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Effect of pH on the stability of quartz in a multi-phase system of kaolinite,

hydrous Al (hydr)oxide and quartz

Article · May 2019

DOI: 10.1007/s42452-019-0398-3

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Research Article

Effect of pH on the stability of quartz in a multi‑phase system

of kaolinite, hydrous Al (hydr)oxide and quartz
Abdullah Musa Ali1 · Eswaran Padmanabhan2 · Abubakar Mijinyawa1,3 · Mohammed Yerima Kwaya1

© Springer Nature Switzerland AG 2019

Abstract
The stability of quartz in a multi-phase system of kaolinite and Al (hydr)oxides and quartz has been addressed in quite
a few studies. However, the impact of pH on these multi-mineral interactions has not been elucidated. Therefore, this
study shows the different dissolution behaviour and surface morphology of quartz admixed with hydrous kaolinite and
aluminium (hydr)oxides under variable pH conditions. This will enhance the predictability of silica behaviour in natural
rock weathering and reservoir systems. Scanning electron microscopy characterization shows that kaolinite and Al (hydr)
oxides exhibit high-quality coating of quartz surface at acidic and alkali pH by creating a surficial secondary layer that
allows agglomeration of other minerals, while Fourier transform infrared analysis showed shifts in peak positions of Si–O
quartz from 691 cm−1 and 692 cm−1 at pH 5 and 7 to 686 cm−1 at pH13, and broadening of characteristic hydroxide and
siloxane peaks as well as the formation of new Si–O–Al bonds at pH 13, suggesting structural changes in hydrous alu-
minosilicates and Al hydroxides (broken bonds of Al–O–Si, Al–O–Al and Si–O–Si) and Al substitution for Si in tetrahedral
sheets. The dissolved silica in quartz–kaolinite–Al (hydr)oxides interactions is relatively lower under alkali conditions
compared to acidic pH. Quartz dissolution was highest at pH 7; signifying the interaction of quartz with Al (hydr)oxides
and kaolinite is favourable for quartz dissolution at neutral pH range. The results indicate that quartz interaction with
kaolinite and Al (hydr)oxides is dependent on pH. Quartz coating by kaolinite and Al (hydr)oxides is more effective under
alkali pH conditions, given the low solubility of Al within this pH range.

Keywords  Kaolinite · Al (hydr)oxides · FTIR characterization · Quartz dissolution

1 Introduction interactions take place under different pH conditions,

depending on the environment of deposition and diage-
Quartz is a fundamental material in reactions that affect netic processes. Despite this association and ubiquitous
porosity, permeability, capillarity buffering and sorption coexistence of quartz, kaolinite and Al (hydr)oxides, major-
capacity of sandstones [11, 26, 49]. Recently, related stud- ity of previous studies dealt with these minerals separately
ies have focused on quartz dissolution [4, 7, 20] because [27, 47]. Moreover, in the natural and man-made high
of the rising demand for rate information in composition- pH environments, little is known regarding the effect of
ally intricate solutions derived from extreme conditions kaolinite and dissolved aluminium on the dissolution of
generated in systems such as nuclear waste disposal facili- quartz. It is thus pertinent to elucidate the multi-mineral
ties and oil wells. Quartz grains are often associated with interactions of quartz, kaolinite and hydrous Al (hydr)oxide
clays and aluminium (hydr)oxides in natural environments across the pH spectrum to enhance the predictability of
rather than as discrete separate forms. These multi-mineral silica behaviour in natural rock weathering and reservoir

*  Abdullah Musa Ali, alicorp07@gmail.com | 1Department of Geology, Bayero University Kano, Kano, Nigeria. 2Department
of Geosciences, Universiti Teknologi PETRONAS, Seri Iskandar, Malaysia. 3Centre for Geodesy and Geodynamics, National Space Research
and Development Agency, Abuja, Nigeria.

SN Applied Sciences (2019) 1:388 | https://doi.org/10.1007/s42452-019-0398-3

Received: 11 November 2018 / Accepted: 23 March 2019

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systems. Deciphering these interactions will also help that kaolinite dissolves congruently at pH < 5 and > 11 [21].
explain the dissolution behaviour and phase transition of It should be stated that the concentrations were selected
silicates in alkali–acid leaching processes, which are crucial arbitrarily, and the effect of the clay concentration was not
to microcrystalline purification and geochemical processes considered. Buffer solutions of NaCl, KCl, NaOH and HCl were
[5, 6, 8, 29, 48, 50, 51]. used to regulate the pH. The pH was adjusted with NaCl in
The stability of quartz in a multi-phase system of kaolin- drop-wise approach with constant stirring to attain a pH of 5
ite, Al (hydr)oxides and quartz has been addressed in quite and 7. For pH of 13, 0.5 mol of NaOH was slowly added to the
a few studies [2–4, 7, 14, 15]. Bickmore et al. [7] reported solution with the pH constantly measured. Solutions were
that dissolved Al ions at concentrations below the solubil- immediately poured into the airtight polyethylene reaction
ity of Al-(hydr)oxide significantly inhibit the dissolution of vessels. The resultant slurry was briskly stirred using a mag-
quartz. Since aluminium solubility increases with increas- netic stirrer for 15 min until a homogeneous mixture was
ing pH in the basic region, its influence on dissolution rates obtained and left to rest for a period of 20 days.
will be important, whether the aluminium is derived from Batch experiments were designed to measure quartz
natural dissolution processes or by synthetic inclusion [7]. dissolution. Bottles were placed in a constant temperature
This study thus explores the role of pH in the interactions bath of 60 °C. The amount of dissolved silica was measured
between quartz, kaolinite and Al-(hydr)oxide. Kaolinite after 20 days of ageing using molybdate spectrophotom-
was specifically included because the utilization of kao- etry (HACH D2800). Upon removal from the bath, each bottle
linite is closely related to its reactivity and surface prop- was unfastened and partly submerged in a beaker of the
erties [19, 53, 54], which can be modified by interactions hot bath water for pH measurement at a temperature close
with quartz and Al-(hydr)oxides. The study also examines to that of the bath. Solution pH was measured using a pH
the coating of quartz grains by kaolinite and Al (hydr) meter (EUTECH, Model: Cyberscan) with automatic tempera-
oxides under different pH conditions. Scanning electron ture correction. pH measurements were made only to show
microscopy (SEM) and Fourier transform infrared (FTIR) that pH drift significantly during mineral interactions, which
spectroscopy were used because they effectively enable can affect their respective dissolutions.
the characterization of mineral species [31, 38–42].
2.2 Sample characterization

2 Materials and methods FTIR spectra were used for composition analysis and to iden-
tify disparity in chemical bonds. This method is based on the
2.1 Sample preparation and synthesis interaction between infrared (IR) electromagnetic radiation
and the vibrational motion of atomic clusters. FTIR spectra
A series of experiments were carried out to explore the were recorded at room temperature using a Shimadzu FTIR
combined effect of kaolinite and oxides/hydroxides of Al on 8400S, which was linked to a desktop computer loaded
quartz morphology and dissolution. White quartz sand used with the software: Shimadzu labsolutions IR, to process the
in the experiments was 99.8% ­SiO2 according to energy-dis- recorded spectra. Well-crystallized kaolinite was used in the
persive X-ray (EDX) analysis. The quartz crystals were crushed experiment. Morphological characterizations of the sam-
in a mortar grinder to increase the exposed surface area ples were performed using scanning electron microscopy
and then sieved to obtain > 50 μm mesh fraction. This pre- (SEM: Carl Zeiss Supra). The SEM–EDX analysis was carried
treatment dissolved sharp edges, adhering fine particles and out under low vacuum conditions to allow analysis of the
other surface contaminants without introducing metals or uncoated samples by protecting against the build-up of
corrosive agents to the system that might affect subsequent static charge on the particle surfaces. Images of the surfaces
dissolution rate measurements. The quartz grains were then were taken relative to the mounting, and by rotating and tilt-
ultrasonified in cold ­HNO3 solution to remove any carbonate ing the SEM stage to an angle between 45° and 55°. The bulk
coatings and ferruginous contamination. The raw kaolinite chemical results are based on the mapped data and exclude
used as precursor mineral was ground in an agate mor- the direct influence of the carbon sticky pad.
tar, passed through a 125 μm sieve and then washed with
hydrogen peroxide ­(H2O2) to remove organic residue. 0.1 g
of kaolinite was added to ­Al2O3 dissolved in distilled water. 3 Result
Solutions were prepared using reagent grade NaOH, NaCl
and ­Al2O3. In the first experiment, 0.1 g of kaolinite and 1 g 3.1 Quartz dissolution and pH measurement
of Aluminium oxides (­ Al2O3) were admixed with 2 g of quartz
substrates in polyethylene bottles at variable pH of ≈ 5, 7, Data on the experimental conditions for different admix-
13 to reflect different environment of deposition, given tures of quartz (Q), kaolinite (K), aluminium (hydr)oxides

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as well as measured silica dissolved from quartz are solutions into the quartz grains, which accounts for the
presented in Table 1. As observed, pH varies with the low silica in the system. Thus, the amount of dissolved
amount of dissolved silica in the system. At pH 5 and 13, silica in quartz–kaolinite interactions is relatively lower
the pH remained relatively steady after 20 days of age- under alkali conditions compared to acidic pH. The dis-
­ H− ions dissolved from kaolinite
ing. In acidic conditions, O solution of pure quartz grains was included in the experi-
­(Al2SiO5(OH)4) and aluminium (hydr)oxide (Al(OH)3) (since ment as control sample (Table 1). The amount of silica dis-
both compounds are soluble at low pH) are released into solved from pure quartz is significantly higher compared
the solution, causing the pH to increase. However, the to the admixtures.
pH dropped drastically at pH 7 to 4.75. The Q + K + Al sys-
tem records values of 8.3 mg/L at pH 5, 9.2 mg/L at pH 7 3.2 Morphological characterization using SEM
and 1.7 mg/L at pH 13 (Table 1). The steep decline in pH
from 7 to 4.75 and concomitantly high silica is character- The dissolution process of kaolinite in HCl and NaOH
ized by distinctive grain bridging (Fig. 2b). Under neutral solution was confirmed through changes in morphology
pH, the available O ­ H− ions are involved in the dissolu- from booklets to granulations and clay flakes as shown
tion of quartz, and with continuous protonation, the pH in Fig. 1. The dissolved kaolinite has no integral crystal
declines over the duration of ageing. The agglomeration structure and appears more like a transitional mineral
of the hydrous aluminosilicates over the quartz grains at phase, from booklets to granulations, clay flakes and
pH 13 possibly limits the dissolution route of the alkaline platelets (Fig. 1). SEM micrographs were obtained for

Table 1  Experimental conditions for the admixture of Al (hydr)oxides (Al), kaolinite (K) and quartz (Q)
Sample Time of age- Ageing tem- Initial pH Final pH Dissolved silica Characteristic features
ing (days) perature (°C) (mg/L)

Q 20 60 12 11.8 35.6 Triangular etch pits; kink crystal faces

Q + K + Al 20 60 5.00 5.30 8.30 Grain coating and bridging
Q + K + Al 20 60 5.00 5.50 7.80
Q + K + Al 20 60 5.00 5.40 8.10
Q + K + Al 20 60 7.00 4.75 9.20 Grain coating and bridging
Q + K + Al 20 60 7.00 5 9.70
Q + K + Al 20 60 7.00 5.20 9.60
Q + K + Al 20 60 13.00 13.20 1.70 Shallow dissolution pits; higher grain coating
Q + K + Al 20 60 13.00 13.30 2.20
Q + K + Al 20 60 13.00 13.10 1.65

Fig. 1  SEM micrographs showing changes in the morphology of kaolinite from a booklets in low pH to b granulations near neutral pH, c
clay flakes at neutral pH and d platelets at high pH

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Fig. 2  SEM micrographs of
Q + K + Al samples showing
a slight grain bridging at pH
5, b quartz grain bridging by
kaolinite and Al (hydr)oxides at
pH 7, c agglomeration of the
quartz grains by kaolinite and
Al (hydr)oxides at pH 13

different admixtures of quartz (Q), kaolinite (K) and Al The bridging of the quartz grains is more prominent
oxides aged in acidic, neutral and alkali pH media. The and distinctive in samples aged in neutral solution (pH
most discernible feature is the agglomerations or clus- 7), as observed in Fig. 2b. In alkali solution, the quartz
tering of the quartz grains by kaolinite and hydrous Al grains are characterized by shallow dissolution pits
oxide phase, as shown in Fig. 1. The bridging type, result- filled with kaolinite with relatively higher grain coating
ing from the adsorption of the kaolinite and hydrous Al compared to the samples aged in acidic and neutral pH
hydroxides on quartz, is not dependent on the Al con- solutions (Fig. 2c). This suggests that quartz grains are
centration. As explained in the sample preparation and better coated and agglomerated by aluminosilicates
experiment section, the concentration of quartz, kao- under alkali pH conditions. At alkali pH, dissolution
linite and aluminium oxides were maintained with only and etched pits are present on the quartz surfaces in
the pH being varied. The Al distribution is clearly differ- some places.
ent across pH, indicating that the bridging type is rather
dependent on the dissolution and adsorption of Al on 3.3 Micro‑elemental distribution
the quartz surface.
The SEM images of each of the analysed particle The surface elemental composition of the samples was
surfaces are presented in Fig. 2. The samples generally characterized using SEM–EDS to build a detailed picture
have a rounded morphology, although less smoothed, of their surface structure and composition. The nature
and a highly porous interior consisting of fine, irregu- of compositional differences was investigated based
lar voids. Features characterizing the cluster of quartz, on individual element maps and the results of targeted
kaolinite and aluminium oxides (Q + K + Al) vary with pH point analysis of different surface chemical phases. The
(5, 7 and 13), as shown in Fig. 2. For acidic and neutral elemental distribution maps of Si, O and Al for surfaces
pH media, observed features include coating and bridg- of Q + K + Al samples are shown in Figs. 3, 4 and 5. Al
ing of quartz grains by kaolinite. At pH 5, the quartz showed the most spatial heterogeneity in their distribu-
grains are slightly cemented, as shown in Fig. 2a. Also tions. The concentrations of Si and O are strongly local-
observed is the deteriorating and flaking of the quartz ized across the quartz surface in the areas that appear
surface (Fig.  2a) due to etching in the acid solution. darker on the SEM image. The Q + K + Al sample aged

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Fig. 3  EDX elemental map-

ping of quartz surface at pH 5,
indicating Al accumulations in
the fractures and crevices but
absent on the smooth surface

at pH 5 showed that Al is aggregated at the fractured element is more retained on the quartz surface under
faces and crevices, while the smooth quartz surface alkali conditions.
remains bare, as indicated by the elemental distribu-
tion (Fig. 3), where Si and O are uniformly distributed, 3.4 FTIR spectroscopic analysis
while Al accumulates in the surface defects. The isolated
Al ions are embedded in the surface of the particle. The 3.4.1 Low wave FTIR region
EDX mapping of the Q + K + Al sample aged at pH 7
(Fig. 4) shows that Al is relatively absent on the quartz The characteristic IR peaks for the different samples
surface, but rather forms the bulk composition of the were identified. In the low wave number region of the
bridge connecting the quartz grains. The EDX mapping FTIR spectra (1400–400 cm−1) shown in Fig. 7, the dis-
of the Q + K + Al sample aged at pH 13 (Fig. 5) shows that tinct absorption bands at 1030 cm−1 and 1006 cm−1 are
Al leached from the kaolinite and Al (hydr)oxides are ascribed to framework Si–O–Si stretching vibrations. The
evenly distributed over the entire quartz surface, which absorption bands at 936 cm−1 and 914 cm−1 represent the
suggest that quartz grains are better coated under alkali Al–OH bending vibrations. The band at 936 cm−1 is also
conditions. attributed to the non-bonding inner-surface or surface
Elemental mapping of the sample aged under alkali (nanostructure) OH. The bands at 775 cm−1 and 697 cm−1
conditions (pH 13) shows that Si and O are uniformly correspond to Al–OH or perpendicular surface ligands
distributed on the quartz surface. The wt% of the ele- (translational OH). The absorption bands at 936 cm−1 rep-
ments shows that Al is more dominant at pH 13 and resenting the Al–OH bending are conspicuously absent at
less at pH 5, as shown in Fig. 6. This suggests that the Al pH 13. In contrast, the absorption band at 864 cm−1 band
for pH 13 (characteristic of the deformation vibration of

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Fig. 4  EDX elemental mapping

of the bridged quartz grains at
pH 7, indicating the predomi-
nance of Al in the bridge con-
necting the quartz grains

bonded OH groups) is absent at pH 5 and 7. In addition, groups, indicating the presence of 4 OH stretching modes
the Si–O–Al stretching peak shifted from 540 cm−1 at pH [34]. For the sample admixed at pH 5, three OH stretch-
13 to 545 cm−1 and 547 cm−1 at pH 5 and 7, respectively. ing vibration bands (3695, 3652 and 3620 cm−1) emerged,
Also observed is the band shifting of Si–O quartz peak while the characteristic hydroxyl peak at 3668 cm−1 is
from 691 cm−1 and 692 cm−1 at pH 5 and 7 to 686 cm−1 at absent. Apart from the hydroxyl protons, there exists
pH 13. The siloxane (Si–O–Si) peak shifted from 657 cm−1 the proton of the physically adsorbed water in natural
at pH 7 to 644 cm−1 at pH 13. This peak is absent at pH 7. kaolinite. The peak at 3695 cm−1 can be assigned to the
The broadening of the peak with increased pH indicates in-phase stretching mode of inner-surface OH groups or
decreased crystallinity of the solid kaolinite phase [24]. The Al–OH stretching bond, while the peak at 3652 cm−1 can
peaks at 1406 cm−1 and 1433 cm−1, which are indicative be ascribed to out-of-phase stretching modes of inner-sur-
of Al–O as Si cage (Si–O–Al), are only present in samples face OH groups. The peak at 3620 cm−1 denotes stretching
aged at pH 13. The presence of Si–O quartz characterized of the inner OH group resulting from the bonding between
by the peak at 1084 cm−1 only for the sample aged at pH a proton and an oxygen that is also coordinated to ­Al3+
7 suggests the poor kaolinite coating at neutral pH due to in an octahedral site [18, 30]. These peaks become indis-
its non-dissolution at this pH. tinct with increase in pH. At pH 7, the absorption peaks at
3652 cm−1 and 3668 cm−1 are absent, while the absorption
3.4.2 Variations in hydroxide bonds band at 3695 cm−1 is the only prominent hydroxide band
at pH 13 due to peak broadening and increased asymme-
Given that structural order can influence morphology, try caused by OH adsorption, as shown in Fig. 8.
it is important to examine the band parameters (bond
variations) of inner OH deformation vibration and peak
intensity as functions of the structural order/morphology. 4 Discussion
The inner hydroxyls of kaolinite–Al hydroxides are sited
in the shared planes of octahedral sheet with the proton- The results show that quartz interaction with kaolinite
end affixed in the ditrigonal hole [52]. The inner-surface and Al (hydr)oxide is controlled by pH. SEM characteri-
hydroxyls are derived from the bonding of hydrogen zation showed variations in grain coating and quartz
atoms with oxygen atoms of neighbouring S­ iO4 tetrahe- morphology for the different clusters. At acidic pH,
dral sheet. The basic unit cell of the hydroxyls holds 4 OH relatively less Al is retained on the quartz surface, with

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Fig. 5  EDX elemental mapping

of quartz surface at pH 13, indi-
cating the even distribution of
Al on the quartz surface

Fig. 6  Bulk chemical charac- 60

terization of particle surfaces
showing a plot of elemental 50
weight (wt%) against pH for
Si, Al, O
40
wt%

30

20

10

0
4 6 8 10 12 14
pH
Si Al O Linear (Si) Linear (Al) Linear (O)

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Fig. 7  Overlapping FTIR spectra of Q + K + Al synthesized at pH 5, 7 and 13 between 500 cm−1 and 1500 cm−1 showing the presence of Si–O–
Al and inner Al–OH deformation for the sample synthesized at pH 13

morphological analysis indicating the outcome of etched observed that Al had a hindering effect on fused silica dis-
quartz surfaces and low clay coating. Under neutral and solution in 0.1 M NaOH at 95 °C (pH ~ 11.3), while Diallo
alkali conditions, grain bridging and agglomerations et al. [16] showed that the dissolution rate of quartz was
were observed, respectively. This pH dependency of kao- reduced by about a factor of 4 in the presence of Al in 0.1 N
linite dissolution has been attributed to the adsorption NaOH or KOH (pH ~ 11.8) at 70 °C. Labrid and Duquerroix
of ­H+ and ­OH− ions to aluminium and silicon reaction [25] also observed that Al at 30 °C and pH 11.5 inhibited
sites [9, 10, 12], in addition to the formation of positively, quartz sand dissolution rates. This study expands this
neutral and negatively charged aluminosilicate activated theory by explaining possible interpretations of the phe-
complexes at acid, near neutral and alkaline pH [1, 23]. nomenon at different pH.
In addition, the dissolved Al inhibits quartz dissolution in The different IR peak positions and intensities of the
alkaline solutions; however, this study relates the inhibi- samples are attributed to the broken bonds of Al–O–Si,
tion of quartz dissolution to the adsorption of Al ions Al–O–Al and Si–O–Si and the Al substitution for Si in
to the quartz surfaces, as shown in the SEM images and tetrahedral sheets [51]. The position of the hydroxyl and
EDX analysis. siloxane bonds depends on the outer chemical environ-
The structural changes in pure quartz with pH have ment and on the morphology as a secondary structure
been published in earlier papers [4, 35]. Quartz dissolu- [43]. The shifts and intensity disparity of the charac-
tion is generally higher at alkali pH, particularly hydrox- teristic peaks can be attributed to changes or shifts
ides of monovalent ions such as ­K+ and ­Na+ because of in charges sited at the edges of kaolinite crystals [54],
their solvent properties (low hydrated cation radii and possibly resulting from the ageing process. The edge
high hydrolysis constants). The dissolved quartz surface is surface area is independent of the highly variable state
typified by wide triangular etch pits and deep kink crystal of the interlayer space [54] but rather controlled by the
faces. However, in this current paper, the dissolving effect broken fringes, particle diameter and shape. The sur-
is being inhibited by the presence of Al, insolubility of kao- face broken bonds are the source of the pH-dependent
linite at high pH and the occluding clay particles, which charges, which become altered differently in variable
prevent the solution from reaching the bare quartz sur- pH media. For samples aged in alkali solution, bands
face. This explains the relatively low amount of dissolved characterizing OH groups at 3620 cm −1 and 3650 cm −1
silica from quartz at alkali pH when admixed with kaolinite disappeared completely, leaving behind a very low
and Al (hydr)oxide. intensity peak at 3695  cm −1 . At the same time, the
The notion that sorbed Al inhibits quartz dissolution bands related to Si–O and Al–O vibrations in the range
rates in alkaline solutions has substantial support in lit- 1100–400 cm−1 were visibly broadened, indicating that
erature [17, 22, 44–46]. Adsorbed Al species have been the solid phase was gradually amorphous while the
revealed to qualitatively reduce silica dissolution rates in octahedral aluminium evolved into amorphous alumi-
mildly alkaline solutions. In highly alkaline solutions, Al nosilicate structure [24]. These physical changes allow
decreases silica dissolution to a larger extent, although the absorption of Al ions onto the quartz grains, as indi-
most of the reviewed studies did not consider the satu- cated by the peak at 1400 cm −1. Kaolinite dissolves in
ration states of Al-(hydroxides). For example, Sasaki [37] alkaline media, giving rise to silica [­ SiO 2 (OH) 2] 2− and

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to the increase of the structural defects in kaolinite lay-

ers, the competing Al ions are expected to impact on
peak intensity. As shown in Fig. 9, the peak characteriz-
ing inner ­OH− deformation for pH 13 suggests structural
changes in Al–OH and Si–OH bonds. It also indicates that
the inner-surface hydroxyls form the hydrogen bond with
the oxygen of the adjacent ­SiO4 tetrahedral sheet at this
pH range.
As compared to the spectra of pristine kaolinite and
quartz (Fig. 9), the intensity of absorbance peaks of kao-
linite decreased considerably with interaction with quartz.
The intensity of the %transmittance is highest at pH 5 and
lowest at pH 7. This can be attributed to the fact that kao-
linite dissolution generally decreases from pH 1 to 7, but
increases from pH 8 to 12 [13]. The hydrous clay minerals
and Al (hydr)oxides provide a relatively higher coating of
quartz grains under alkali conditions. Spectral subtract of
the Q + K + Al admixture aged at pH 13 from the spectra
of pristine quartz, and kaolinite (Fig. 10) shows the for-
mation of new bonds at 1400 and 864 cm−1, which are
characteristic of Si–O–Al and inner OH/Al–OH deforma-
tion, respectively.
Therefore, it can be inferred that the dissolution of
quartz in natural and engineered systems will not only be
affected by pH, but also influenced by its interaction with
hydrous oxides and clay minerals. Similar atomic propor-
tions of Al and Si in several areas within the interior regions
of quartz coatings are supportive evidence for the bond-
ing of kaolinite and quartz [32, 33]. To effectively predict
the transport and reactivity of quartz in aquatic environ-
ments, the aggregation mechanisms between quartz and
Fig. 8  Stacked FTIR spectra of Q + K + Al synthesized at pH 5, 7 and hydrous oxides and clay minerals and quartz should be
13 between 3200  cm−1 and 4000  cm−1 showing the variations in taken into consideration.
hydroxide bonds at the different pH

5 Conclusion
[SiO(OH)3]− as well as aluminium [Al(OH) 4]−, which can
inter-react to yield an aluminosilicate that precipitates The dissolution of quartz in a multi-phase system of
in the form of a ­N a 2O–Al 2O 3–SiO 2–H 2O gel or zeolite quartz, hydrous oxides and clay minerals is controlled by
[28, 36, 48]. pH. The results showed that Al oxides creates a surficial
The changes in position of the surface OH groups secondary phase that allows agglomeration of other min-
can also be followed in the OH deformation range erals as well as produce derivative surface defects that
(950–850 cm−1). The changes in the deformation coor- mask the quartz morphology. Quartz grains are better
dinates of surface OH groups influence the position of coated and agglomerated by aluminosilicates under neu-
the inner OH groups by changing the bond lengths/bond tral and alkali pH conditions. The competing interactions
angles [54]. Since the inner OH groups are inert ones as of Al (hydr)oxides and hydrous kaolinite are indicated
compared to the surface OH groups, they can potentially by the presence of Si–O–Al bonds and the broadening
be an indicator of the morphological variations that of quartz siloxane bonds, particularly under alkali condi-
reflect changes in chemical environment, particularly tions, which suggests that structural deformation is more
pH. Although Zhang et al. [51] reported that the inten- active at high pH.
sity changes of all kaolinite bands are mainly attributed

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Fig. 9  Overlapping FTIR spectra of quartz, kaolinite and admixture inner Al–OH deformation, and the absence of surface OH for the
of quartz, kaolinites and aluminosilicates aged at pH 13 between sample synthesized at pH 13
500  cm−1 and 1500  cm−1 showing the presence of Si–O–Al and

2. Ali A, Padmanabhan E (2013) Quartz surface morphology of

tertiary rocks from North East Sarawak, Malaysia: implications
for paleo-depositional environment and reservoir rock quality
predictions. Pet Explor Dev 41:6
3. Ali AM, Padmanabhan E (2017) The impact of pH and tempera-
ture on gibbsite reactivity with quartz. Int J Petrochem Res
1(1):40–45
4. Ali AM, Padmanabhan E, Baoiumy H (2017) Characterization of
alkali induced quartz dissolution rates and morphologies. Arab
J Sci Technol 42(6):2501–2513
5. Arias M, Barral MT, Diaz-Fierros F (1995) Effects of iron and alu-
minum oxides on the colloidal and surface properties of kaolin.
Clays Clay Miner 43:406–416
6. Arias M, Barral MT, Diaz-Fierros F (1997) Comparison of func-
tions for evaluating the effect of Fe and A1 oxides on the par-
ticle size distribution of kaolin and quartz. Clay Miner 32:3–11
7. Bickmore BR, Nagy KL, Gray AK, Brinkerhoff AR (2006) The
effect of Al(OH)4 on the dissolution rate of quartz. Geochim
Cosmochim Acta 70:290–305
8. Bish D (1989) Rietveld refinement of non-hydrogen atomic
positions in kaolinite. Clays Clay Miner 37(4):289–296
9. Blum AE, Yund RA, Lasaga AC (1990) The effect of dislocation
Fig. 10  FTIR spectral subtract of Q + K+Al from the spectra of pris-
density on the dissolution rate of quartz. Geochim Cosmo-
tine quartz and kaolinite
chim Acta 54:283–297
10. Brady PV, Walther JV (1989) Control on silicate dissolution
Funding  The study was supported by the graduate assistantship rates in neutral and basic pH solutions at 25 °C. Geochim Cos-
scheme provided by the Universiti Teknologi PETRONAS. No part of mochim Acta 53:2823–2830
the manuscript has been published or under consideration in other 11. Brantley SL, Kubicki JD, White AF (2008) Kinetics of water–rock
journals. interactions. Springer, New York
12. Carroll-Webb SA, Walther JV (1988) A surface complex reac-
tion model for the pH-dependence of corundum and Kaolinite
Compliance with ethical standards  dissolution rates. Geochim Cosmochim Acta 52:2609–2623
13. Carroll-Webb SA, Walther JV (1990) Kaolinite dissolution at
Conflict of interest  The authors declare that they have no conflict of 25 °C, 60 °C and 80 °C. Am J Sci 290:797–810
interest. 14. Coston JA, Fuller CC, Davis JA (1995) ­Pb2+ and ­Zn2+ adsorption
by a natural aluminum- and iron-bearing surface coating on
an aquifer sand. Geochim Cosmochim Acta 59:3535–3547
15. Davis JA, Coston JA, Kent DB, Fuller CC (1998) Application of
References the surface complexation concept to complex mineral assem-
blages. Env Sci Technol 32:2820–2828
1. Aagaard P, Hegelson HC (1982) Thermodynamic and kinetic 16. Diallo MS, Jenkins-Smith NL, Bunge AL (1987) Dissolution rates
constraints on reaction rates among minerals and aqueous for quartz, aluminum bearing minerals, and their mixtures
solutions-I. Theoretical considerations. Am J Sci 282:237–285 in sodium and potassium hydroxide, SPE paper 16276. In:

Vol:.(1234567890)
SN Applied Sciences (2019) 1:388 | https://doi.org/10.1007/s42452-019-0398-3 Research Article

International symposium on oilfield chemistry, San Antonio, 38. Schwertmann U, Taylor RM (1977) Iron oxides. In: Dixon JB,
Texas, Feb. 4–6, pp 359–368 Weed SB (eds) Minerals in soil environments. Soil Science Soci-
17. Dove PM (1995) Kinetic and thermodynamic controls on silica ety of America, Madison, pp 145–180
reactivity in weathering environments. In: White AF, Brantley 39. Schwertmann U, Murad E (1977) Effect of pH on the formation
SL (eds) Chemical weathering rates of silicate minerals, vol 31. of goethite and hematite from ferrihydrite. Clays Clay Miner
Mineralogical Society of America, Short Course, Chantilly, pp 31(4):277–284
236–290 40. Schwertmann U, Taylor RM (1989) Iron oxides. In: Dixon JB,
18. Farmer VC (1998) Differing effects of particle size and shape in the Weed SB (eds) Minerals in soil environments, 2nd edn. Soil
infrared and Raman spectra of kaolinite. Clay Miner 33:601–604 Science Society of America, Madison, pp 379–438
19. Huang G, Guo H, Zhao J, Liu Y, Xing B (2016) Effect of co-exist- 41. Schwertmann U, Cornell RM (1991) Iron oxides in the labora-
ing kaolinite and goethite on the aggregation of graphene tory. VCH, Weinheim, p 137
oxide in the aquatic environment. Water Res 102:313–320 42. Schwertmann U, Fitzpatrick RW (1992) Iron minerals in surface
20. Hoch AR, Linklater CM, Noy DJ, Rodwell WR (2004) Modelling environments. In: Skinner HCW, Fitzpatrick RW (eds) Biomin-
the interaction of hyperalkaline fluids with simplified rock eralization processes of iron and manganese: modern and
mineral assemblages. Appl Geochem 19:1431–1451 ancient environments, vol 21. Catena Supplement. Catena
21. Huertas FJ, Chou L, Wollast R (1999) Mechanism of kaolinite Verlag, Reiskirchen, pp 1–6
dissolution at room temperature and pressure part II: kinetic 43. Táborosi A, Kurdi R, Szilágyi RK (2014) The positions of inner
study. Geochim Cosmochim Acta 63:3261–3275 hydroxide groups and aluminium ions in exfoliated kaolinite
22. Iler RK (1955) The colloid chemistry of silica and silicates, 1st as indicators for external chemical environment. Phys Chem
edn. Cornell University Press, Ithaca, p 324 Chem Phys 16:25830–25839
23. Knauss KG, Wolery TJ (1988) The dissolution kinetics of quartz 44. Van Bennekom AJ, Buma AGJ, Nolting RF (1991) Dissolved
as a function of pH and time at 70 °C. Geochim Cosmochim aluminum in the Weddell–Scotia confluence and effect of
Acta 52(1):43–53 Al on the dissolution kinetics of biogenic silica. Mar Chem
24. Krol M, Mozgawa W, Jastrzebski W, Barczyk K (2012) Application 35:423–434
of IR spectra in the studies of zeolites from D4R and D6R struc- 45. Van Cappellen P, Qiu LQ (1997) Biogenic silica dissolution in
tural groups. Microporous Mesoporous Mater 156:181–188 sediments of the Southern Ocean. 1. Solubility. Deep Sea Res
25. Labrid J, Duquerroix JP (1991) Thermodynamic and kinetic II 44:1109–1128
aspects of the dissolution of quartz–kaolinite mixtures by alka- 46. Van Cappellen P, Qiu LQ (1997) Biogenic silica dissolution in
lis. Revue de L’Institut Francais du Pétrole 46:41–59 sediments of the Southern Ocean. 2. Kinetics. Deep Sea Res II
26. Lasaga AC, Luttge A (2001) Variation of crystal dissolution rate 44:1129–1149
based on a dissolution stepwave model. Science 291:2400–2404 47. Van Ranst E, Padmanabhan E, Vandenberghe RE, De Grave E,
27. Li H, Feng Q, Ou L, Long S, Cui M, Weng X (2013) Study on wash- Mees F (2016) Yellowing of a red south African Kandiudult
ability of microcrystal graphite using float–sink tests. Int J Min studied by means of Mössbauer spectroscopy. Soil Sci 181:2
Sci Technol 23(6):855–861 48. Wang H, Feng Q, Liu K (2016) The dissolution behavior and
28. Liu Y, Naidu R (2014) Hidden values in bauxite residue (red mechanism of kaolinite in alkali–acid leaching process. Appl
mud): recovery of metals. Waste Manag 34(12):2662–2673 Clay Sci 132–133:273–280
29. Liu Q, Li X, Cheng H (2016) Insight into the self-adaptive 49. White AF, Bullen TD, Schulz M, Blum AE, Huntington TG, Peters
deformation of kaolinite layers into nanoscrolls. Appl Clay Sci NE (2001) Differential rates of feldspar weathering in granitic
124–125:175–182 regoliths. Geochim Cosmochim Acta 65:847–869
30. Madejova J, Komadel P (2001) Baseline studies of the clay min- 50. Yang L, Steefel CI (2008) Kaolinite dissolution and precipita-
erals society source clays: infrared method. Clays Clay Miner tion kinetics at 22  °C and pH 4. Geochim Cosmochim Acta
49:410–432 72(1):99–116
31. Murad E (2010) Mössbauer spectroscopy of clays, soils and 51. Zhang M, Xu N, Peng Y (2015) The entrainment of kaolinite par-
their mineral constituents. Clay Miner 45:413–430 ticles in copper and gold flotation using fresh water and sea
32. Padmanabhan E, Mermut AR (1996) Sub-microscopic structure water. Powder Technol 286:431–437
of Fe-coatings on quartz grains in tropical environments. Clays 52. Zhu X, Zhu Z, Lei X, Yan C (2016) Defects in structure as the
Clay Miner 44(6):801–810 sources of the surface charges of kaolinite. Appl Clay Sci
33. Padmanabhan E, Kessler F (2008) Fabric variability within 124–125:127–136
layered Fe-oxide deposits in Mid-Late Miocene sedimentary 53. Zsirka B, Horváth E, Makó É, Kurdi R, Kristóf J (2015) Preparation
formations, NW Borneo: impact on facies architectural inter- and characterization of kaolinite nanostructures: reaction path-
pretations. Bull Geol Soc Malays 54(1):165–169 ways, morphology and structural order. Clay Miner 50:329–340
34. Prost R, Dameme A, Huard E, Driard J, Leydecker JP (1989) 54. Zsirka B, Horváth E, Jarvas Z, Dallos A, Makó É, Kristóf J (2016)
Infrared study of structural OH in kaolinite, dickite, nacrite, Structural and energetical characterization of exfoliated kaolin-
and poorly crystalline kaolinite at 5 to 600 K. Clays Clay Miner ite surfaces. Appl Clay Sci 124–125:54–61
37(5):464–468
35. Rimstidt JD (2015) Rate equations for sodium catalyzed quartz Publisher’s Note Springer Nature remains neutral with regard to
dissolution. Geochim Cosmochim Acta 167:195–204 jurisdictional claims in published maps and institutional affiliations.
36. Samal S, Ray AK, Bandopadhyay A (2013) Proposal for
resources, utilization and processes of red mud in India—a
review. Int J Miner Process 118:43–55
37. Sasaki B (1962) The corrosive action of aqueous solutions of
several electrolytes on the silicic solid surfaces. Bull Chem Res
Inst Non-Aqueous Solut Tohoku Univ 2:113–129

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