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Comparative study of groundwater resources in the basement complex and sedimentary terrain of Talata Mafara town and environs, Zamfara State, Northwestern
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All content following this page was uploaded by Abdullah Musa Ali on 25 April 2019.
http://dx.doi.org/10.5455/sf.18584
* Corresponding author Abdullah Musa Ali alicorp07@gmail.com Department of Geology, Bayero University, Kano, Nigeria.
© 2019 Faculty of Science, ATBU Bauchi. All rights reserved
A. M. Ali et al. / Science Forum (Journal of Pure and Applied Sciences) 16 (2019) 10 – 17 11
interactions. This study conducted experiments on correlated these data using the empirical regression
quartz and humic acid as representative inorganic and given by Eq. 1 below:
organic phases present in the natural aquatic environ- 74800
ment. The purpose of this article is twofold: (1) to con- r = 0.646 exp − + 11200 [Na + ] 0.33 [OH− ]0.44
RT
cisely review the reported mechanisms of quartz dis-
solution in acids and (2) morphologically characterize 74800
r = exp −
(1)
the features of quartz grains dissolved in humic acid. RT
1.1. Mechanism of quartz dissolution in acidic solutions One of the highlights of the proposed empirical
Quartz dissolution in acid results in either partial or regression of the data by Rimstidt is that the dissolution
complete disruption of the silicate structure. Generally, reaction in the acidic region is dependent only on the
the dissolution reactions are supposed to be dependent temperature (first term of the right-hand side of Eq. 1).
on the phenomena occurring at the interface between However, each of these models has significant lim-
the quartz and dissolving solvent (acid). The main dis- itations. The adsorption model is unable to accurately
solution models used to interpret the kinetic data for predict the orders of reaction unless isotherms with
the dissolution of quartz and other minerals include: randomly modifiable parameters are employed. The
(i) the adsorption model (Warren and Devuyst, 1973), surface complexation model theorizes that the rate
(ii) the surface complexation model (Furrer and of dissolution is proportional to the concentration of
Stumm, 1986; Wieland et al., 1988), (iii) the precursor a species on the surface; the presence of which is not
version of the surface complexation model (Oelkers et proved. Rimstidt (2015) suggested the combination of
al., 1994), and (iv) Crundwell’s theory that envisages these models into a “unified” theory to resolve their
the removal of material from the surface to form ions respective limitations. To provide a deeper insight,
in solution leaving behind a charged surface vacancy Crundwell (2017) posits that dissolution occurs by the
(Crundwell, 2014). The adsorption model (Warren separate, parallel, removal of oxygen and silicon units,
and Devuyst, 1973) and surface complexation mod- both of which are dependent on the potential differ-
els (Furrer and Stumm, 1988; Oelkers et al., 1994) ence across the Stern layer (interface between the
are related in the sense that these models all predict solute and quartz). The removal of these units creates
the formation of surface species that subsequently surface vacancies. The mechanism that is proposed
depart from the surface. These models differ from the for the dissolution of quartz in acidic solutions in this
ion-transfer mechanism as they do not view the solid model is shown in Figure 1. The silicon–oxygen bonds
as dissociating into its constituent ions prior to part- are broken to form anions as either HSiO43− or HSiO3−,
ing from the surface. and cations as either Si4+ or SiO2+ in separate parallel
In the adsorption model, the dissolution reactions reactions. The H+ ion attacks the SiO44− or SiO32− sites
are assumed to be dependent on the phenomena to form a potential dependent activated complex in
occurring at the interface, rather than on the diffu- the Helmholtz layer. In a parallel “partial” reaction, Si4+
sion of material through the alteration layer. The or SiO2+ sites form an activated complex with water
surface complexation models measure and correlate molecules in solution. Once these activated complexes
dissolution rates as a function of pH, ionic strength, break down into products, they subsequently react
and temperature; however, this approach provides with species at the outer Helmholtz plane to form the
no information about the molecular processes at the final products in solution. The rate of dissolution in
mineral surface. Crundwell’s model of dissolution acidic solutions is the same as that presented for the
reaction (Crundwell, 2014) reports that bridging dissolution of forsterite, and is given by Eq. 2:
bonds between the Si (siloxane (Si-O-Si) and silanol r = kH [H+ ]X t (2)
H H
summary, the dissolution mechanism appears to be a by approximately 20%, followed by a 100% increase
good description of the rate-determining processes in in apparent quartz solubility at 25°C. The resulting
dissolution of the quartz. model developed by the study suggested that dissolved
Thus, the mechanism of dissolution of quartz in organic compounds in natural waters at near-neutral
acidic solutions is summarized as follows: (i) the reac- pH and low temperatures can accelerate the dissolu-
tion of surface silicate tetrahedra with H+ ions across tion of quartz and increasing its solubility.
the Helmholtz layer; (ii) the reaction of discrete sur- Vermeer et al. (1998) studied the adsorption of
face silicon atoms with H2O across the Helmholtz humic acid to mineral particles in relation to the polye-
layer; and (iii) the reaction of products of the pre- lectrolyte behavior of the humic acid. At high pH and low
ceding two steps with species in solution to form the salt concentration, the adsorption was found to be low
final product. The bond-breaking may also preferen- and the humic acid molecules were adsorbed relatively
tially produce hydrated HSiO3− and SiO2+ entities in flat on the mineral surface, while at low pH and high salt
steps (i) and (ii), instead of the hydrated SiO44− and concentration, a substantial fraction of the adsorbed
Si4+ entities. Nevertheless, the dissolved surface mor- humic acid was not directly connected to the surface,
phological features of quartz are rarely characterized resulting in a moderately high adsorbed amount. Based
in these proposed dissolution mechanisms. Thus, this on adsorption experiments and self-consistent field
paper emphasizes on detailing the resultant features (SCF) calculations, the results of the study indicated that
of quartz dissolved in humic acid. a well-developed layer is a result of the adsorption and
that lateral interactions within this layer determined to
1.2. Quartz dissolution in organic (humic) acid
a large extent the adsorption process.
Organic electrolytes are frequently found in natu-
ral waters and are a vital component of many rock– 2. Characterization of Quartz Dissolution in Humic
water interactions. However, the influence of organic Acid
electrolytes on silica mobility, quartz solubility, and
quartz dissolution kinetics remains to be fully elu- 2.1. Experiment
cidated. Bennett (1991) investigated the kinetics of 2.1.1. Materials and methods
quartz dissolution in dilute aqueous organic-acid
solutions between 25°C and 70°C to determine the The quartz grains used were cleaned following the
influence of both organic and inorganic electrolytes. procedure reported by Ali et al. (2018). The prelimi-
The results of the study showed that multi-functional nary preparation of the quartz crystals involved crush-
organic acids such as citrate and oxalate accelerate ing in a mortar to increase the exposed surface area.
quartz dissolution by decreasing the activation energy The crushed material is subsequently sieved to gain
A. M. Ali et al. / Science Forum (Journal of Pure and Applied Sciences) 16 (2019) 10 – 17 13
>50 µm mesh sized grains. Next, approximately 20 g the quartz grains was dissolved at ambient labora-
of the quartz grains were subjected to an ultrasonifier tory temperatures (25°C ± 2°C) in bottles containing
in 0.1 mols L−1 HCl to eliminate the carbonate miner- aqueous solutions of 0.05 mol L−1 HCl maintained at
als and chelated iron oxide materials. Afterward, the pH 1 with a speed of 40 rpm to ensure the solution was
ultrasonified samples were immersed in 35% H2O2 always in contact with the quartz surface.
to detach organic fragments. The quartz grains were
2.1.3. Sample characterization
washed in de-ionized water and then dried in an oven
set at 60°C for 24 hours. Separate grains varied from Morphological characterization of the samples was
200 to 400 µm in size. This pre-treatment process performed using scanning electron microscopy (SEM:
dissolved sharp edges and removed secondary-phase Carl Zeiss Supra). Energy-dispersive X-ray (EDX) was
materials adhering clay particles, heavy minerals, performed to determine the composition of the dis-
organics, and surface artefacts that might cause errors solved quartz surface. Fourier transform infra-red
in the dissolution rate measurements. The final sam- (FTIR) analysis was utilized to examine the adsorp-
ples comprised subhedral to subround grains with tion of humic compounds on the quartz surface. FT-IR
surface defects that included conchoidal fractures and spectra were recorded at room temperature using a
cleavage planes (Fig. 2). Shimadzu FTIR 8400S, which was linked to a desk-
top computer loaded with the Shimadzu lab solutions
2.1.2. Quartz dissolution in humic acid
infrared (IR) software to process the recorded spectra.
Fifty milliliter of humic acid was dissolved in 0.1 M KCl This method is based on the interaction between IR
and regulated to pH 11 using 0.1 M KOH. The sample electromagnetic radiation and the vibrational motion
was agitated in a shaker for 1 hour, while testing the of atomic clusters.
pH intermittently. The quartz grains were then added
2.2. Results and discussion
to the humate suspension; an appropriate amount of
humate stock was slowly added. The humic acid sus- 2.2.1. Surface characterization of quartz dissolved in
pensions were acidified to ≈ pH 6 with 0.1 M HCl. The humic acid
samples were agitated for 18 hours at 25°C in a shaker;
then, the pH was adjusted as needed. Deionized water Based on silicamolybdate spectrophotometry measure-
was used to prepare all solutions. All reagents were ments, a mean concentration of 0.8 mg/l of SiO2 was dis-
analytical grade and were used without further treat- solved every hour under the experimental conditions.
ment. The pH of solution was monitored in all titration This confirms the dissolution of quartz. The SEM micro-
and ageing experiments using a pH meter (EUTECH, graphs show the quartz surface is intensely etched after
Model: Cyberscan). The batch system was used for dissolution (Fig. 3A and B), albeit at varying degrees.
the dissolution experiments, which involved the use Etch pit development is elucidated in earlier research
of sealed 50 mL polyethylene bottles. Five gram of on defect distribution and dissolution morphologies on
low-index surfaces of α-quartz (Ali et al., 2017; Yanina
Figure 2. FESEM image of a clean subhedral quartz grain with conchoidal fractures and smoothed edges.
14 A. M. Ali et al. / Science Forum (Journal of Pure and Applied Sciences) 16 (2019) 10 – 17
et al., 2006), while Ostapenko et al. (2007) analysed interaction of electrolytes (H+) with quartz in an array of
the asymmetry of growth and dissolution on the differ- geological implications that reflect natural environments
ent faces of quartz. The variations in the quartz surface such as oxidized vapour dominated geothermal systems,
texture were attributed to differences in the densities of acid crater lakes, and acid mine drainage settings.
pre-existing steps on the initial crystal surface or dislo-
2.2.2. Adsorption of humic compounds on quartz
cation points. The smooth surface of quartz surface in
surface
some areas suggests the dissolution of ledges of plas-
tered amorphous quartz and “cleaving off” adhering Concomitant with the quartz dissolution is the adsorp-
silicate particles. The edges and interfaces of adjacent tion of humic acid onto the quartz surface via hydro-
quartz grains promote dissolution, whereas, a smooth gen-bond interaction. Figure 4 shows the flakes of
boundary and middle of the crystal would be thermody- amorphous material, possibly humic material, adher-
namically more stable, which accounts for the relatively ing to the quartz surface. Figure 5 depicts the fibrous
higher etching at the edges. The kinked face of the deep and wiry structures of the humic acid molecules accu-
etch pits (Fig. 3D) exhibited the highest steep retreat, mulating in the etch and dissolution pits of the quartz
while the flat overlapping face (Fig. 3C) denotes small surface. Also observed are platelets of the humic
and intermediate retreat. The sloping sides of the etch material plastered on the quartz surface. Therefore,
pits merge with pointed adjacent edges and bottoms, in addition to mineral dissolution, humic acid serves
which indicates the etch pits originate from dislocation as organic binders in siliciclastics. The bonded aggre-
defects in the mineral surface. These resultant dissolu- gates acting as bridging and infill materials (Fig. 5)
tion features can be used to characterize the effects of can be attributed to clustering of dissolved silica and
dissolution on quartz-rich systems such as hot dry rocks humic acid molecules via chemisorption or physisorp-
(HDR). This study provides empirical evidence on the tion (Zhou et al., 2014).
Figure 3. (A) Etched quartz grains, (B) close view of intensely dissolved grain quartz, (C) flat overlapping
face, and (D) deep etch pits.
A. M. Ali et al. / Science Forum (Journal of Pure and Applied Sciences) 16 (2019) 10 – 17 15
2.2.3. EDX analysis 2.2.4. FTIR analysis of quartz dissolved in humic acid
The EDX spectra of the dissolved quartz surface (Fig. 6) The FTIR spectra of the quartz grains dissolved in
indicate the presence of a range of elements. The Si is humic acid is shown in Figure 7. The IR bands at 693
derived from the quartz grains and dissolved silica, C and 775 cm−1 are assigned to S–O quartz bond derived
signifies humic compounds adsorbed on the quartz, K from Si-O-Si inter tetrahedral bridging bonds in SiO2.
and Cl denote the potassium and chlorine content of the The peak at 606 cm−1 characterizes Si-O-Si (silox-
reagent solution used to dissolve the humic compounds, ane) bond of quartz. The broadband at 3,152 cm−1
and Fe and Al indicate the minor presence of iron and is attributable to O–H stretching vibrations, validat-
aluminium oxides associated with humic acids. ing the presence of free and intermolecular bonded
alcohols/phenols/amines and possible carboxylic
Figure 4. Closer view of quartz dissolved in humic acid, with inset arrow indicating
the presence of adsorbed materials.
Figure 5. (A) Fibrous humic acid molecules aggregating in etch pits. (B) Platelets of humic material adsorbed on the quartz surface.
16 A. M. Ali et al. / Science Forum (Journal of Pure and Applied Sciences) 16 (2019) 10 – 17
Figure 7. FTIR spectra showing characteristic peaks for Fe-O, Si-O-Si, C-H, and H-O-H bonds.
acids (Rodrigues et al., 2009), while the other asym- overlapping crystal faces. This study posits the disso-
metric band at around 3,336 cm−1 is assigned H–O–H lution of quartz in humic acid creates surface defects
stretching bond (hydrogen bonded molecular H2O) or such as etch pits and leads to associated adsorption of
absorbed water (Graetsch 1994; Kronenberg, 1994). humic acid molecules on the quartz surface via hydro-
The band at 2102 suggests C-H stretching bond from gen-bond interaction.
humate material.
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