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Morphological features of quartz dissolved in Humic acid

Article · January 2019

DOI: 10.5455/sf.18584

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Abdullah Musa Ali Mohammad Yerima Kwaya

Bayero University, Kano Bayero University, Kano
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 SCIENCE FORUM (JOURNAL OF PURE AND APPLIED SCIENCES) 16 (2019) 10 – 17

http://dx.doi.org/10.5455/sf.18584

Science Forum (Journal of Pure and Applied Sciences)

j o u r n a l h o m e p a g e : w w w. a t b u s c i e n c e f o r u m . c o m

Morphological features of quartz dissolved in humic acid

Abdullah Musa Ali*, Mohammed Yerima Kwaya
Department of Geology, Bayero University, Kano, Nigeria

ABSTRACT ARTICLE INFO

Quartz dissolution plays a significant role in controlling the concentration of silica in Article history:
hydrothermal systems, thus providing controls on natural waters and artificial systems. Received 23 November 2018
However, the kinetics of quartz dissolution, particularly in humic acid, is yet to be clearly Received in revised form
elucidated because of the varying explanations proffered in different studies. Therefore, 03 January 2019
this study reviews the empirical quartz dissolution models to present a unified approach. Accepted 03 January 2019
Published 11 January 2019
In addition, quartz grains were dissolved in humic acid and then characterized using scan-
Available online 09 January 2019
ning electron microscopy and Fourier transform infrared. The review postulates that dis-
solution mechanism of the quartz in acidic solutions involves the reaction of the metal KEYWORDS
atoms with water to form solvated cations, and subsequent reaction of the silicate groups
Quartz dissolution
with H+ to form hydrated anions. Thus, quartz surface is intensely etched after dissolution Surface morphological features
to form varying degrees of deep etch pits and flat overlapping crystal faces. Fibrous, wiry, Etch pits
and platelet structures of the humic acid molecules accumulate in the etch pits created on Flat overlapping crystal faces
the quartz surface by dissolution. Therefore, in addition to mineral dissolution, humic acid
serves as organic binders in siliciclastics. This study posits that quartz dissolution in humic
acid creates surface defects such as etch pits and adsorption of humic acid molecules onto
the quartz surface via hydrogen-bond interaction.

1. Introduction due to the intense conditions generated in engineered

systems, such as nuclear waste facilities and oil fields
Quartz (SiO2) is a common silicate mineral in earth’s
(Bickmore et al., 2008) and on elevated sorption
crust and the most prevalent after feldspar (Nesbitt
capacity (adsorption and co-precipitation) due to
and Young, 1984). Therefore, quartz is a key determi-
the formation and precipitation of secondary miner-
nant in geochemical processes, such as the formation
als; mineral dissolution can alter pore structure and
of mineralized economic deposits. Notably, quartz dis-
flow behavior through the matrix in siliciclastics, thus
solution and crystallization control silica concentra-
creating more complex interactions between reaction
tion in water and hydrothermal systems (Iler, 1979).
and transport processes in the subsurface.
On the other hand, numerous interactions between
However, the kinetics of quartz dissolution is yet to
minerals and organic substances occur on the earth’s
be clearly elucidated because of the varying explana-
surface, which play a significant role in the geochem-
tions proffered in different studies (Rimstidt, 2015).
ical cycle of materials including environmental issues
In order to elucidate quartz dissolution behavior, we
such as water pollution, soil contamination, and land
must simplify the interactions that occur in the nat-
degradation. Moreover, there is a growing demand
ural systems and investigate mechanism of these
for information on compositionally complex solutions

* 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
interactions. This study conducted experiments on
quartz and humic acid as representative inorganic and
organic phases present in the natural aquatic environ-
ment. The purpose of this article is twofold: (1) to con-
cisely review the reported mechanisms of quartz dis-
solution in acids and (2) morphologically characterize
the features of quartz grains dissolved in humic acid.
1.1. Mechanism of quartz dissolution in acidic solutions
Quartz dissolution in acid results in either partial or
complete disruption of the silicate structure. Generally,
the dissolution reactions are supposed to be dependent
on the phenomena occurring at the interface between
the quartz and dissolving solvent (acid). The main dis-
solution models used to interpret the kinetic data for
the dissolution of quartz and other minerals include:
(i) the adsorption model (Warren and Devuyst, 1973),
(ii) the surface complexation model (Furrer and
Stumm, 1986; Wieland et al., 1988), (iii) the precursor
version of the surface complexation model (Oelkers et
al., 1994), and (iv) Crundwell’s theory that envisages
the removal of material from the surface to form ions
in solution leaving behind a charged surface vacancy
(Crundwell, 2014). The adsorption model (Warren
and Devuyst, 1973) and surface complexation mod-
els (Furrer and Stumm, 1988; Oelkers et al., 1994)
are related in the sense that these models all predict
the formation of surface species that subsequently
depart from the surface. These models differ from the
ion-transfer mechanism as they do not view the solid
as dissociating into its constituent ions prior to part-
ing from the surface.
In the adsorption model, the dissolution reactions
are assumed to be dependent on the phenomena
occurring at the interface, rather than on the diffu-
sion of material through the alteration layer. The
surface complexation models measure and correlate
dissolution rates as a function of pH, ionic strength,
and temperature; however, this approach provides
no information about the molecular processes at the
mineral surface. Crundwell’s model of dissolution
reaction (Crundwell, 2014) reports that bridging
bonds between the Si (siloxane (Si-O-Si) and silanol
[(Si-O−, Si-OH), Si-quartz] are broken by reaction with
protons (H+), which implies that the silicon tetrahe-
dral with four oxygen atoms are cleaved from the sur-
face by breaking bonds with other Si atoms. In addi-
tion, Rimstidt (2015) examined the data compiled
from the literature by Dove (1994) and Bickmore
et al. (2008) for 285 dissolution experiments in acid
and alkaline solutions between pH values of 1 and 12
and at temperatures ranging from 25°C to 300°C. He
11
correlated these data using the empirical regression
given by Eq. 1 below:
 74800 
r = 0.646 exp  −  + 11200 [Na + ] 0.33 [OH− ]0.44

 RT 
 74800 
r = exp  − 
 (1)
 RT 
One of the highlights of the proposed empirical
regression of the data by Rimstidt is that the dissolution
reaction in the acidic region is dependent only on the
temperature (first term of the right-hand side of Eq. 1).
However, each of these models has significant lim-
itations. The adsorption model is unable to accurately
predict the orders of reaction unless isotherms with
randomly modifiable parameters are employed. The
surface complexation model theorizes that the rate
of dissolution is proportional to the concentration of
a species on the surface; the presence of which is not
proved. Rimstidt (2015) suggested the combination of
these models into a “unified” theory to resolve their
respective limitations. To provide a deeper insight,
Crundwell (2017) posits that dissolution occurs by the
separate, parallel, removal of oxygen and silicon units,
both of which are dependent on the potential differ-
ence across the Stern layer (interface between the
solute and quartz). The removal of these units creates
surface vacancies. The mechanism that is proposed
for the dissolution of quartz in acidic solutions in this
model is shown in Figure 1. The silicon–oxygen bonds
are broken to form anions as either HSiO43− or HSiO3−,
and cations as either Si4+ or SiO2+ in separate parallel
reactions. The H+ ion attacks the SiO44− or SiO32− sites
to form a potential dependent activated complex in
the Helmholtz layer. In a parallel “partial” reaction, Si4+
or SiO2+ sites form an activated complex with water
molecules in solution. Once these activated complexes
break down into products, they subsequently react
with species at the outer Helmholtz plane to form the
final products in solution. The rate of dissolution in
acidic solutions is the same as that presented for the
dissolution of forsterite, and is given by Eq. 2:
r = kH [H+ ]X t (2)
H H
The order of reaction for this rate expression is
xHtH, and the value of which is calculated as follows.
The value of tH is one because only one H+ ion is envis-
aged as forming an activated complex with the SiO44−
and SiO32− sites. The value of xH is one half, because
the value of both transfer coefficients is close to 0.5.
Consequently, the calculated order of reaction, xHtH,
is 0.5, in agreement with the experimental values. In
12 A. M. Ali et al. / Science Forum (Journal of Pure and Applied Sciences) 16 (2019) 10 – 17
Figure 1. Proposed mechanism of quartz dissolution in acidic solution [After
Crundwell (2014)].
summary, the dissolution mechanism appears to be a
good description of the rate-determining processes in
dissolution of the quartz.
Thus, the mechanism of dissolution of quartz in
acidic solutions is summarized as follows: (i) the reac-
tion of surface silicate tetrahedra with H+ ions across
the Helmholtz layer; (ii) the reaction of discrete sur-
face silicon atoms with H2O across the Helmholtz
layer; and (iii) the reaction of products of the pre-
ceding two steps with species in solution to form the
final product. The bond-breaking may also preferen-
tially produce hydrated HSiO3− and SiO2+ entities in
steps (i) and (ii), instead of the hydrated SiO44− and
Si4+ entities. Nevertheless, the dissolved surface mor-
phological features of quartz are rarely characterized
in these proposed dissolution mechanisms. Thus, this
paper emphasizes on detailing the resultant features
of quartz dissolved in humic acid.
1.2. Quartz dissolution in organic (humic) acid
Organic electrolytes are frequently found in natu-
ral waters and are a vital component of many rock–
water interactions. However, the influence of organic
electrolytes on silica mobility, quartz solubility, and
quartz dissolution kinetics remains to be fully elu-
cidated. Bennett (1991) investigated the kinetics of
quartz dissolution in dilute aqueous organic-acid
solutions between 25°C and 70°C to determine the
influence of both organic and inorganic electrolytes.
The results of the study showed that multi-functional
organic acids such as citrate and oxalate accelerate
quartz dissolution by decreasing the activation energy
by approximately 20%, followed by a 100% increase
in apparent quartz solubility at 25°C. The resulting
model developed by the study suggested that dissolved
organic compounds in natural waters at near-neutral
pH and low temperatures can accelerate the dissolu-
tion of quartz and increasing its solubility.
Vermeer et al. (1998) studied the adsorption of
humic acid to mineral particles in relation to the polye-
lectrolyte behavior of the humic acid. At high pH and low
salt concentration, the adsorption was found to be low
and the humic acid molecules were adsorbed relatively
flat on the mineral surface, while at low pH and high salt
concentration, a substantial fraction of the adsorbed
humic acid was not directly connected to the surface,
resulting in a moderately high adsorbed amount. Based
on adsorption experiments and self-consistent field
(SCF) calculations, the results of the study indicated that
a well-developed layer is a result of the adsorption and
that lateral interactions within this layer determined to
a large extent the adsorption process.
2. Characterization of Quartz Dissolution in Humic
Acid
2.1. Experiment
2.1.1. Materials and methods
The quartz grains used were cleaned following the
procedure reported by Ali et al. (2018). The prelimi-
nary preparation of the quartz crystals involved crush-
ing in a mortar to increase the exposed surface area.
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
>50 µm mesh sized grains. Next, approximately 20 g
of the quartz grains were subjected to an ultrasonifier
in 0.1 mols L−1 HCl to eliminate the carbonate miner-
als and chelated iron oxide materials. Afterward, the
ultrasonified samples were immersed in 35% H2O2
to detach organic fragments. The quartz grains were
washed in de-ionized water and then dried in an oven
set at 60°C for 24 hours. Separate grains varied from
200 to 400 µm in size. This pre-treatment process
dissolved sharp edges and removed secondary-phase
materials adhering clay particles, heavy minerals,
organics, and surface artefacts that might cause errors
in the dissolution rate measurements. The final sam-
ples comprised subhedral to subround grains with
surface defects that included conchoidal fractures and
cleavage planes (Fig. 2).
2.1.2. Quartz dissolution in humic acid
Fifty milliliter of humic acid was dissolved in 0.1 M KCl
and regulated to pH 11 using 0.1 M KOH. The sample
was agitated in a shaker for 1 hour, while testing the
pH intermittently. The quartz grains were then added
to the humate suspension; an appropriate amount of
humate stock was slowly added. The humic acid sus-
pensions were acidified to ≈ pH 6 with 0.1 M HCl. The
samples were agitated for 18 hours at 25°C in a shaker;
then, the pH was adjusted as needed. Deionized water
was used to prepare all solutions. All reagents were
analytical grade and were used without further treat-
ment. The pH of solution was monitored in all titration
and ageing experiments using a pH meter (EUTECH,
Model: Cyberscan). The batch system was used for
the dissolution experiments, which involved the use
of sealed 50 mL polyethylene bottles. Five gram of
Figure 2. FESEM image of a clean subhedral quartz grain with conchoidal fractures and smoothed edges.
13
the quartz grains was dissolved at ambient labora-
tory temperatures (25°C ± 2°C) in bottles containing
aqueous solutions of 0.05 mol L−1 HCl maintained at
pH 1 with a speed of 40 rpm to ensure the solution was
always in contact with the quartz surface.
2.1.3. Sample characterization
Morphological characterization of the samples was
performed using scanning electron microscopy (SEM:
Carl Zeiss Supra). Energy-dispersive X-ray (EDX) was
performed to determine the composition of the dis-
solved quartz surface. Fourier transform infra-red
(FTIR) analysis was utilized to examine the adsorp-
tion of humic compounds on the quartz surface. FT-IR
spectra were recorded at room temperature using a
Shimadzu FTIR 8400S, which was linked to a desk-
top computer loaded with the Shimadzu lab solutions
infrared (IR) software to process the recorded spectra.
This method is based on the interaction between IR
electromagnetic radiation and the vibrational motion
of atomic clusters.
2.2. Results and discussion
2.2.1. Surface characterization of quartz dissolved in
humic acid
Based on silicamolybdate spectrophotometry measure-
ments, a mean concentration of 0.8 mg/l of SiO2 was dis-
solved every hour under the experimental conditions.
This confirms the dissolution of quartz. The SEM micro-
graphs show the quartz surface is intensely etched after
dissolution (Fig. 3A and B), albeit at varying degrees.
Etch pit development is elucidated in earlier research
on defect distribution and dissolution morphologies on
low-index surfaces of α-quartz (Ali et al., 2017; Yanina
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
the asymmetry of growth and dissolution on the differ-
ent faces of quartz. The variations in the quartz surface
texture were attributed to differences in the densities of
pre-existing steps on the initial crystal surface or dislo-
cation points. The smooth surface of quartz surface in
some areas suggests the dissolution of ledges of plas-
tered amorphous quartz and “cleaving off” adhering
silicate particles. The edges and interfaces of adjacent
quartz grains promote dissolution, whereas, a smooth
boundary and middle of the crystal would be thermody-
namically more stable, which accounts for the relatively
higher etching at the edges. The kinked face of the deep
etch pits (Fig. 3D) exhibited the highest steep retreat,
while the flat overlapping face (Fig. 3C) denotes small
and intermediate retreat. The sloping sides of the etch
pits merge with pointed adjacent edges and bottoms,
which indicates the etch pits originate from dislocation
defects in the mineral surface. These resultant dissolu-
tion features can be used to characterize the effects of
dissolution on quartz-rich systems such as hot dry rocks
(HDR). This study provides empirical evidence on the
Figure 3. (A) Etched quartz grains, (B) close view of intensely dissolved grain quartz, (C) flat overlapping
face, and (D) deep etch pits.
interaction of electrolytes (H+) with quartz in an array of
geological implications that reflect natural environments
such as oxidized vapour dominated geothermal systems,
acid crater lakes, and acid mine drainage settings.
2.2.2. Adsorption of humic compounds on quartz
surface
Concomitant with the quartz dissolution is the adsorp-
tion of humic acid onto the quartz surface via hydro-
gen-bond interaction. Figure 4 shows the flakes of
amorphous material, possibly humic material, adher-
ing to the quartz surface. Figure 5 depicts the fibrous
and wiry structures of the humic acid molecules accu-
mulating in the etch and dissolution pits of the quartz
surface. Also observed are platelets of the humic
material plastered on the quartz surface. Therefore,
in addition to mineral dissolution, humic acid serves
as organic binders in siliciclastics. The bonded aggre-
gates acting as bridging and infill materials (Fig. 5)
can be attributed to clustering of dissolved silica and
humic acid molecules via chemisorption or physisorp-
tion (Zhou et al., 2014).
 A. M. Ali et al. / Science Forum (Journal of Pure and Applied Sciences) 16 (2019) 10 – 17 15

2.2.3. EDX analysis
The EDX spectra of the dissolved quartz surface (Fig. 6)
indicate the presence of a range of elements. The Si is
derived from the quartz grains and dissolved silica, C
signifies humic compounds adsorbed on the quartz, K
and Cl denote the potassium and chlorine content of the
reagent solution used to dissolve the humic compounds,
and Fe and Al indicate the minor presence of iron and
aluminium oxides associated with humic acids.
2.2.4. FTIR analysis of quartz dissolved in humic acid
The FTIR spectra of the quartz grains dissolved in
humic acid is shown in Figure 7. The IR bands at 693
and 775 cm−1 are assigned to S–O quartz bond derived
from Si-O-Si inter tetrahedral bridging bonds in SiO2.
The peak at 606 cm−1 characterizes Si-O-Si (silox-
ane) bond of quartz. The broadband at 3,152 cm−1
is attributable to O–H stretching vibrations, validat-
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 6. EDX of humate coating on quartz.

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-
metric band at around 3,336 cm−1 is assigned H–O–H
stretching bond (hydrogen bonded molecular H2O) or
absorbed water (Graetsch 1994; Kronenberg, 1994).
The band at 2102 suggests C-H stretching bond from
humate material.
3. Conclusion
The dissolution mechanism of the quartz in acidic
solutions is based on the following simple steps: reac-
tion of the metal atoms with water to form solvated
cations; and reaction of the silicate groups with H+ to
form hydrated anions. The site of the breaking of the
bond is between the silicate group and the solid lat-
tice, and between the metal atom and the solid lattice.
The quartz surface is intensely etched after dissolu-
tion to form varying degrees of deep etch pits and flat
overlapping crystal faces. This study posits the disso-
lution of quartz in humic acid creates surface defects
such as etch pits and leads to associated adsorption of
humic acid molecules on the quartz surface via hydro-
gen-bond interaction.
References
Ali AM, Padmanabhan E, Baioumy H. Characterization of
alkali-induced quartz dissolution rates and morphol-
ogies. Arab J Sci Eng 2017; 42(6):2501–13.
Ali AM, Padmanabhan E, Baioumy H. Incorporation of silica
into the goethite structure: a microscopic and spectro-
scopic study. Acta Geochim 2018; 37(6):911–21.
Bennett PC. Quartz dissolution in organic-rich aqueous
systems. Geochimica et Cosmochimica Acta 1991;
55(7):1781–97.
Bickmore BR, Wheeler JC, Bates B, Nagy KL, Eggett DL.
Reaction pathways for quartz dissolution determined
 A. M. Ali et al. / Science Forum (Journal of Pure and Applied Sciences) 16 (2019) 10 – 17
by statisticaland graphical analysis of macroscopic
experimental data. Geochim Cosmochim Acta 2008;
72:4521−36.
Crundwell FK. The mechanism of dissolution of minerals in
acidic and alkaline solutions: Part II Application of a
new theory to silicates, aluminosilicates and quartz.
Hydrometallurgy 2014; 149:265–75.
Crundwell FK. On the mechanism of the dissolution of
quartz and silica in aqueous solutions. ACS Omega
2017; 2:1116−27.
Dove PM. The dissolution kinetics of quartz in sodium
chloride solutions at 25° to 300°C. Am J Sci 1994;
294:665−712.
Furrer G, Stumm W. The coordination chemistry of weath-
ering: I. Dissolution kinetics of δ-Al2O3 and BeO.
Geochim Cosmochim Acta 1986; 50:1847−60.
Graetsch H. Structural characteristics of opaline and
micro-crystalline silica minerals. Rev Mineral 1994;
29:209–32.
Kronenberg AK. Hydrogen speciation and chemical weaken-
ing of quartz. Rev Mineral 1994; 29:123–76.
Iler RK. The chemistry of silica: solubility, polymerization,
colloid and surface properties, and biochemistry.
Wiley Interscience, New York, NY, 1979.
Oelkers EH, Schott J, Devidal J-L. The effect of aluminium,
pH, and chemical affinity on the rates of aluminos-
ilicate dissolution rates. Geochim Cosmochim Acta
1994; 58:2011−24.
Ostapenko GT, Tarashchan AN, Mitsyuk BM. Rutile-quartz
geothermobarometer. Geochem Int 2007; 45:506–8.
View publication stats
17
Nesbitt HW, Young GM. Prediction of some weathering
trends of plutonic and volcanic rocks based on ther-
modynamicand kinetic considerations. Geochim
Cosmochim Acta 1984; 48:1523−34.
Rimstidt JD. Rate equations for sodium catalyzed quartz
dissolution. Geochim Cosmochim Acta 2015;
167:195−204.
Rodrigues A, Brito A, Janknecht P, Proençac MF, Nogueira R.
Quantification of humic acids in surface water: effects
of divalent cations, pH, and filtration. J Environ Monit
2009; 11:377–82.
Vermeer AWP, van Riemsdijk WH, Koopal LK. Adsorption of
humic acid to mineral particles. 1. Specific and electro-
static interactions. Langmuir 1998; 14(10):2810–9.
Warren IH, Devuyst E. In: Evans DIJ, Shoemaker RS (eds.).
Leaching of oxide. International Symposium on
Hydrometallurgy, Chicago, ILAIME, New York, NY, pp
229−64, 1973.
Wieland E, Wehrli B, Stumm W. The coordination chemistry
of weathering: III. A generalization in the dissolution
rates of minerals. Geochim Cosmochim Acta 1988;
52:1969−81.
Yanina SV, Rosso KM, Meakin P. Defect distribution and disso-
lution morphologies on low-index surfaces of α-quartz.
Geochim Cosmochim Acta 2006; 70:1113–27.
Zhou Y, Zhang Y, Li P, Li G, Jiang T. Comparative study on
the adsorption interactions of humic acid onto natu-
ral magnetite, hematite and quartz: effect of initial HA
concentration. Powder Technol 2014; 251:1–8.