite ranges from
0.05 to 31 mg/kg, and it is high in vein-type MVT barite
deposits as compared to bedded deposits (Parker 2003).
Genetically the barite deposits of Lasbela District are MVT
and SEDEX (Ahsan and Mallick 1999). Moderately high
loading of second factor (0.525) on PCA diagram shows
incorporation of Hg in barite crystals due to its genetic
association (Fig. 4). Majority of the barite samples of study
area either have traces of Hg or are found below the
detection limit of the instrument, only nine samples have
high ([50 mg/kg) content of Hg (av. 116 mg/kg). High
Hg-bearing sites are confined in Chilro and surrounding
areas (Fig. 1). High Hg in the barite samples of the Lasbela
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area can be removed by simple leaching treatment, as
suggested by Holmes et al. (2008). The quantity of Hg may
also be reduced by mixing the low-Hg-bearing barite. Due
to high vulnerability of Hg for human beings, the maxi-
mum allowable limit is *1 mg/kg for barite used in dril-
ling (API 2010). Discharge of drilling mud contaminates
the environment (Parker 2003). Mercury is highly poi-
sonous element, and exposures can result in neurological,
cardiovascular collapse, renal failure and gastrointestinal
damage (WHO 2005).
Cadmium
Geochemically it is chalcophile element and prefers to form
sulfides, mainly as greenockite (CdS), and originates in
anoxic hydrothermal environments of SEDEX and MVT
affinity (Fleurance et al. 2013). High loading (0.815) of sec-
ond factor for Cd, associated with barite deposits of the study
area, reflect sulfide deposition (Fig. 4). Cadmium is mainly
found in association with zinc ore, because both of them have
close geochemical behavior; however, it is also associated
with the minerals of Pb, Cu, Ba and Hg (Fatoye et al. 2014).
Majority of the studied samples either have very low Cd
concentration or are found below the detection limit;
however, its value is low in sample GM7 (3.7 mg/kg),
moderate in GM1 (17.1 mg/kg) and high in PL3 (30.9 mg/
kg). These values are higher than the permissible limit of
3 mg/kg (API 2010) set for drilling mud (Table 1). The
presence of high-Cd-bearing rocks poses health threat to
the inhabitants of the area and may concentrate in the soil,
groundwater and vegetation (Burke et al. 2016). Cadmium
intoxication can lead to the damage of excretory, skeletal,
respiratory and reproductive system; in addition, it is also
suspected for carcinogenicity in humans (Godt et al. 2006).
Strontium
Strontium (Sr) is an alkaline earth metal and strong litho-
phile element; its abundance in the crustal rocks is 375 mg/
kg. Celestite (SrSO4) is capable of existing as solid solution
in barite (BaSO4) in nearly all geological environments
(Hanor 2000). In hydrothermal environment, Sr may enter
into the lattice, substituting Ba from barite; therefore, high
SrSO4 2.33–3.42 % is the signature of hydrothermal origin.
The average content of Sr in barite samples of Lasbela area
is 1.19 % (Table 2), which corresponds to 2.54 % SrSO4.
Strontium in low quantities is beneficial along with Ca
and vitamin D to strongly bind the bone tissues and
increase bone density, thus reducing the process of osteo-
porosis in humans (Jonathan 2003). On the contrary, pro-
long consumption of high Sr ([4 mg/l) may interfere the
Ca, which often leads to fractures and osteodystrophy
(Khan et al. 2010; Polyakova and Synzynys 2010).
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Environ Earth Sci (2016) 75:1115
Arsenic
Arsenic is more widespread in hydrothermal stage in the
form of arsenide (niccolite, NiAs), sulfides (orpiment,
As2S3 and realgar, AsS) along with barite. The associated
arsenic minerals of barite gradually leached out from the
drilling mud may contaminate the soil and groundwater of
the area. In aqueous phase, As is prefer to form oxyanions
arsenide and arsenate ions depending upon the pH of the
system (Smedley and Kinniburgh 2002).
Nearly 60.6 % samples of barite of study area have very
low amount of As (Table 2). Remaining samples (13 nos.),
have an average content of 53.7 mg/kg, while one sample
(KH5) has indicated very high content (527 mg/kg).
Arsenic can cause damage to the human cardiovascular,
gastrointestinal, dermal, hepatic, pulmonary, renal, neuro-
logical, respiratory and reproductive systems (Kumar 2015;
Mandal and Suzuki 2002).
Lead
Small deposits of galena are seen associated with barite
deposits in the study area. Wide fluctuation in Pb content is
seen as indicated by very low content to as high as
45,675 mg/kg in the KH5 locality near Khinyar in District,
Lasbela; however, the average Pb content in barite samples
is about 3418 mg/kg (Table 2). During the drilling activity
in a region, Pb gradually accumulates with age in bones,
kidney, liver and spleen. Adewole et al. (2010) recom-
mended controlling higher Pb in the disposed drill wastes
material and keeping it to 0.005 mg/l with the threshold
level of 0.05 mg/l.
Barium
Barite (BaSO4) and witherite (BaCO3) are the two main
minerals of Ba, commonly associated with sediment-hosted
stratiform barite deposits (Lingang et al. 2014). In general,
barite is considered harmless due to high insolubility, but
in contrast witherite is not inert and can easily dissolve
during weathering process and disperse in the areas of
occurrence (Salisu et al. 2015). Similarly during drilling
operation a number of acids, alkalis and chemicals are
added in the mud, which may mobilize Ba from barite and
witherite and accumulate it in the soil and groundwater of
the area (Fig. 2). Drinking water with high Ba when enters
the human body gets quickly absorbed in the intestine and
obstructs K in the cell and mimics the functions of Ca in
muscle contraction (WHO 2001). Prolong exposure of
barium compounds is responsible for hypertension, gas-
trointestinal disturbances, renal function and muscular
weakness. Experiment on animals revealed no evidence of
carcinogenic symptoms of Ba salts (NTP 1994).
Environ Earth Sci (2016) 75:1115
Barite and silicosis
Ingestion of pure barite powder is nearly harmless, some-
times direct contact may cause dryness and itching on skin.
The inhalation of barite powder by mine workers, pro-
cessers and drillers may cause several disorders in respi-
ratory system. Excessive barite dust may cause nuisance
condition such as coughing, sneezing and nasal irritation.
Silica (SiO2) in the form of quartz and other polymorphs
are generally associated with barite, and during pulver-
ization fine quartz (\10 lm) particle may separate from
barite matrix (Fig. 2). Prolonged breathing in of fine silica
particles may induce pneumoconiosis in the workers,
commonly known as silicosis (Seaton et al. 1986). Silicosis
is the commonest occupational lung disease worldwide
(Glazer and Newman 2004). Excessive inhalation of fine
crystalline silica dust may cause a progressive development
of silicosis; with passage of time (*10 years), it may turn
to acute and chronic silicosis, and sometimes predisposed
to develop tuberculosis in the workers (Salisu et al. 2015).
The range of SiO2 in the barite of Lasbela area is from
1.83 to 8.88 % with a mean of 4.73 % (Table 2). The level
of SiO2 in the barite is less (10 %) as specified in the API
(2010) document. Despite the fact of low silica in the study
area, reasonable efforts are necessary to reduce the risk of
silicosis in the persons either involved in milling industry
or at well site.
Conclusions
The Mississippi Valley type (MVT) and sedimentary
exhalative type (SEDEX) barite deposits are widespread in
rocks of FG of Jurassic age. The density of barite samples
varies from 3.85 to 4.42 g/cm3 (av. 4.21 g/cm3), higher
than the API-13A specified value. The amount of BaO in
the barite samples is 40.18–60.91 % with minor content of
Sr, Fe, Mn, Al and Ca. The quantity of water-soluble
alkaline earth metals found is very low (av. 50.76 mg/kg)
and is safe to be used in drilling mud. The retained amount
of particles of size 75 lm and particles finer than 6 lm are
within the recommended value of API 13A. The image of
the fine particles of some selected samples displays equant,
subrounded to rounded shape. In the majority of the barite
samples, the amounts of certain trace elements were in safe
limit; however, some of the samples have elevated quan-
tities of Hg, Cd, As and Pb. The average amount of Sr is
noted to be 1.19 %, indicating hydrothermal origin and
both Ba and Sr are toxic in biological functions. The PCA
factor loadings of major and trace elements also reflects
either MVT or SEDEX mineralization and subsequent
hydrothermal alteration, which substitute Ca, Mg and Fe of
host rocks of the study area. Some of the samples have
Page 9 of 10 1115
elevated amount of SiO2 (1.83–8.88 %) which may cause
risk of silicosis in the persons either involved in milling
industry or at well site. Considering all the physical,
chemical and toxic trace element, it is concluded that the
barite samples match API (1993) specification as men-
tioned in Section 13A, and with few exceptions, it can be
improved by applying different techniques. Overall quality
and quantity of Lasbela barite is satisfactory for use in
Pakistan as well as to promote export potential.
Acknowledgments Special appreciation is extended to Mr. Shabir
Ahmed Baloch, proprietor of the Industrial Mineral Syndicate, Kar-
achi, for many years of cooperation with the authors on the studies of
barite deposits of Lasbela, Pakistan. We thank three anonymous
reviewers for their constructive comments which improved the
manuscript. Services of Mr. Munirullah, Graphic Designer, Depart-
ment of Geology, University of Karachi is acknowledged for graphic
work.
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