Characterization of the Natural and Organomodified Clay Soil of Moukosso (Republic of Congo) by Dimethylsulfoxide: Application to the Adsorption of Lead (II) in Aqueous Solution ()
1. Introduction
Awareness of the environmental problem in general and waste management, in particular, is now an integral part of the development strategies designed and implemented in every country at both national and sectoral levels [1] . Clay minerals are arguably the most encouraging alternatives to expensive adsorbents. Clays are abundant and widely available materials, exhibiting good chemical and mechanical stability and having unique adsorption and ion exchange properties [2] [3] [4] . Due to their local availability, technical feasibility and cost-effectiveness, studies have been conducted on the use of clay minerals for wastewater treatment applications [5] - [10] . Thanks to their interesting surface properties, clays behave as natural cleaning agents and absorb organic and inorganic contaminants present in water, both by ion exchange and by adsorption. The modification of the surface of clays most often promotes the creation of new materials that can have many practical applications in several fields of materials science. Organic and inorganic pollutant adsorbents, rheology control agents, paints, cosmetics, personal care products, catalysts, soil remediation, electrodes and nano-composite precursors are among examples of the results of modification of clay surfaces [3] [4] [11] [12] [13] . Due to their relatively low production cost and high adsorption capacity, adsorption by organoclays has been used for the removal of organic and inorganic contaminants in waters [14] [15] [16] . As part of the valorization of local materials, we have conducted a study of the Moukosso’s clay soil and its application in the adsorption of Pb2+ ions. Environmental pollution by heavy metals is a public health problem. Several treatment processes have been developed to remove these metals. Clays, thanks to their nanometric sizes and their sheet structures, offer a large adsorption surface. They are thus used in many pollutant removal processes [17] [18] [19] . It is in this context that we have, after characterization, used the Moukosso’s clay soil (raw and chemically modified clay) as an adsorbent to eliminate the Pb2+ ions.
2. Methodology
2.1. Location of the Sampling Site
The clay material that is the subject of this study comes from the locality of Moukosso in the department of Bouenza, Republic of Congo. The geographical coordinates of the sampling site are: latitude: 03˚74.963E, longitude: 9˚539.466N. This material was sampled at a depth of 2.5 meters.
2.2. Intercalation of the Clay Fraction by DMSO
The intercalation of DMSO was made in the phyllite fraction extracted from the material. 2.5 g of the fine fraction and 15 mL of the DMSO were mixed in a flask. The mixture was then refluxed for 12 hours at 150˚C. The solid material obtained was washed several times with isopropanol; then separated by centrifugation. The solid obtained is dried at 60˚C in an oven [20] .
2.3. Samples Characterization
1) Determination of cation exchange capacity
The cation exchange capacity of the studied material was determined by the ammonium acetate method [21] .
2) Thermogravimetric analysis (TGA)
The thermogravimetric analysis (TGA) was carried out by a Diamond Pyris 6000 device Perkin-Elmer TGA/DTA in the temperature range of 30˚C to 850˚C using aluminum crucibles under N2 flow at a heating rate of 20˚C/min. The temperature accuracy of the device is ±0.5˚C. Data were processed using Origin software.
3) Fourier Transform Infrared Analysis
The infrared spectroscopy measurements were carried out on a Nicolet iS 10 Smart FT-IR device. The infrared spectrum of the material was realized in the range 4000 - 500 cm−1. Data were processed using Origin software.
4) X-ray diffraction Analysis
The mineralogical analysis by X-ray powder diffraction was carried out on a Panalytical X’ Pert Pro MPD type device using the Kα line of copper with a wavelength
. The data was processed using QualX software.
2.4. Adsorption Test
In order to study the adsorption isotherms, the mass of adsorbent was kept constant and we varied the concentration of the adsorbate. In 50 mL beakers, we introduced 0.05 g of clay and 10 mL of lead chloride solution of concentration in mol/L (0.0002; 0.0003; 0.0005; 0.001; 0.002 and 0.003). The solutions are stirred using a magnetic stirrer for 60 minutes, centrifuged and filtered. After filtration, the solutions were assayed by a UV-visible spectrophotometer at 300 nm. The isotherms are obtained by plotting the adsorbed quantity curve Qe (mg/g) as a function of the equilibrium concentration Ce (mg/L).
3. Result and Discussion
3.1. Cation Exchange Capacity (CEC)
The cation exchange capacity of this material is 7.4 meq/100g. This value between 3 and 15 could be linked to the presence of kaolinite [22] . The low value of the CEC could explain the absence of smectites in this material [23] .
3.2. Thermogravimetric Analysis
Figure 1 and Figure 2 present the TGA curves of raw and intercalated materials from Moukosso.
The thermograms obtained have the same appearance, thus showing a loss of
Figure 2. TGA curve of intercaleted clay.
mass through the stepped profile. The one in Figure 1 shows several differences in level, between
· 0˚C and 100˚C, accompanied by a low mass loss of about 0.8%, would correspond to the departure of surface water from the clay soil [24] ;
· 200˚C and 250˚C with a mass loss of 1.6% would correspond to the departure of adsorbed water in the interfoliar space [24] ;
· 280˚C and 300˚C, presents a mass loss of 1.1% which could correspond to the combustion of organic residues and the loss of carbonates [25] ;
· 450˚C and 600˚C, with a mass loss of 5.7% would correspond to the dehydroxylation of kaolinite [26] . This phenomenon leads to the formation of metakaolinite, an amorphous phase [27] .
· 600˚C and 850˚C, the authors observed a progressive loss of mass, a phenomenon which could correspond to the dehydroxylation of muscovite [27] .
· On the other hand, that of Figure 2 shows two significant differences in level between:
· 0˚C and 280˚C accompanied by a strong loss of mass of approximately 17.5%, which would correspond to the departure of surface and interfoliar waters and to the decomposition of DMSO. This mass loss is much higher than that obtained with raw clay; which could confirm the success of the intercalation of this clay by DMSO. These results are in agreement with those found in the literature [28] .
· 400˚C and 850˚C with a mass loss of 7.5% which could be attributed to the dehydroxylation of kaolinite and muscovite [27] .
3.3. Fourier Transform Infrared
Figure 3 and Figure 4 present the infrared spectra of the materials studied.
Figure 3. Infrared spectrum of raw material.
Figure 4. Infrared spectrum of intercaleted material.
For the raw material, we observe the elongation vibration bands at 3697 and 3621 cm−1 which could correspond to the OH groups of the kaolinite [29] [30] . The presence of two bands instead of four (3695, 3669, 3650 and 3620 cm−1) would indicate that the kaolinite is poorly crystallized [31] . The band at 3621 cm−1 could also be related to the vibration of the OH group of muscovite [32] [33] . The band at 1647 cm−1 would correspond to that of hygroscopic water [34] . Bands at 1140 and 1020 cm−1 could correspond to Si-O stretching vibrations of kaolinite. The band at 1020 cm−1 would also be that of muscovite [32] . The Al-OH deformation vibration characteristic of kaolinite appears at 906 cm−1 [35] . The presence of quartz would be indicated by the bands at 813 and 703 cm−1. Compared to the infrared spectrum of the raw material, two bands appear at 3550 cm−1 and at 2900 cm−1 in the infrared spectrum of the organomodified material. The band at 3550 cm−1 would correspond to a new hydroxyl group. However, that at 2900˚C could correspond to the symmetrical stretching mode of CH2 and CH3 [36] ; it could also be attributed to the valence vibrations of the CH2 and CH3 bonds. This confirms that the clay has been intercalated by DMSO, with the presence of the characteristic bands of the S=O bond at 905 cm−1 which splits the Al-OH bond of the kaolinite and of the CH3-S bond at 1008 cm−1 [36] .
3.4. X-Ray Diffraction
Figure 5 shows us the diffractogram of the raw clay of Moukosso.
The qualitative analysis showed the following mineral phases in angular positions (degree): muscovite (8.88; 17.80; 19.86; 20.86; 24.89; 25.52; 26.81; 27, 87; 31.25…), kaolinite Al2Si2O5(OH)4 (12.38; 19.86; 21.32; 24.76; 34.92; 36.94; 39.48…), anatase TiO2 (25 .32; 36.94; 37.74; 47.96) and quartz SiO2 (20.86; 26.64; 36.55; 39.47; 40.29; 42.45; 45.8, etc.). These results were also observed by [37] [38] . In contrast, quantitative analysis revealed 58.9% quartz, 29.7% muscovite, 8.9% kaolinite and 2.4% anatase.
3.5. Absorption Spectrum of Lead Chloride
The spectrophotometric dosage of lead chloride made it possible to find the
Figure 5. XRD spectrum of raw clay from Moukosso.
wavelength at the maximum of adsorption (λmax) of the Pb2+ ions. The results are shown in Figure 6.
Observation of this curve shows that the wavelength at the adsorption maximum is
. This value will be used in the remainder of this study.
3.6. Influence of Stirring Time on the Amountadsorbed
The authors determined the quantity adsorbed by the untreated fine fraction and by the organomodified fine fraction from the formulas:
(1)
(2)
With:
Co: initial concentration of lead in aqueous solution
Ce: equilibrium concentration (mol/L) of lead in aqueous solution
m: sorbent mass
V: volume of solution
Doi: initial optical density of the solution
Doe: equilibrium optical density of the solution
a) Influence of stirring time on the quantity adsorbed by the fine fraction
Figure 7 shows the evolution of the quantity of Pb2+ ions adsorbed by the fine fraction as a function of contact time.
The analysis of this figure shows a rapid adsorption of Pb2+ ions by the clay between 5 and 15 minutes of adsorbate-adsorbent contact, followed by a slow increase until equilibrium. This curve shows a balance between 25 and 30 minutes. This equilibrium time could correspond to the maximum efficiency of the adsorption of Pb2+ ions on this material. These results are in agreement with those found by [18] [39] [40] .
b) Influence of stirring time on the quantityadsorbed by the organomodifiedclay
Figure 6. Absorption spectrum of lead chloride.
Figure 7. Quantity adsorbed as a function of contact time.
Figure 8 shows the evolution of the adsorbed quantity of Pb2+ ions by organomodified clay as a function of stirring time.
There is a strong adsorption of Pb2+ ions by the clay between 5 and 15 minutes of agitation, followed by a slow increase between 15 and 30 minutes, which could be related to the saturation of the pores. The clay intercalated by DMSO has a greater adsorption capacity than that of the fine fraction, which would lead to maximum adsorption at the start of contact with the Pb2+ ions.
3.7. Adsorption Isotherms of the Fine Fraction and Intercalated Clay
The adsorption isotherms (Figure 9 and Figure 10) are obtained by plotting the curve of the quantity adsorbed at equilibrium of Pb2+ ions by the fine fraction and by the organomodified fraction as a function of the equilibrium concentration of Pb2+ ions.
The analysis of these figures shows that these adsorption isotherms exhibit the same behavior. These isotherms would be of type S presenting at low concentration, concavities facing upwards [41] [42] . The maximum adsorbed quantities of Pb2+ ions are 25.32 mg/g with the fine fraction and 34.45 mg/g with the organomodified fine fraction. The quantity adsorbed by the organoclay is greater than that obtained with the fine fraction; which could be explained by the fact that DMSO increases the interlayer distance of kaolinite and therefore promotes adsorption [20] .
3.8. Modeling of the Adsorption Isotherm
The authors have adopted the classic models of Langmuir and Freundlich adsorption isotherms, which allow by linear regression to obtain the values of the constants (Qmax, KL, 1/n and KF) in order to better interpret the adsorption results obtained.
a) Langmuir model
Figure 11 and Figure 12 give the Langmuir model obtained respectively from the fine fraction and the organomodified clay. This model is obtained by drawing the line:
Figure 8. Quantity adsorbed as a function of contact time.
Figure 9. Adsorption isotherm of the fine fraction.
Figure 10. Adsorption isotherm of the intercaleted clay.
Figure 11. Langmuir model on Pb2+ by crude fine fraction.
Figure 12. Langmuir model on Pb2+ by organomodifiedclay.
(3)
with:
: monolayer capacity of the adsorbent (mg/g)
: Langmuir adsorption constant
: origin coordinate
slope
The linearization of the Langmuir equations made it possible to determine the parameters grouped in Table 1.
The parameter Qmax (mg/g) which expresses the maximum adsorption capacity of the monolayer of the material is 22.471 mg/g for the fine fraction and 41.493 mg/g for the organomodified clay. This high maximum quantity in the organomodified clay would confirm the success of the intercalation of DMSO in this clay. The KL coefficient, which is the equilibrium constant, is equal to 1.07 × 10−2 L/mg for the fine fraction and 5.9 × 10−3 L/mg for the organomodified clay. These values being low would induce a fairly strong adsorption of lead particles by the two matrices [43] .
b) Freundlich model
Figure 13 and Figure 14 present the Freundlich model obtained from the fine fraction and the organomodified clay by drawing the straight line:
(4)
The linearization of the Freundlich equations made it possible to determine the parameters grouped together in Table 2.
KF and 1/n are Freundlich constants related to the temperature, the nature of the adsorbate and the adsorbent. In both cases, the determined KF coefficient is the same and equal to 4.09 L/mg. It is the same for 1/n which is close to 0.62; which would indicate a strong adsorption of Pb2+ ions by the studied materials [29] .
In view of the values of the coefficients (Qmax, KL, 1/n et KF) obtained, we
Table 1. Lines and linearization coefficients of the Langmuir model.
Table 2. Parameters of the linearization of the Freundlich model.
Figure 13. Freundlich model on Pb2+ by the crude fine fraction.
Figure 14. Freundlich model on Pb2+ by the organomodifiedclay.
deduce that the Langmuir model may be adequate to model the adsorption isotherm of lead by the clay studied.
4. Conclusion
X-ray diffraction analysis revealed that theMoukosso’s soil consists of muscovite (29.7%), kaolinite (8.9%), anatase (2.4%) and quartz (58.9%). Muscovite is the dominant clay species in the Moukosso’s soil. The infrared spectrum of the intercalated clay showed, in addition to bands of muscovite (3621 and 1020 cm−1) and kaolinite (3697, 3621, 1020 cm−1), DMSO-specific bands at 1008 and 1070 cm−1. The thermogravimetric analysis showed that the overall mass loss of the organoclay (25%) is greater than that obtained with the raw clay (8.5%), thus confirming the success of the intercalation. The authors observed rapid adsorption of Pb2+ ions between 5 and 15 minutes of stirring time in the cases of raw clay and clay intercalated with DMSO. The isotherms obtained are of type S with an adsorption quantity of 22.471 mg/g of the fine fraction and 41.493 mg/g of the intercalated clay. The adsorption of Pb2+ ions by the fine fraction and by the organoclay can be interpreted by the Langmuir model.