Arabian Journal of Geosciences (2018) 11:385

https://doi.org/10.1007/s12517-018-3691-3

S. I. GEOLOGY OF AFRICA

Characterisation of the Egyptian Pliocene bentonite

from the Sohag region for pharmaceutical use
Abdelhamid Elshater 1 & Abdelaziz Elhaddad 1 & Attef Elattaar 1 & Magdy Abugharbia 2 & Waffa Soliman 1

Received: 28 November 2017 / Accepted: 15 June 2018

# Saudi Society for Geosciences 2018

Abstract
This paper aims to prepare purified Na-bentonite with improved properties for its use in the pharmaceutical industry. Calcium
bentonite from the Sohag region of Egypt was activated with various proportions of sodium carbonate (2, 3, 5 and 8 wt.%).
Additionally, bentonite was purified by sedimentation to eliminate impurities, especially quartz. The results of X-ray diffraction
(XRD) and swelling volume data confirmed that raw bentonite was converted to sodium bentonite using 5% Na2CO3. The
sodium bentonite (M5) obtained by activation met the chemical and microbiological requirements set by the pharmacopoeias
regarding toxic trace elemental contents (As, Pb and Cd), the absence of E. coli, the total contents of aerobic microbes and
physicochemical properties such as swelling volume, pH and sedimentation volume. Therefore, (M5) bentonite can be desig-
nated as being potentially appropriate for pharmaceutical applications. The cation exchange capacity (CEC), surface area,
porosity, pH, gel formation and swelling volume data indicated that M5 bentonite could be used to formulate oral suspensions
and in topical application.

Keywords Bentonite . Sohag . Soda activation . Microbial contents . Pharmaceutical uses . Egypt

Introduction (Hermosín et al. 1981; Alvarez 1984; Galań et al. 1985).

These minerals can be used either in their current state or after
Products destined for use in medicines, whether as raw mate- undergoing diverse chemical treatments to highlight one of
rials or as active pharmaceutical ingredients, must fulfil sev- their particular qualities.
eral requirements regarding safety, stability and high degree of The use of these minerals for beautifying and health pur-
chemical inactivity. For a product to be used for pharmaceu- poses has improved in the previous decade as a result of the
tical purposes, it must be chemically and microbiologically cumulative achievement of normal medications. Especially,
harmless. Its other physical attributes (e.g. taste, colour, tex- healing requests for clay have been well documented for inte-
ture and water content) are also important. Taste and colour rior uses (Veniale 1997) as well as for the grounding of ther-
can affect its acceptance by the patient, whereas texture and mal mud (i.e. poultices entitled peloids which are produced by
water content can disturb technical processes. Silica and mixing clays with mineral water after their suitable matura-
phyllosilicates such as smectites, kaolinite and fibrous clays tion) that are used in sauna centres for the cure (pelotherapy)
are amongst the most widely used minerals in medicines of rheumatism, soreness and bone-muscle hurtful damages as
well as in the action of skin diseases (Cara et al. 2000; Sanchez
This article is part of the Topical Collection on New Advances and
et al. 2002; Veniale et al. 2007).
Research Results on the Geology of Africa A spa in Safaga that is located along the Egyptian Red Sea
coast uses a mixture of bentonite and radioactive black sand to
* Abdelhamid Elshater treat the psoriasis and other skin infections (Abdel-Motelib et
[email protected] al. 2011). Because the compositions and textures of natural
clay samples may vary significantly, it is highly important to
1
Geology Department, Faculty of Science, Sohag University, perform a series of precise methodological and pharmacolog-
Sohag, Egypt ical tests to estimate their potential pharmaceutical uses and,
2
Botany Department, Faculty of Science, Sohag University, when possible, to obtain a certain profile and pharmaceutical
Sohag, Egypt information (Viseras and Lopez-Galindo 1999).
385 Page 2 of 12 Arab J Geosci (2018) 11:385

Bentonite has diverse terminologies when used by min- Material and methods
eralogists, chemists or pharmacists. The term bentonite (or
bentonitic clays) is used to label mudstones that largely Raw bentonite
comprise smectite clays. Pharmaceutically, bentonite is a
naturally existing, crystalline, hydrated aluminium silicate Raw bentonite was collected from a bentonitic bed (5–9 m
and clay-like mineral that is obtainable as an odourless pale thick) confined to the Madmoud Formation (El Haddad
buff or cream- to greyish-coloured fine powder free from 2014; Refaey et al. 2015; El Shater et al. 2015; Soliman
fine sand (Raymond et al. 2003). 2016). Seventeen representative samples were collected
The US Pharmacopoeia (US Pharmacopeia 2004a, b) de- from four columnar sections covering the clays of this for-
scribes bentonite as a native, colloidal, hydrated aluminium mation and exposed in four sites in the investigated area
silicate and uses the term purified bentonite to characterise a (Table 1 and Figs. 1 and 2). Nine samples were collected
colloidal montmorillonite that has been processed to remove from Wadi Abu Gelbana (site I), five samples from Wadi
its grit and non-expandable components. Dir El-Haddid (site II and site III) and three samples from
Currently, bentonites are considered to be the most im- Wadi El-Kiman (site IV).
portant types of clays used for various purposes because The bentonite is dark grey and brown in colour and
their surface area and cation exchange capacity (CEC) mainly consists of montmorillonite with minor kaolinite,
values are high, and they can swell in water. Therefore, the illite, quartz and felspars (El Shater et al. 2015; Soliman
aim of this study is to examine the appropriateness of some 2016). It was soaked in distilled water for 48 h and was
types of Egyptian bentonites from Sohag region for their use stirred twice, once after every 24-h period of soaking time.
in new fields, including medication and ecological applica- The dispersed clay was passed through a 45-μm sieve
tions, following the physical treatment and activation of (ASTM) and allowed to settle. The water was then
these samples by Na2CO3. The specifications of each appli- decanted, and the slurry was dried at 60 °C. To obtain fine
cation are described for both treated and untreated samples. powder, the dried sample (sample M1 from Wadi Abu
Gelbana) was ground, passed through a 125-μm sieve
and labelled (M0).
Geological setting of the studied area
Granulometry and micromorphology
The study area lies at the eastern side of the Nile Valley of
Sohag Province, Upper Egypt. It occupies the area between The representative samples were mechanically analysed by
the foot of the eastern limestone plateau and the floodplain of wet sieving, using a standard sieve with openings of
the Nile between latitudes 26° 00′N to 27° 00′N and longitude 0.063 mm that was placed in a mechanical shaker for ap-
31° 15′E to 32° 15′E (Fig. 1). The study area comprises various proximately 15.0 min. The fine-grained (i.e. mud) fractions
sediments ranging in age from Lower Eocene to Recent (Said of the examined samples (i.e. particles with diameters of
1975, 1990; Omer 1996; Omer and Issawi 1998; Hassan et al. less than 63 μm) were determined using the pipette meth-
2005) as shown in Fig. 1. The studied samples were collected od. The fractions retained in the sieve and the mud
from the Madmoud Formation (Pliocene) deposits that are analysed by the pipette method were weighted, and their
characterised by their high fine earth fraction and smectite con- percentages were calculated and plotted (Table 1 and
tent (El Shater et al. 2015; Refaey et al. 2015; Soliman 2016). Figs. 3 and 4).
The Madmoud Formation forms a single lithostratigraphic The morphology of the Madmoud clays in representative
unit (Said 1981) and includes estuarine fine clastic sediments samples was examined using a JOEL JSM-35C scanning elec-
formed as a result of the rising and invasion of the tron microscope equipped with an energy dispersive X-ray
Mediterranean Sea through a long gulf extending from Cairo (EDX) detector at the Central Lab, Sohag University, Sohag,
to Aswan in the Pliocene (Issawi et al. 1978; Hassan et al. Egypt. Samples were mounted on Al stumps using conductive
2005). This formation was divided into two main divisions glue. Then, the surfaces of the stumps (samples) were coated
(lower and upper members) based on its deposition environ- with a thin layer of Au.
ment and facies (Omer 1996). The lower part is composed
mainly of bedded to massive dark brown (chocolate) clay to Sample preparation and Na activation
dark grey marine clay with thin interbeds of fine sand and silt
(Fig. 2). The upper part is dominated by fluvial sediments According to Yildiz and Calimli (2002), bentonite samples
consisting of fining upwards cycles. The sediments are sloped can be activated using sodium carbonate (Na2CO3). To govern
towards the cultivated flood plain covered with the younger the optimum activation dosage, soda samples with few mass
sediments and widespread in both the surface and subsurface ratios of 2, 3, 5 and 8 g per 100 g of bentonite sample, labelled
in the study area. M2, M3, M5 and M8, respectively, were added to 1000 mL of
Arab J Geosci (2018) 11:385 Page 3 of 12 385

Fig. 1 Location of the studied area (Sohag Governorate, Upper Egypt), locations of the selected columnar sections of Madmoud Formation and
geological map of east of Sohag Governorate (modified from Mahran 1995)

boiling water. The suspension was agitated slowly and constant- 24 h to permit impurities, particularly quartz, to settle. After 24 h,
ly with a magnetic stirrer and heated for 1 h. Next activation, it the supernatant was decanted, and the sedimentation process was
was endorsed to become cold at chamber temperature, and it was repeated until the supernatant became clear. The collected super-
diluted with distilled water to reach a concentration of 5 g of natants were centrifuged at 10,000 rpm to allow the clay samples
activated clay per 1000 mL of distilled water. The diluted sus- to settle; they were then dried at 60 °C. Each dried sample was
pension was homogeneously dispersed and allowed to stand for further ground to get fine powder for experimental use.
385 Page 4 of 12 Arab J Geosci (2018) 11:385

third was heated at 550 °C for 3 h. Similarly oriented samples of

raw (M0) and activated bentonite were obtained to investigate
the extent to which Na activation and purification affected the
Madmoud clays. The X-ray diffraction patterns of the natural,
treated and activated samples were recorded using a Philips X-
ray diffraction equipment model PW/1710 with a monochro-
mator and Cu-κα radiation (λ = 1.54 Å) at conditions of 40 kV
and 35 mA in the Department of Physics, Assiut University,
Egypt. The X-ray diffraction records were analysed with the
Xpowder 2012 computer program. Identification and semi-
quantitative estimates of clay minerals were made according
Fig. 2 Representive columnar sections of Madmoud Formation in the to the position and the area of the (001) basal reflections on
studied area showing the different vertical facies and sample distribution the three XRD patterns (Moore and Reynolds 1997).

To determine the activation dose for the optimum Na Chemical composition

activation of calcium bentonite, X-ray diffraction (XRD)
and swelling capacity analyses were used to characterise The chemical compositions of untreated and activated sam-
the raw and purified activated samples. The raw and Na- ples were obtained using a Philips PW 1404 WD-XRF spec-
activated bentonites were further characterised using X-ray trometer in the Department of Chemistry, Avido University,
fluorescence (XRF), determination of their CEC values, Spain, for the major oxides of SiO2, Al2O3, Fe2O3, TiO2,
N2 adsorption-desorption at T = 77.35 K, microbial tests MnO, MgO, CaO, Na2O, K2O, P2O5 and loss on ignition
and pharmacopeial tests (i.e. pH and gel formation). (L.O.I.). An atomic absorption spectrometer in the
Chemistry Department of Sohag University, Egypt, was used
X-ray diffraction to determine the trace element contents (As, Pb and Cd) of the
investigated clays.
Mineralogical analyses were performed using classical X-ray With the Hendershot and Duquette (1986) method, the
diffraction techniques. Three oriented samples of the < 2-μm CEC values of the samples were determined. The contents
bentonite fraction were set by sedimentation on glass slides. of major cations (Ca2+, Mg2+, and K+ and Na+) and major
Whilst the first was dried out at room temperature (natural), anions (Cl−, SO42− and PO43−) were measured using an ICP-
the second, i.e. ethylene-glycolated at 40 °C for 24 h, and the OES (Perkin Elmer-Optima 3000XL) and a San+2

Table 1 Grain size fractions of

Madmoud deposits according to Formation Site Samples Grain size analysis pipette method
the sedimentation method
4Ø % 5Ø % 6Ø % 7Ø % 8Ø % 9Ø %

Madmoud Wadi Abu Gilbana 1 M 8.8 7.2 12.1 15.2 10.4 46.3
(site I) 2 M 14.2 21.5 15.8 10.8 4.2 33.5
3 M 17.3 18.4 4 10 4.6 45.7
4 M 13.5 12 5.3 9.4 7.3 52.5
5 M 10 12 10.3 13.4 3.3 51
6 M 5 16.7 6.8 24 7 40.5
7 M 7.4 7.2 15 9.6 8 52.8
8 M 9.5 12 18.5 7.5 10.5 42
9 M 8 12 10 19 15 36
Wadi Dir El Haddid 10 M 8.4 12.3 13 11.8 20 34.5
(sites II and III) 11 M 6 7.3 11.3 17.3 19.5 38.6
12 M 5.1 9.8 10.4 16.8 12.2 45.7
13 M 4.7 11.7 15.2 3.4 22.3 42.7
14 M 11.8 11.1 10.1 3.7 30.8 32.5
Wadi El-Kiman 15 M 7.4 5 8.8 15.3 12.3 51.2
(site IV) 16 M 5.4 14.6 10.1 6.7 14.8 48.4
17 M 7.1 8 8.8 18.3 22.1 35.7
Arab J Geosci (2018) 11:385 Page 5 of 12 385

Fig. 3 Sediment nomenclature

based on sand-silt-clay ratios
(after Shepard 1954)

Automated Wet Chemistry Analyser-Continuous Flow Microbiological analysis

Analyser (CFA), Earth Surface Science, Institute for
Biodiversity and Ecosystem Dynamics (IBED), University The culture studies planned for microbiological examina-
of Amsterdam, Science Park 904, 1098 XH Amsterdam, the tions considered the transfer of colony-forming units
Netherlands, respectively. (CFU) to a nutrient medium. In all cases, clay suspensions
were composed of a known quantity of clay, and the ag-
gregates were split with a blender via Na4P2O7 as a dis-
Specific surface area and pore size distribution persing agent. Then, serial dilutions were made, and rep-
licate 1-mL portions were transferred to each culture me-
The nitrogen adsorption-desorption isotherms of the raw and dium for incubation. The adopted medium and incubation
Na-activated samples were obtained at 77–196 °C using a conditions used to estimate the total aerobic viable
Micromeritics ASAP 2010 analyser, Chemistry Department, microorganisms were described in EPC (1990) and
Sohag University, Egypt, after outgassing the samples at USPC (1990a, b). The presence of Escherichia coli,
110 °C for 4 h with a residual pressure of 10–5 mmHg. By Pseudomonas aeruginosa, Staphylococcus aureus, and
using the software supplied with the equipment following the Candida albicans was also stabilised by the discriminating
recommendations of Sing et al. (1985), the BET surface areas adjustments of media and circumstances. When possible,
of the internal and external surfaces (equivalent to the micro- single-plate colonies were counted. The number of single
pore and mesopore surface areas) were calculated. colonies was equivalent to that of single CFU in the

Fig. 4 Examples of histograms %

60
showing the grain size
distribution of Madmoud
sediments 50

40

4Ø %
5Ø %
30
6Ø %
7Ø %
8Ø %
20 9Ø %

10

0
1M 2M 3M 4M 5M 6M 7M 8M 9M 10M 11M 12M 13M 14M 15M 16M 17M
Sample Number
385 Page 6 of 12 Arab J Geosci (2018) 11:385

Table 2 Mineralogical
composition of Madmoud Formation Locality Samples Montmorillonite% Kaolinite% Quartz% Feldspars%
deposits following the method of
Moore and Reynolds (1997) Madmoud Wadi Abu Gilbana 1 M 82 8.7 8.5 Trace
(site I) 2 M 84.2 6.3 9.5 0
3 M 85.5 6.7 7.5 0
4 M 85.1 7 7.9 0
5 M 76.4 14.9 8.7 0
6M 87 7 6 0
7M 79.5 13.6 4.2 Trace
8M 75.7 12.8 8.4 3.1
9M 79 14.9 4.1 Trace
Wadi Dir ELHa-did 10 M 73.4 12.3 10.7 3.6
(sites II and III) M11 79.7 14.5 4 Trace
M12 80.8 12.5 6.5 Trace
M13 77.1 11.2 10.5 Trace
M14 81.7 7.2 9.9 Trace
M15 79 11.8 8.1 Trace
Site (IV) 16 M 88.6 8.6 2.4 Trace
17 M 77.8 14.2 6.8 Trace
Average 82 10 7 Trace

suspension. If the plate count was not appropriate, dilu- possible number (MPN) of CFU. Five replicates were
tion counts were made, and the greatest dilution that made of each inoculation for three adequate sequential
could still supply growth was equated with the most dilutions.

Fig. 5 BSE images of the studied

clays. a, b A loose texture of
detrital clay particles exhibiting
poorly developed plates with
irregular outlines. c Matrix
microstructure. d The clay
particles showing poorly
developed plates with irregular
outlines or have ragged edges. e, f
Deformed honeycomb textures. g
Undulated laminae. h Turbulent
microstructure type. i Clay
minerals showing a flocculent
texture
Arab J Geosci (2018) 11:385 Page 7 of 12 385

sample was added to 200 mL of water, which was subse-

17Å quently centrifuged with a speedy mixer at 10,000 rpm.
Then, 100 mL of each suspension was added to a 100-mL
graduated cylinder. Afterwards, the sedimentation volume
14.6Å was measured by determining the clear supernatant vol-
560 ume after 24 h.
Intensity(Counting)

7.1Å
pH measurement
336

In line with the pharmacopoeia specifications for bentonite, after

112 2 min of continuous stirring, the pH values of clay-water suspen-
sions (4 g/200 mL) were measured (US Pharmacopoeia 2007).
5 10 15
2 Theta Results and discussion
Fig. 6 A representative XRD pattern of clay fraction selected samples
(black line: air-dried, blue line: glycolated, rose line: 550 °C heated) Granulometry and micromorphology

Based on the ternary diagram of Shepard (1954), the size

fractions of the bentonitic deposit samples in the study area
Pharmaceutical tests fall in the fields of silty clay and clayey silt (Fig. 3). The
grain size distributions of the sediments studied here are
Swelling power illustrated by histograms (Fig. 4). It is evident that there
are no variation trends in any of the studied sediments.
The swelling capacity was determined based on the US Additionally, it appears that there is regularity in the distri-
Pharmacopoeia method (2007), in which 2 g of bentonite bution of particles in the sand range of the studied samples.
was added in portions to a 100-mL graduated cylinder con- Although the commercial product was rich in silty particles
taining 100 mL of distilled water. Then, the swelling capaci- (54%), it also contains a notable concentration of sandy
ties were measured by determining the apparent sediment vol- particles (8.8%). Veniale et al. (2007) noted that an adequate
umes after 2 h. peloid must contain at least 70–80% clay-sized particles.
Additionally, Armijo and Maraver (2006) reported that
Gel formation most Spanish thermal centres apply peloids containing ap-
proximately 57–70% particles between 2 and 20 μm in size.
The technique defined by the European Pharmacopoeia In this sense, the studied Madmoud deposits that have not
(2005) was used to assess the sedimentation volume and been subjected to mechanical grinding represent the best
to quantify gel formation. Six grams of each bentonite materials for medical purposes. Based on the mineral

Fig. 7 A representative XRD 860

pattern of the M0 sample (M =
M
montmorillonite, K = kaolinite,
I = Illite, Q = quartz, F = feldspar) 700
M
Intensity(Counting)

540 Q
K
380 M
K F K Q
220 Q MK Q
F
60
4 18 32 46 60 74
2 Theta
385 Page 8 of 12 Arab J Geosci (2018) 11:385

Fig. 8 XRD Patterns of raw and

soda-activated bentonite samples
(M0 = fine powder dried sample

Intensity(Counting)
M1 from Wadi Abu Gelbana 784
ground, passed through a 125-μm
sieve; M2 = activated sample with 560 M8
2 Na2CO3 per 100 g of bentonite; M5
M23 = activated sample with 2 336
Na2CO3 per 100 g of bentonite;
M3
M5 = activated sample with 2 112
M2
Na2CO3 per 100 g of bentonite; M0
M8 = activated sample with 2
Na2CO3 per 100 g of bentonite) 10 20 30 40 50 60 70
2 Theta

composition and the shape and degree of dispersion of pri- were identified: inter-granular and intra-granular micropores.
mary clay particles, as well as sedimentation conditions, the The first type is illustrated in Fig. 4e, f and h, where the
microaggregates in clayey sediments can take different contact types of micrograins or microcrystals are face-to-
forms and range in diameter from fractions to scores of edge or edge-to-edge (Fig. 5e, f) and face-to-face (parallel
micrometres (Grabowska-Olszewskab et al. 1984). platelets), as in Fig. 4h. The second type was probably created
In the samples collected from the Madmoud deposits that by diagenetic dissolution or leaching processes (Fig. 5i). Here,
contain up to nearly 90% smectite (Table 2), the obtained BSE the pores almost reach an isometric form and are several mi-
images (Fig. 5a–i) of clay particles show wide variations in crons in diameter.
their sedimentary microstructures. The first and most common
microstructure is that of poorly developed plates, which ex-
hibit the irregular outlines and loose texture of detrital clay Mineral composition and the effects of soda
particles (Fig. 5a, b, d). The second-most recorded microstruc- activation
ture of the Madmoud smectite is allogenic layering, which
often forms undulating laminae (Fig. 5g). The third-most re- Mineralogy
corded microstructure is the turbulent type (Fig. 5h), in which
the orientation of clay materials causes the pronounced anisot- The diffraction patterns of the untreated, ethylene glycol-
ropy of the physical and mechanical effects. A deformed hon- solvated and heated samples are shown in Fig. 6. In the inves-
eycomb microstructure was also recorded in these clays. One tigated sediments, the shift of (001) basal spacing of the main
of its features is the presence of open, nearly isometric cells clay mineral phase after ethylene glycol solvation from 15 to
that are 2–5 μm in size, in which the cell walls are mostly 17 Å and the collapse to d = 9.6 Å suggests that the main clay
montmorillonite (Fig. 4e, f). mineral present is Ca-montmorillonite (Lim and Jackson
Additionally, some smectite samples show matrix micro- 1986). The detected clay minerals include smectite (with an
structures and flocculent textures (Fig. 5c, i). Based on mutual average value of 82%) with minor amounts of kaolinite
grain-to-grain relationships, two main types of micropores (10%), whilst the non-clay minerals include quartz and feld-
spar (sanidine) (Table 2 and Fig. 7).

Fig. 9 Swelling volume of raw

and soda-activated samples
Arab J Geosci (2018) 11:385 Page 9 of 12 385

The XRD patterns of the original and purified Na2CO3- Table 4 Specific surface area and porosity of raw (M0) and purified
sample (M5)
activated samples are illustrated in Fig. 8. The quartz con-
tent decreases in the Na-activated samples. The Na- Properties M0 M5
montmorillonite obtained by soda activation at a concen-
tration of 5 g Na2CO3/100 g bentonite has a lower d001 BET surface area (m2/g) 66.84 86.015
spacing (~12.6 Å) than the original Ca-montmorillonite Micropore area (m2/g) 31.73 36.43
(15 Å) (Fig. 8), suggesting that Na+ ions replaced Ca2+ Total pore volume (cm3/g) 0.066 0.089
ions in the montmorillonite interlayer. According to Micropore volume (cm3/g) 0.013 0.016
Viseras et al. (2006), the quartz content should be less Average pore diameter (nm) 5 4.47
than 2% due to adequate evidence of carcinogenicity in
laboratory animals and, to some extent, in humans (IARC
1997). The quartz in the bentonite studied here was suc- Chemical composition
cessfully removed by soda activation followed by sedi-
mentation (Fig. 8). Table 3 shows the results of the major elemental analyses of
the raw and activated samples. These analyses illustrated that
their Al2O3/SiO2 ratio was 1/3, as expected for the studied
Swelling volume sediment samples, where montmorillonite represents the ma-
jor component of these clays. The slight decrease in SiO2 and
The swelling volumes (mL) of the Madmoud bentonite sam- increase in Al2O3 after Na2CO3 activation followed by sedi-
ples before and after their activation by different concentra- mentation confirmed that the minor amounts of quartz impu-
tions of Na2CO3 are displayed in Fig. 9. The swelling vol- rities in these samples were removed and that there was a
ume of the original bentonite was 6 mL, but it increased to proportional increase in the clay mineral content, in accor-
30 mL as the concentration of Na2CO3 increased to 5 g/ dance with the results of XRD analyses (Fig. 8).
100 g Na2CO3 (sample M5) (Fig. 8). At higher Na2CO3 Whilst the content of Na2O increased, that of CaO signif-
concentrations, the swelling volume did not increase. The icantly decreased, in accordance with the conversion of calci-
increase in swelling volume with higher concentrations of um bentonite to sodium bentonite. In contrast, the content of
Na2CO3 indicates the progressive replacement of exchange- MgO was unaffected. Small amounts of K2O and CaO
able Ca+2 by Na+, thereby facilitating swelling due to the remained in the purified samples. The presence of K2O is most
weak electrostatic interactions between the Na+ ions and the likely due to illite, whereas the presence of CaO is most likely
negatively charged smectite layer. This allows the entrance
of excess water molecules.
The maximum possible replacement of Ca+2 was noticed at
5% Na2CO3, i.e. sample M5, which displays a maximum
swelling volume in accordance with the results of XRD anal-
yses (Fig. 8, pattern M5).

Table 3 Major oxide

compositions (wt.%) of Wt.% M0 M5
samples studied
SiO2 47.32 46.07
Al2O3 17.61 18.84
Fe2O3 10.18 9.34
MnO 0.15 0.13
MgO 2.92 3.16
CaO 4.61 4.11
Na2O 0.8 3.76
K2O 0.76 0.41
TiO2 1.5 0.13
P2O5 0.21 –
L.O.I. 13.68 – Fig. 10 N2 adsorption-desorption isotherms of samples M0 (red line) and
M5 (blue line)
385 Page 10 of 12 Arab J Geosci (2018) 11:385

Table 5 Results of the microbial analysis (no. of UFC/g sample) as they show the H4 hysteresis loop, suggesting that slit-
M0 M5 shaped porosity exists between plate-like particles (Fig. 10).
The hysteresis loop is caused by the capillary condensation
Total aerobic bacteria 200 175 of nitrogen in slit-like mesopores. The small hysteresis below
E. coli Absent Absent P/P0 values of approximately 0.45 and the steeply sloped part
Staphylococcus aureus Absent Absent at P/P0 values of 0.98–1.00 indicate the presence of micro-
Pseudomonas aeruginosa Absent Absent pores and macropores, respectively. The isotherms of samples
Total spores Absent Absent M0 and M5 are comparable; the only noticeable difference is
the increase in the area of the hysteresis loop in the Na-
activated sample, indicating the increased mesoporosity and
higher adsorption volume relative to the original sample
due to trace amounts of calcite and/or feldspar. Finally, the
(Fig. 10). Additionally, the Na-activated sample (M5) contains
percentages of Fe2O3, TiO2 and MnO illustrated slight de-
a higher BET specific surface area and a lower average pore
creases in the activated samples, which increased the purity
size than the untreated sample M0 (Table 4).
and whiteness of the purified clay.
The studied bentonite clay was free of the toxic trace ele-
ments Pb and As, as the concentrations of both elements fell Microbiological analysis
below the detection limits of AAS (i.e. 0.05 and 0.01 ppm for
As and Pb, respectively), which are considerably lower than The microbial test (Table 5) revealed that both the raw and Na-
the limits allowed by pharmacopoeia, i.e. 40 and 5 ppm, re- activated samples are free of pathogenic bacteria and that the
spectively, for raw bentonite (US Pharmacopoeia 2007), and total bacteria count fell within the permitted range of different
15 and 3 ppm, respectively, for purified bentonite (Lopez- pharmacopoeia (i.e. the raw samples had a value of CFU/g
Galindo and Viseras 2004). The concentration of Cd was very and the Na-activated samples had a value of 175 CFU/g), i.e.
low, i.e. < 0.02 ppm. < 103 CFU/g, as established for the safe use of bentonite in
preparing pharmaceutical products (US Pharmacopoeia
2007). The samples did not display contamination by E. coli
Exchangeable cations or salmonella species. Hence, the absence of E. coli required
by pharmacopoeias was fulfilled by the studied bentonite (US
The CEC value of the raw sample (M0) was 67 meq/100 g Pharmacopoeia 2007). Based on these results, both the raw
bentonite. This high CEC value indicates that it can be utilised and activated forms of bentonite were microbiologically clean
for pharmaceutical use. The Na activation did not affect the and could be utilised for pharmaceutical purposes.
CEC of the sample. Therefore, the Na-activated bentonite can
also be utilised for pharmaceutical purposes. Pharmacopoeia requirements

The pH values of the 5% aqueous dispersions (Table 6) match

Specific surface area and porosity the pharmacopeial requests, with values varying from 8.2 to 9.9.
The supernatant volume prepared for sediment volume measure-
The values of the BET surface area, average pore size, micro- ments or gel formation indicates that the activated Egyptian ben-
pore volume and area and total pore size volume obtained from tonite samples exhibit little differences compared to the
the N2 adsorption-desorption isotherms by applying the BET Wyoming samples and pharmacopeial requirements because
method to the raw and purified activated bentonite samples are the former are not pure sodic types, even after activation. This
summarised in Table 4. According to the classification of the result also suggests that the Egyptian bentonite can be used as a
International Union of Pure and Applied Chemistry (IUPAC) pharmaceutical excipient after undergoing extensive purification,
(Gregg and Sing 1982), the observed isotherms are of type IV, with or without activation. This activated bentonitic clay may be

Table 6 Physical properties of

samples M0, M2, M3, M5 and M0 M2 M3 M5 Wyoming US Pharmacopoeia
US Pharmacopoeia specification bentonite specification

Gel formation < 2 mL < 2 mL < 1 mL < 1 mL 1 mL ≤ 2 mL

(6 g/200 mL)
Swelling volume 8 mL 22 mL 26 mL 29 mL 35 mL ≥ 24 mL
(2 g/100 mL)
pH (4 g/200 mL) 8.2 9.4 9.8 10 9.8 9–10.5
Arab J Geosci (2018) 11:385 Page 11 of 12 385

utilised as an adsorbent for drugs or as a tablet in drug release El Haddad B (2014) Evolution of the geological history of the Egyptian
Nile at Sohag area using sedimentological studies and remote sens-
operations, as it has a comparatively high CEC value.
ing techniques, M. Sc. thesis, Geology Department, Faculty of
Science, Sohag University, Egypt. 215+7 pp
El Shater A, El-haddad A, El-Attaar A, Soliman W (2015) Bentonite in
Conclusion the Paleonile sediments of Sohag region, Egypt. The Second
International Conference on New Horizons in Basic and Applied
Science, Hurghada, Egypt
In this study, clarified sodium bentonite powder was prepared EPC (European Pharmacopoeia Convention) (1990) Control de la
by Na activation and precipitation, and its appropriateness for c o n t a m i n a c i ó n m i c r o b i a n a e n p ro d u c t o s n o o b l i g a t o ri
pharmaceutical use was studied. The d001 basal spacing de- amenteestériles. Dirección General de Farmacia y Productos
Sanitarios. Ministerio de Sanidady Consumo, Madrid, V. 2.1–8
creased from 15 to 12.6 Å. The swelling volume increased as
European Pharmacopoeia (2005) Bentonite. In: European pharmacopoeia,
the concentration of Na2CO3 increased up to 5%. At higher 5th edition. European Pharmacopoeia Convention, Strasbourg p. 1068
concentrations, the swelling volume remained at an almost Galań E, Liso MJ, Forteza M (1985) Minerales utilizadosen la industria
constant value, thus indicating that the complete conversion farmacéutica. Bol Soc Esp Mineral 8:369–378
Grabowska-Olszewskab B, Osipov V, Sokolov V (1984) Atlas of the
of calcium bentonite to sodium bentonite occurred at a
microstructure of clay soils. Wyd. Nauk. PWN. 414 pp
Na2CO3 concentration of 5%. Gregg SJ, Sing KSW (1982) Adsorption, surface area and porosity.
Sedimentation rendered activated bentonite mineralogically Academic Press, New York
substantial, which is desirable for pharmaceutical use. Sodium Hassan M., El-Haddad A., Omer A., Ibrahim, M (2005). Geochemical
bentonite (M5) is chemically and microbiologically substantial characteristics of the surficial Nile basin sediments and their envi-
ronmental relevance, Sohag area, Egypt (M.Sc. thesis) South Valley
and fulfils the pharmacopoeia requirements regarding its Pb and University (Sohag), Egypt
As contents, the absence of E. coli and its total aerobic micro- Hendershot H, Duquette M (1986) A simple barium chloride method for
bial contents and physicochemical properties, including its determining cation exchange capacity and exchangeable cations.
swelling and sedimentation volumes as well as its pH values. Soil Sci Soc Am J 50:605–608
Hermosín MC, Cornejo J, White J, Hem SL (1981) Sepiolite, a po-
Additionally, the samples acquired using lower concentrations tential excipient for drugs subject to oxidative degradation. J
of sodium carbonate could be adopted for specific pharmaceu- Pharm Sci 70:189–192
tical uses. The chemical, mineralogical and microbial purity of IARC (1997) Silica. IARC monographs on the evaluation of carcinogenic
purified activated bentonite (labelled M5) allow its safe use as a risks to humans. IARC Scientific Publications, Lyon 41 pp
Issawi B., Hassan M., Osman R (1978). Geological studies in the area
raw pharmaceutical material, particularly as an excipient. of Kom Ombo, Eastern Desert, Egypt. Ann. Geol. Survey, Egypt
The clarified bentonite could be used as a suspension agent in VIII. pp 187–235
the formularization of oral and topical purposes due to its high Lim CH, Jackson ML (1986) Expandable phyllosilicate reaction with
swelling volume and high sedimentation volume. Additionally, lithium on heating. Clay Clay Miner 34:346–352
Lopez-Galindo A, Viseras C (2004) Pharmaceutical and cosmetic application
the high swelling volume of activated bentonite recommends its of clays. In: Wypych F, Satyanarayana KG (eds) Clay surfaces: funda-
use as a disintegrant agent in tablet formulation. The high CEC mentals and applications. Elsevier, Amsterdam, pp 267–289
and high surface area of the activated sample (M5) suggest its Mahran TM (1995) Sedimentological development of the upper Pliocene–
utility as a good adsorbent of drugs. However, the performance Pleistocene sediments in the area of El-Salamony and El-Sawamha
Sharq, Northeast Sohag, Egypt. Qatar Univ Sci J 15(1):183–194
of a specific drug adsorption study is advisable. Moore DM, Reynolds RC (1997) X-ray diffraction and the identification
and\ analysis of clay minerals, second ed. Oxford University Press
Acknowledgements We wish to thank Prof. Dr. Kamal Khalil, Chemistry Inc., New York 400 pp
Department, Sohag University, Egypt, for the help during the specific sur- Omer A (1996) Geological, mineralogical and geochemical studies on the
face area analyses. We wish to extend our thanks to the staff of the labora- Neogene and Quaternary Nile basin deposits, Qena-Assiut stretch,
tories of the Faculty of Chemistry, Avido University, Spain, and to the staff Egypt (Ph.D. Thesis), Geology Dept., Fac. Sci. Sohag, South Valley
of the Chemistry lab, Faculty of Science, Sohag University, Egypt. University (320 pp)
Omer AA, Issawi B (1998) Lithostratigraphical, mineralogical and geo-
chemical studies on the Neogene and Quaternary Nile basin de-
posits, Qena-Assuit stretch, Egypt. The 4th International conference
References on geology of the Arab world, Cairo. (abstract)
Raymond CR, Paul JS, Paul JW (2003) Handbook of pharmaceutical
Abdel-Motelib A, Abdel Kader A, Ragab Y, Mosalamy M (2011) excipients. Pharmaceutical Press; American Pharmaceutical
Suitability of a Miocene bentonite from North Western Desert of Association, Washington, pp 42–44
Egypt for pharmaceutical use. Appl Clay Sci 52:140–144 Refaey Y, Jansen B, El-Shater A, El-Haddad A, Kalbitz K (2015) Clay
Alvarez A (1984) Sepiolite properties and uses. In: Singer A, Galań E minerals of Pliocene deposits and their potential use for the purifi-
(eds) Palygorskite–Sepiolite. Occurrences, genesis and uses. cation of polluted wastewater in the Sohag area, Egypt. Geoderma
Elsevier, Amsterdam, pp 253–287 Reg 5:215–225
Armijo F, Maraver F (2006) Granulometría e textura de lospelói des Said R (1975) The geological evolution of the River Nile. In: Wendorf F,
españoles. An Hidrol Méd 1:79–86 Maks AF (eds) Problems in prehistory of northern Africa and
Cara S, Carcangiu G, Padalino G, Palomba M, Tamanini M (2000) The Levant. Southern Methodist University Press, Dallas, pp 1–44
bentonites in pelotherapy: thermal properties of clay pastes from Said R (1981) The geological evolution of the River Nile. Springer-
Sardinia (Italy). Appl Clay Sci 16:125–132 Verlag, New York 151 pp
385 Page 12 of 12 Arab J Geosci (2018) 11:385

Said R (1990) The geology of Egypt. Egyptian General Petroleum USPC United States Pharmacopoeial Convention (1990a) Activated
Corporation, Conoco, Hurghada Inc. and Repsol Exploration, Attapulgite. In: The United States Pharmacopoeia XXII. United
S.A., Balkema, Rotterdam, Brookfield, 731 pp States Pharmacopoeial Convention, Rockville, pp 125
Sanchez CJ, Parras J, Carretero MI (2002) The effect of maturation upon USPC United States Pharmacopoeial Convention (1990b) Colloidal
the mineralogical and physicochemical properties of illitic-smectitic Activated Attapulgite. In:The United States Pharmacopoeia XXII.
clays for pelotherapy. Clay Miner 37:457–464 United States Pharmacopoeial Convention, Rockville, pp 125
Shepard F (1954) Nomenclature based on sand-silt-clay ratios. J Veniale F (1997) Applicazioni e utilizzazioni medico-sanitarie di
Sediment Petrol 24:151–158 materiali argillosi (naturali e modificati). In: Morandi N, Dondi M
Sing KSW, Everett DH, Haul RA, Moscou L, Pierotti RA, (eds) Argillee minerali delle argille. Guidaalladefinizione di
Rouquerol J, Siemieniewska T (1985) Reporting Physio- caratteristiche e propietàpergliusi industriali. Corso di Formazione,
sorption data for gas/solid systems with special reference Gruppo Italiano AIPEA, Rimini, pp 205–239
to the determination of surface area and porosity (recom- Veniale F, Jobstraibizer AB, Setti M (2007) Thermal muds: perspectives
mendations 1984). Pure Appl Chem 57:603–619 of innovations. Appl Clay Sci 36:141–147
Soliman W (2016) Mineralogy and industrial uses of clayey sediments in Viseras C, Lopez-Galindo A (1999) Pharmaceutical applications of some
east of sohag, Egypt (M.Sc. thesis) Sohag University, Egypt Spanish clays (sepiolite, palygorskite, bentonite): some
US Pharmacopeia (2004a) Bentonite, 27. US Pharmacopoeia preformulation studies. Appl Clay Sci 14:69–82
Convention, Rockville, MD, p 2826 Viseras C, Cultrone G, Cerozo P, Aguzzi C, Baschini MT, Valles J,
US Pharmacopeia (2004b) Purified bentonite, 27. US Pharmacopoeial Lopez-Galindo A (2006) Characterization of northern Patagonian
Convention, Rockville, pp 2827–2828 bentonites for pharmaceutical uses. Appl Clay Sci 31:272–281
US Pharmacopoeia (2007) Bentonite. P. 1066 In: US pharmacopoeia 30 and Yildiz N, Calimli A (2002) Alteration of three Turkish Bentonites by
National Formulary 25. US Pharmacopoeial Convention, Rockville treatment with Na2CO3 and H2SO4. Turk J Chem 26:393–401