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Manuscript_860c34503f761748013237823174220f

1 The aggregation and charging of natural clay allophane: critical

2 coagulation ionic strength in the presence of multivalent counter-ions

3
4 Maolin Li a, Motoyoshi Kobayashi b,*
a
5 Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1
6 Tennodai, Tsukuba, Ibaraki, 305-8572, Japan
b
7 Faculty of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai,
8 Tsukuba, Ibaraki, 305-8572, Japan
9
*
10 Corresponding author.
11 E-mail address: kobayashi.moto.fp@u.tsukuba.ac.jp (M. Kobayashi).
12
13 ABSTRACT:
14
15 Allophane is an amorphous aluminosilicate clay mineral which is typically found in young
16 volcanic ash soils. The aggregation-dispersion and charging behaviors of allophane may
17 affect the usability and protection of the volcanic ash soils and surrounding environment. To
18 understand the aggregation-dispersion and charging of natural allophane, dynamic and
19 electrophoretic light scattering experiments were carried out at pH 5 as a function of
20 potassium salt concentration and counter-ion (Cl-, SO42-, Fe(CN)63-, and Fe(CN)64-) valence.
21 The temporal increase of particle hydrodynamic diameters and electrophoretic mobilities
22 (EPM) were measured, and the stability ratio, critical coagulation concentration (CCC),
23 critical coagulation ionic strength (CCIS), zeta potential, and surface charge density were
24 further obtained. The experimental results of stability ratio and EPM of allophane particles
25 were affected by the counter-ion valence, and the CCCs strongly depended on the counter-ion
26 valence. The behavior was well described by the well-known empirical Schulze-Hardy rule.
27 The allophane particles showed a low surface charge density in the presence of multivalent
28 counter-ions. Thus, Derjaguin-Landau and Verwey-Overbeek (DLVO) theory with the
29 Debye-Huckel (DH) approximation was applied to consider the CCIS. The experimental
30 relationship between CCIS and surface charge density was well explained by DLVO theory
31 by taking account of particle size. We conclude that, in the presence of multivalent
32 counter-ions, the DLVO theory with DH approximation has a good applicability to the
33 aggregation-dispersion of natural clay allophane particles.
34
35
36 ARTICLE INFO:
37 Keywords:
38 Dynamic and electrophoretic light scattering
39 Stability ratio
40 Electrophoretic mobility
41 Critical coagulation concentration
42 DLVO theory

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43
44 1. Introduction
45
46 The aggregation-dispersion and charging of natural colloidal particles, such as clay
47 minerals and natural organic matters, vary in different water systems and affect many
48 properties of colloids related to soil usage and environment protection [1-6]. Allophane is one
49 of the typical colloidal clay minerals among the young volcanic ash soils. Volcanic ash soil is
50 one of the most fertile soils in the world, and the proper management of volcanic ash soil is
51 valuable to agricultural production and soil environment [7,8]. Thus, it is meaningful to
52 understand the aggregation and charging behaviors of allophane.
53 Allophane is an amorphous aluminosilicate mineral and exists as 100-500 nm sized
54 irreversible aggregates of hollow sphere-shaped nano-colloid particles in water [9]. The outer
55 diameter of single allophane particle is about 3.5-5.0 nm, while the wall of the particle is
56 around 0.7-1.0 nm thick [10-13]. There are a large number of pores with a diameter about 0.3
57 nm on the surface of the allophane particles [10]. The outer surface of the allophane particles
58 is alumina-like and the interior is silica-like [9,10]. It is reported that the SiO2/Al2O3 ratio of
59 allophane varies from 1.0 to 2.0 which depends on the place of origin [11,12,14]. Due to the
60 extremely small particle size and its structure, the specific surface area can reach 800 m2/g
61 [12]. In addition, allophane has a pH-dependent charge and can be positively charged at pH＜
62 6 [14-16]. Its specific surface area and charge density have a profound effect on its own
63 ability of adsorption [14]. Also, these specific structures and properties may affect the
64 aggregation-dispersion and charging of allophane particles.
65 A fairly complete explanation for the aggregation-dispersion of model colloidal particles is
66 given by the Derjaguin-Landau and Verwey-Overbeek (DLVO) theory [17,18]. The DLVO
67 theory states that the stability of colloidal suspension is determined by the attractive van der
68 Waals interaction and the repulsive electrical double layer interaction between the colloid
69 particles [19]. The addition of electrolyte in the colloidal suspension may reduce the
70 electrostatic interaction and the colloidal particles will aggregate. With increasing electrolyte
71 concentration, the aggregation rate accelerates and then reaches a maximum plateau after a
72 critical concentration where the electrostatic interaction disappears. To distinguish these two
73 states, the corresponding electrolyte concentration regions are divided into slow aggregation
74 region and fast aggregation region, respectively. The critical concentration value between
75 these two regions is called critical coagulation concentration (CCC) which can quantitatively
76 reflect the stability of colloidal suspension. Therefore, from the rate of aggregation, one can
77 notice whether the aggregation-dispersion of colloidal particles follows the DLVO theory
78 [20].
79 The DLVO theory has been proved that it is suitable for aggregation-dispersion based on
80 charge behaviors of many other colloidal particles in electrolyte solutions such as polystyrene
81 latex [20-23], carbon nanohorn [24], cellulose nanmaterials [25,26], colloidal hematite
82 particles [27], etc.. However, there are few studies focusing on the quantitative applicability
83 of DLVO theory to natural clay minerals. Recently, Takeshita et al. [9] showed that the
84 DLVO theory works for the prediction of CCC of natural clay allophane in the presence of
85 different monovalent counter-ions. Nevertheless, the validity of DLVO theory for allophane
86 in the presence of multivalent counter-ions is still lacking.

2
 87 In addition, the DLVO theory has quantitatively explained an empirical Schulze-Hardy rule
88 which states that the aggregation ability of an electrolyte to a colloidal suspension is
89 determined by the counter-ion valence [28-31]. That is, the CCC is inversely proportional to
90 sixth power of the counter-ion valance. The theoretical explanation of Schulze-Hardy rule by
91 the DLVO theory is based on the assumptions that symmetric z:z electrolytes are used and
92 particles are highly charged. However, in the presence of multivalent ions, symmetric
93 electrolytes are almost insoluble. Most of the electrolytes used in previous experiments are
94 asymmetric z:1 or 1:z electrolytes [28-32]. In addition, multivalent counter-ions reduce the
95 surface charge of colloidal particles by their adsorption [28-34]. When the surface potential is
96 quite low, the Debye-Huckel (DH) approximation describing the electrical double layer
97 interaction is available [29,30,33,34]. Within the DH approximation, ionic strength is a
98 valuable parameter which can be obtained from the composition of ions. It is useful to
99 consider the critical coagulation ionic strength (CCIS) instead of CCC. That is because the
100 CCIS strongly depends on the particle surface charge density or diffuse layer potential but it
101 is independent of the counter-ion valence [29]. Trefalt et al. [29] focused on the colloidal
102 stability of sliver-iodide particles and several polystyrene latex particles in the presence of
103 multivalent counter-ions and found that DLVO theory with DH approximation and surface
104 charge quantitatively describes CCIS of the particles. However, it is still unknown whether
105 the DLVO theory with DH approximation and charge density is quantitatively applicable for
106 the CCIS and the stability of natural allophane particles in the presence of multivalent
107 counter-ions.
108 In this context, the present study has focused on the effect of multivalent counter-ions on
109 the aggregation and charging behaviors of natural allophane particles. We have aimed to test
110 the applicability of DLVO theory to the natural allophane in the presence of multivalent
111 counter-ions. For this aim, dynamic and electrophoretic light scattering experiments were
112 carried out at pH 5 for allophane suspension to obtain the effect of multivalent counter-ions
113 on the aggregation and charging of allophane particles. Further, the relationship between
114 CCIS and surface charge density was investigated to confirm the applicability of DLVO
115 theory within DH approximation to the aggregation-dispersion of allophane. Our work can
116 give further insight into the stability of natural colloidal particles like other clay minerals or
117 humic substances in the presence of multivalent counter-ions.
118
119 2. Materials and method
120
121 We measured the temporal increase in particle hydrodynamic diameters and electrophoretic
122 mobilities (EPMs) as a function of potassium salt concentration and counter-ion valence by
123 dynamic and electrophoretic light scattering methods. From the experiments, we obtained the
124 stability ratio, CCC, CCIS, zeta potential, and surface charge density. All the experiments
125 were carried out at pH 5 and 20 ℃.
126
127 2.1 Materials
128
129 The allophane used in this research was from the collected soil of the pumice layer in the
130 Kitakami area of Iwate, Japan. The SiO2/Al2O3 ratio of this allophane sample used in the

3
131 present research is 1.19 [9,11]. Separation and purification of allophane were carried out
132 using the collected soil [9,10,35]. First, we removed the imogolite film covered the soil
133 surface carefully and washed the surface. The washed sample was immersed into 6% H2O2
134 solution and placed in a drying oven at 110 ℃ for one hour to decompose the organic matter.
135 After the heating, the granular sample was ground into a slurry and passed through a 0.42 mm
136 sieve. Then the sample was re-immersed into 6% H2O2 solution and heated to decompose
137 organic matter until no more small bubbles were produced. Then, the pH of the sample was
138 adjusted to 8.5~9.0 with NaOH and the sample was dispersed by ultrasonication. We
139 collected the upper part of suspension containing particles with the Stokes diameter less than
140 0.2 μm. Here, we assumed that the density of allophane is 2.65 g/cm3 [10]. Then we added
141 NaCl to aggregate and settle the allophane. We removed the supernatant, concentrated the
142 sample, and desalted the sample by dialysis until the conductivity of the equilibrium solution
143 became less than 2.0 μS/cm. Then, we concentrated the desalted allophane sample under
144 reduced pressure by using a vacuum pump (FDU-1200). Finally, we identified the allophane
145 sample by the transmission electron microscope (Supplementary Information), and prepared
146 the allophane suspension.
147 Potassium salts with different multivalent anions, KCl, K2SO4, K3[Fe(CN)6] and
148 K4[Fe(CN)6] · 3H2O (Wako Pure Chemical Industries, Ltd) were used to prepare the
149 electrolyte solutions. All the reagents were JIS special grade. We dissolved and diluted these
150 electrolytes with deionized water (Elix Advantage 5, Millipore) to obtain different
151 concentrations of electrolyte solutions. During the preparation, we also used the 0.2 µm
152 disposable membrane filter unit (DISMIC-25HP, ADVANTEC) to filter the solution.
153 During the preparation process, we added a small amount of 0.1 mol/L HCl solution to
154 adjust the pH of the suspension to 5, where the allophane shows a positive charge [36]. The
155 suspension pH was 5. 34 ±0.19 which measured by a compact pH meter (B-212, HORIBA).
156
157 2.2 Dynamic lighting scattering
158
159 Dynamic light scattering (DLS) has been used as a method of measuring the average
160 hydrodynamic diameter dh of particles, which can help us to understand the aggregation of
161 colloidal particles [9,14,21,22,27,37-39]. The experiments were carried out with 6 mg/L
162 allophane samples at pH 5 using the Zetasizer NANO (Malvern). The allophane samples were
163 prepared by mixing appropriate amount of allophane suspension, deionized water, and
164 electrolyte solutions with different concentrations. At each salt concentration, 200 sets of data
165 were continuously monitored or we stopped recording when the dh reached over 1000 nm.
166 The measurement interval was 20 seconds and the z-average size was recorded as the
167 hydrodynamic diameter. Then, we repeated the above steps by replacing the concentration
168 and type of electrolyte solution. We performed the experiment in duplicate and averaged the
169 results for the analysis.
170 From the experiments, the change in the hydrodynamic diameter of the particles with time
171 (ddh/dt) representing the aggregation rate can be observed. Due to the certain complexity and
172 uncertainty in the later stages of aggregation, the initial aggregation rate (k=(ddh/dt)0) which
173 corresponds to the early stages of aggregation was observed. To better examine the
174 aggregation rate, we introduce the stability ratio (W) [39,40]:

4
 /
/
(1)

175 where kf is the average of initial aggregation rates in the fast aggregation region in which the
176 rate is independent of salt concentration. In this research, kf is the average value of ddh/dt
177 obtained for KCl above 0.1 M. By observing the change of stability ratio with salt
178 concentration, we can distinguish clear slow and fast aggregation regions. Critical coagulation
179 concentration (CCC) could be obtained by the empirical formula for the stability ratio:
1 1
(2)
1

180 where Cs is the salt concentration, β is the slope dlog(1/W)/dlog(CS) in the slow aggregation
181 region [40]. From the CCC, the critical coagulation ionic strength (CCIS) could be calculated
182 by:
1 (3)
2

183 where zi is the valence of i-th ion and Ci is the concentration of i-th ion.
184
185 2.3 Electrophoretic mobility
186
187 Electrophoretic light scattering has been used to study the charging behaviors of colloidal
188 particles by measuring the electrophoretic mobility (EPM) of particles
189 [9,21,22,27,37,38,41,42]. The experiments were carried out with 6 mg/L allophane samples at
190 pH 5 using the Zetasizer NANO (Malvern). The allophane samples were prepared by mixing
191 appropriate amount of allophane suspension, deionized water and electrolyte solutions with
192 different concentrations. For each salt concentration, the EPM was recorded 3 times and
193 returned an average value by the Zetasizer. We repeated the above steps by replacing the
194 concentration and type of electrolyte solution. Then we performed the experiment in duplicate
195 and averaged the results for the analysis. From the measured EPM (μ), the zeta potential (ζ)
196 and surface charge density (σ) could be further obtained.
197 It is worth mentioning that, in general, the zeta potential and surface charge density are
198 calculated form EPM without considering the effect of particle size for moderate zeta
199 potential and
≫1 (4)
200 where a is the particle radius and κ is the reciprocal of Debye length given by:

" "# $%
!
(5)
2&

201 where q is the elementary charge (q = 1.6×10-19 C), kB is the Boltzmann constant, T is the
202 absolute temperature, ε0 is the permittivity of free space, εr is the relative dielectric constant of
203 the dispersion medium.
204 However, in this research, the values of κa are among 0.86~15.66. Thus, it is better to
205 consider the effect of particle size, where the Henry-Ohshima equation for the calculation of
206 zeta potential is available [41]:

5
 2" "# ( 1
' *1 4
3) 2 1 2.5/, -1 2. /0 12 3
(6)

207 where η is dynamic viscosity of the dispersion medium. Further, the surface charge density is
208 estimated by [34]:
1
5 " "# 61 7( (7)

209
210 3. Results and discussion
211
212 3.1 The electrophoretic mobility of allophane in the presence of multivalent counter-ions
213
214 The electrophoretic mobility (EPM) of allophane is plotted in Fig. 1 as a function of salt
215 concentration. Different symbols represent potassium salts with different multivalent
216 counter-ions. At the lowest salt concentrations, the EPM shows a positive value which
217 indicates the allophane particle has a positive charge. With increasing salt concentration, the
218 EPM has a decreasing tendency due to the compression of diffuse electric double layer and
219 the adsorption of counter-ions. The tendencies of EPM curves are different for the case with
220 different counter-ions indicating the EPM results are affected by the counter-ion valence. One
221 phenomenon is very interesting that the EPM increases slightly at early KCl concentration
222 and a mobility maximum shows up, which due to the relaxation effect [19].
223 In the presence of di-, tri- and tetravalent counter-ions, Fig. 1 demonstrates that allophane
224 particles undergo a charge neutralization at the isoelectric point (IEP) and then a charge
225 reversal at high salt concentration. Thus, a new electric double layer, where the monovalent
226 K+ ion represents the counter-ion, is formed. With higher counter-ion valence, the charge
227 neutralization occurs at lower IEP concentrations and the charge reversal is pronounced.
228 These trends can be explained by the larger screening effect of high valence ions and the
229 larger adsorption capability of high valence counter-ion to the allophane surface [26,44].
230 Meanwhile, at much higher concentration of electrolytes with tri- and tetravalent counter-ions,
231 the magnitude of negative EPM passes through a maximum and decreases again because of
232 the screening effect of K+ which now represents the counter-ion [44]. Within the DLVO
233 theory, the charge behaviors strongly affect the aggregation of colloidal particles. Therefore,
234 the EPM results are used for the discussion of the results of stability ratio in the section 3.2.
235
236 3.2 The stability ratio of allophane in the presence of multivalent counter-ions
237
238 A typical result of increase in hydrodynamic diameter dh of allophane with different KCl
239 concentrations is given in Fig. 2. At the beginning of the measurement, the hydrodynamic
240 diameter of allophane is 150~200 nm which indicates the presence of irreversible allophane
241 aggregates in the suspension. The hydrodynamic diameter of the particles increases over time.
242 Further, the initial aggregation rate (k=ddh/dt) of the particles also shows an increasing
243 tendency with the increasing electrolyte concentration until a certain maximum value (kf).
244 To further study the aggregation process of allophane, the stability ratio W of allophane
245 against salt concentration is plotted in Fig. 3. Different symbols represent potassium salts with
246 different multivalent counter-ions.

6
247 In the presence of mono-, di- and trivalent counter-ions, the stability ratios curves reduce
248 first and reach to unity with the increasing salt concentration, the suspension changes from
249 unstable to stable. There are clear slow and fast aggregation regions divided by the critical
250 coagulation concentration (CCC). With increasing salt concentration, the stability ratio of
251 allophane decreases first in the slow aggregation region. In this slow region, the electric
252 double layer repulsion induced by the particle electric double layer is reduced and the
253 particles start to aggregate slowly and thus the stability ratio depends on the salt concentration.
254 Above the CCC, the stability ratio reaches unity in the fast aggregation region where the
255 double layer repulsion disappears and the van der Waals attraction dominates. In the fast
256 region, the particles aggregate fast and the stability ratio is not dependent on the salt
257 concentration. In the presence of tetravalent ions, however, three CCCs appear with
258 increasing salt concentration and there is a re-stabilization region in the intermediate
259 concentration. At the low salt concentration, the stability ratio decreases first and reaches
260 unity after the CCC (first CCC) similar to the behaviors for other counter-ions. In the
261 intermediate salt concentration, the stability ratio increases after the second CCC and the
262 aggregation rate slows again. We consider that these behaviors are due to the adsorption of
263 tetravalent counter-ions on the particle surface inducing a charge neutralization and further a
264 charge reversal. At higher salt concentration, the stability ratio decreases and again reach to
265 unity after the third CCC. This is probably due to the screening effect of K+ [44]. These
266 results are also qualitatively consistent with the DLVO theory.
267 We can also discuss the results of stability ratio in comparison to the EPM results. Although
268 there are charge neutralization and charge reversal in the case of di- and tri- valent
269 counter-ions, the new double layer interaction is not strong enough to make the suspension
270 unstable again. Therefore, the stability ratio curves are similar to the monovalent one.
271 However, in the case of tetravalent counter-ions, as we mentioned, there is a re-stabilization
272 region. That may due to the charge reversal is significant and the new double layer interaction
273 make the suspension unstable again and the screening effect of potassium ions makes the
274 suspension back to stable at higher concentration. Therefore, the stability ratio results are in
275 line with the results of EPM and both results can be explained by the DLVO theory.
276 However, there are still some results can hardly be explained by the DLVO theory. At high
277 concentration of tri- and tetravalent ions, the stability ratios became slightly lower than 1.
278 That may be due to weaker charge reversal or due to the additional non-DLVO attractive
279 forces induced by the surface charge heterogeneities [31,45,46]. Besides, while the third CCC
280 appears and then the stability ratio reduces to unity at high tetravalent counter-ion valence, the
281 EPM values still remain high levels. That may be indicating, in addition to the screening
282 effect of K+, the additional attractive forces induced by the surface charge heterogeneities
283 accelerating the aggregation. The more details of the additional non-DLVO attractive forces
284 will discussed in the section 3.3.
285 The accurate CCC values obtained from stability ratio by applying Eq. (2) are summarized
286 in Table 1. To figure out the effect of counter-ion valence on CCC, we further plot the graph
287 of relative CCC against the counter-ion valence as shown in Fig. 4. The symbols are the
288 experimental data. The yellow line is the prediction of empirical Schulze-Hardy rule which
289 assume the presence of highly charged particles and symmetric z:z electrolytes, while the blue
290 line is the theoretical line within the DH approximation for the particles with low charge

7
291 density and asymmetric z:1 or 1:z electrolytes. One point needs to be mentioned here is that
292 the discussion of first CCC is meaningful because the second and third CCCs are seen at the
293 concentration where the charge is reversed. We can notice that the value of (first) CCC is
294 strongly dependent on the counter-ions valence, which follows the empirical Schulze-Hardy
295 rule [28-30].
296 However, it may fail if we try to use DLVO theory for symmetric electrolytes for high
297 surface charge to explain the relationship between first CCC and counter-ion valence due to
298 neither assumption for the explanation of theoretical Schulze-Hardy rule has been realized. In
299 the present study, the electrolytes containing multivalent counter-ions are asymmetric while
300 the zeta potentials are quite low (＜25 mV) under all electrolyte types and concentrations. In
301 this research, we assume that the diffuse layer potential is equal to zeta potential by following
302 previous researches [9,29,31,47]. Therefore, we consider to use the CCIS instead of CCC to
303 better describe the effect of counter-ion valence on the aggregation and charging of allophane
304 particles. The detail is given in the section 3.3.
305
306 Table 1
307 CCC of different multivalent counter-ions in allophane suspension
CCC (mol/L) Cl- SO42- [Fe(CN)6]3- [Fe(CN)6]4-
first CCC 5.8×10-3 1.5×10-4 2.1×10-5 7.8×10-7
second CCC - - - 1.1×10-5
third CCC - - - 2.5×10-4
308
309 3.3 Application of DLVO theory to the relationship between CCIS and surface charge density
310
311 In general, the surface charge densities of colloidal particles are relatively low around
312 critical coagulation ionic strength (CCIS) in the presence of multivalent counter-ions. In that
313 case, the Debye-Huckel (DH) approximation of DLVO theory is available, and it is useful to
314 consider CCIS the instead of CCC. Recently, Trefalt et al. [29] have proved that the
315 experimental relationship between CCIS and surface charge density follows the prediction of
316 DLVO theory for sliver-iodide particles and several polystyrene latex particles in the presence
317 of multivalent counter-ions.
318 The DLVO theory states that the interaction energy (V) between two charged colloidal
319 particles can be expressed as:
8 89:; 8<= (8)
320 where VvdW is van der Waals interaction potential energy and VDL is electric double layer
321 interaction potential energy. The van der Waals interaction energy can be estimated by the
322 help of the Derjaguin approximation as follows [29,48-50]:
B
89:; −
12ℎ
(9)

323 where H is the Hamaker constant characterizing the magnitude of van der Waals interaction
324 between particles and h is the surface separation distance. Meanwhile, according to the DH
325 approximation, the double layer interaction energy can be simply expressed as [50,51]:
8<= 2D " "# E e /G (10)
326 where ψ0 is the diffuse layer potential. Further, the surface charge density can be obtained
8
327 within DH approximation as
5 " "H E . (11)
328 CCC (or CCIS) can be estimated [49], when the interaction energy satisfies the following
329 conditions:
:M
8 0 and 0. (12)
:G

330 The obtained theoretical relationship between CCIS and surface charge density predicted by
331 DLVO theory can be given [29]:
9 1 5
CCIS 3 3
8πe T$ " "# B
(13)

332 However, this expression does not consider the effect of κa. Thus, we also try to use Eq. (7)
333 instead of Eq. (11) to examine the effect of particle size in this research, which may be an
334 improvement of the prediction.
335 In Fig. 5, the symbols show the experimental relationship between CCIS and surface
336 charge density and the lines are predicted ones by DLVO theory. The red symbols correspond
337 to the first CCIS in the presence of multivalent anions and the CCISs from the large to small
338 represent Cl-, SO42-, [Fe(CN)6]3- and [Fe(CN)6]4-, respectively. The blue symbols correspond
339 to different anions with monovalent and CCISs from the large to small represent I-, Br-, BrO3-,
340 Cl-, IO3- and F-, respectively [9]. The green and yellow symbols correspond to the second and
341 third CCIS respectively in the presence of [Fe(CN)6]4-. The solid line is the DLVO prediction
342 within the DH approximation by applying Eq. (13), while the dashed line is the prediction
343 considering the effect of κa. The Hamaker constant is assumed to be 3.5×10-20 J, which is
344 between the values of silica and alumina and is reasonable due to the composition of
345 aluminosilicate allophane [9-13].
346 As shown in Fig. 5(a), the experimental relationship between first CCIS and surface charge
347 density can be described well by the DLVO theory within DH approximation in the presence
348 of different monovalent [9] and multivalent counter-ions. This good agreement demonstrates
349 the validity of DLVO theory for describing aggregation-dispersion of natural clay allophane
350 and extends the applicability of DLVO theory.
351 However, as shown in Fig. 5(b), there is a deviation between the experimental result and
352 the predicted one in the case of second and third CCISs of tetravalent counter-ions. The
353 second and third CCISs are located below the DLVO line, implying that there are some
354 additional non-DLVO attractions between allophane particles at high tetravalent counter-ion
355 concentration. That may be due to the surface charge heterogeneities which can be a cause of
356 charge-patch attraction [46,51-53]. Ion-ion correlation effect [31] or the formation of
357 negatively charged Prussian blue (Fe4[Fe(CN)6]3) [55,56] may also induce the charge
358 heterogeneities. Another possible reason may also lead to this deviation is the errors related to
359 curvature effect, which is not considered by the Derjaguin approximation, while it is pointed
360 out that the errors due to Derjaguin approximation should be canceled [34,57]. In addition, the
361 Hamaker constant may be slightly different due to the surface roughness and retardation
362 effects. However, multiple previous studies pointed that these effects weaken the van der
363 Waals attraction and lead to a small Hamaker constant [31, 58-60]. Thus, we believe this
364 phenomenon should be ignored in this discussion. To unveil the more accurate mechanisms of
365 additional attractions, we need further research in the future.

9
366
367 4. Conclusion
368
369 To study the aggregation-dispersion and charging behaviors of natural allophane particles,
370 the dynamic and electrophoretic light scattering experiments were performed at pH 5. From
371 the experiments, stability ratio, electrophoretic mobility (EPM), critical coagulation
372 concentration (CCC), critical coagulation ionic strength (CCIS), zeta potential and surface
373 charge density were obtained.
374 The stability ratio and EPM are affected by the counter-ion valence, and both results are
375 correlated. Furthermore, the experimental relationship between CCIS and surface charge
376 density can be well described by the DLVO theory within the Debye-Huckel (DH)
377 approximation. This result demonstrates that the DLVO theory has a good applicability to the
378 aggregation-dispersion of natural clay allophane particles in the presence of multivalent
379 counter-ions, and the DH approximation with CCIS is a useful tool to prove it.
380 The current research and the previous research in our group [9] give us a better
381 understanding on the aggregation and charging behaviors of allophane particles. It should be
382 valuable as a comparison and reference to the future studies on allophane particles in the
383 presence of more complex ionic species, such as humic acids and phosphates etc., which are
384 more commonly found in the soil. Further, it will be valuable to the better management of
385 clay minerals and volcanic ash soils, and to the agriculture and soil environment.
386
387 Acknowledgements
388 This study was financially supported by JSPS KAKENHI (19H03020 and 16H06382).
389
390 Reference
391 [1] Hotze, E. M., Phenrat, T., & Lowry, G. V. (2010). Nanoparticle aggregation: challenges to
392 understanding transport and reactivity in the environment. Journal of environmental quality, 39(6),
393 1909-1924.
394 [2] Ryan, J. N., & Elimelech, M. (1996). Colloid mobilization and transport in groundwater. Colloids
395 and surfaces A: Physicochemical and engineering aspects, 107, 1-56.
396 [3] Chen, H., Koopal, L. K., Xiong, J., Avena, M., & Tan, W. (2017). Mechanisms of soil humic acid
397 adsorption onto montmorillonite and kaolinite. Journal of colloid and interface science, 504,
398 457-467.
399 [4] Abe, T., Kobayashi, S., & Kobayashi, M. (2011). Aggregation of colloidal silica particles in the
400 presence of fulvic acid, humic acid, or alginate: Effects of ionic composition. Colloids and
401 Surfaces A: Physicochemical and Engineering Aspects, 379(1-3), 21-26.
402 [5] Hakim, A., Suzuki, T., & Kobayashi, M. (2019). Strength of humic acid aggregates: effects of
403 divalent cations and solution pH. ACS omega, 4(5), 8559-8567.
404 [6] Hakim, A., & Kobayashi, M. (2019). Charging, aggregation, and aggregate strength of humic
405 substances in the presence of cationic surfactants: Effects of humic substances hydrophobicity and
406 surfactant tail length. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 577,
407 175-184.
408 [7] Shoji, S., & Takahashi, T. (2002). Environmental and agricultural significance of volcanic ash
409 soils. Global Environmental Research-English Edition-, 6(2), 113-135.

10
410 [8] Shoji, S., Nanzyo, M., & Dahlgren, R. (1993). Productivity and utilization of volcanic ash soils. In
411 Developments in Soil Science (Vol. 21, pp. 209-251). Elsevier.
412 [9] Takeshita, C., Masuda, K., & Kobayashi, M. (2019). The effect of monovalent anion species on
413 the aggregation and charging of allophane clay nanoparticles. Colloids and Surfaces A:
414 Physicochemical and Engineering Aspects, 577, 103-109.
415 [10] Wada, S. I., & Wada, K. (1977). Density and structure of allophane. Clay minerals, 12(4),
416 289-298.
417 [11] Henmi, T., & Wada, K. (1976). Morphology and composition of allophane. American
418 Mineralogist, 61(5-6), 379-390.
419 [12] Parfitt, R. L., & Henmi, T. (1980). Structure of some allophanes from New Zealand. Clays and
420 Clay Minerals, 28(4), 285-294.
421 [13] Wada, K. (1989). Allophane and imogolite. Minerals in soil environments, 1, 1051-1087.
422 [14] Adachi, Y., Koga, S., Kobayashi, M., & Inada, M. (2005). Study of colloidal stability of allophane
423 dispersion by dynamic light scattering. Colloids and Surfaces A: Physicochemical and
424 Engineering Aspects, 265(1-3), 149-154.
425 [15] Itami, K., & Fujitani, H. (2005). Charge characteristics and related dispersion/flocculation
426 behavior of soil colloids as the cause of turbidity. Colloids and Surfaces A: Physicochemical and
427 Engineering Aspects, 265(1-3), 55-63.
428 [16] Kobayashi, M., Nitanai, M., Satta, N., & Adachi, Y. (2013). Coagulation and charging of latex
429 particles in the presence of imogolite. Colloids and Surfaces A: Physicochemical and Engineering
430 Aspects, 435, 139-146.
431 [17] Deraguin, B. V., & Landau, L. (1941). Theory of the stability of strongly charged lyophobic sols
432 and of the adhesion of strongly charged particles in solution of electrolytes. Acta Physicochim:
433 USSR, 14, 633-662.
434 [18] Verwey, E. J. W., & Overbeek, J. T. G. (1948). Theory of the stability of lyophobic colloids.
435 Elsevier, Amsterdam.
436 [19] Ohshima, H. (2012). Electrical phenomena at interfaces and biointerfaces: fundamentals and
437 applications in nano-, bio-, and environmental sciences. John Wiley & Sons.
438 [20] Nishiya, M., Sugimoto, T., & Kobayashi, M. (2016). Electrophoretic mobility of carboxyl latex
439 particles in the mixed solution of 1: 1 and 2: 1 electrolytes or 1: 1 and 3: 1 electrolytes:
440 Experiments and modeling. Colloids and Surfaces A: Physicochemical and Engineering Aspects,
441 100(504), 219-227.
442 [21] Szilagyi, I., Polomska, A., Citherlet, D., Sadeghpour, A., & Borkovec, M. (2013). Charging and
443 aggregation of negatively charged colloidal latex particles in the presence of multivalent
444 oligoamine cations. Journal of colloid and interface science, 392, 34-41.
445 [22] Cao, T., Sugimoto, T., Szilagyi, I., Trefalt, G., & Borkovec, M. (2017). Heteroaggregation of
446 oppositely charged particles in the presence of multivalent ions. Physical Chemistry Chemical
447 Physics, 19(23), 15160-15171.
448 [23] Oncsik, T., Trefalt, G., Csendes, Z., Szilagyi, I., & Borkovec, M. (2014). Aggregation of
449 negatively charged colloidal particles in the presence of multivalent cations. Langmuir, 30(3),
450 733-741.
451 [24] Omija, K., Hakim, A., Masuda, K., Yamaguchi, A., Kobayashi, M. Effect of counter-ion valence
452 and pH on the aggregation and charging of oxidized carbon nanohorn (CNHox) in aqueous
453 solution. Colloids and Surfaces A: Physicochemical and Engineering Aspects, in press.

11
454 [25] Sato, Y., Kusaka, Y., & Kobayashi, M. (2017). Charging and aggregation behavior of cellulose
455 nanofibers in aqueous solution. Langmuir, 33(44), 12660-12669.
456 [26] Cao, T., & Elimelech, M. (2020). Colloidal stability of cellulose nanocrystals in aqueous solutions
457 containing monovalent, divalent, and trivalent inorganic salts. Journal of Colloid and Interface
458 Science, 584, 456-463.
459 [27] Kobayashi, M., Yuki, S., & Adachi, Y. (2016). Effect of anionic surfactants on the stability ratio
460 and electrophoretic mobility of colloidal hematite particles. Colloids and Surfaces A:
461 Physicochemical and Engineering Aspects, 510, 190-197.
462 [28] Trefalt, G. , Szilagyi, I. , & Borkovec, M. . (2020). Schulze-hardy rule revisited. Colloid and
463 Polymer Science.
464 [29] Trefalt, G., Szilagyi, I., Té llez, G., & Borkovec, M. (2017). Colloidal stability in asymmetric
465 electrolytes: modifications of the Schulze–Hardy rule. Langmuir, 33(7), 1695-1704.
466 [30] Cao, T., Szilagyi, I., Oncsik, T., Borkovec, M., & Trefalt, G. (2015). Aggregation of colloidal
467 particles in the presence of multivalent co-ions: The inverse Schulze–Hardy rule. Langmuir,
468 31(24), 6610-6614.
469 [31] Sinha, P., Szilagyi, I., Montes Ruiz-Cabello, F. J., Maroni, P., & Borkovec, M. (2013). Attractive
470 forces between charged colloidal particles induced by multivalent ions revealed by confronting
471 aggregation and direct force measurements. The journal of physical chemistry letters, 4(4),
472 648-652.
473 [32] Alkan, M., Demirbaş, Ö., & Doğan, M. (2005). Electrokinetic properties of kaolinite in mono-and
474 multivalent electrolyte solutions. Microporous and Mesoporous Materials, 83(1-3), 51-59.
475 [33] Masliyah, J. H., & Bhattacharjee, S. (2006). Electrokinetic and colloid transport phenomena. John
476 Wiley & Sons.
477 [34] Ohshima, H. (2006). Theory of colloid and interfacial electric phenomena. Elsevier.
478 [35] Karube, J., Nakaishi, K., Sugimoto, H., & Fujihira, M. (1996). Size and shape of allophane
479 particles in dispersed aqueous systems. Clays and clay minerals, 44(4), 485-491.
480 [36] Horikawa, Y. (1975). Electrokinetic phenomena of aqueous suspensions of allophane and
481 imogolite. Clay Science, 4(6), 255-263.
482 [37] Kobayashi, M., Juillerat, F., Galletto, P., Bowen, P., & Borkovec, M. (2005). Aggregation and
483 charging of colloidal silica particles: effect of particle size. Langmuir, 21(13), 5761-5769.
484 [38] Gillies, G., Lin, W., & Borkovec, M. (2007). Charging and aggregation of positively charged latex
485 particles in the presence of anionic polyelectrolytes. The Journal of Physical Chemistry B,
486 111(29), 8626-8633.
487 [39] Kretzschmar, R., Holthoff, H., & Sticher, H. (1998). Influence of pH and humic acid on
488 coagulation kinetics of kaolinite: a dynamic light scattering study. Journal of colloid and interface
489 science, 202(1), 95-103.
490 [40] Grolimund, D., Elimelech, M., & Borkovec, M. (2001). Aggregation and deposition kinetics of
491 mobile colloidal particles in natural porous media. Colloids and Surfaces A: Physicochemical and
492 Engineering Aspects, 191(1-2), 179-188.
493 [41] Su, C., & Harsh, J. B. (1993). The electrophoretic mobility of imogolite and allophane in the
494 presence of inorganic anions and citrate. Clays and Clay Minerals, 41(4), 461-471.
495 [42] Sadeghpour, A., Szilágyi, I., & Borkovec, M. (2012). Charging and aggregation of positively
496 charged colloidal latex particles in presence of multivalent polycarboxylate anions. Zeitschrift für
497 Physikalische Chemie, 226(7), 597-612.

12
498 [43] Ohshima, H. (2001). Approximate analytic expression for the electrophoretic mobility of a
499 spherical colloidal particle. Journal of colloid and interface science, 239(2), 587-590.
500 [44] Pavlovic, M., Huber, R., Adok-Sipiczki, M., Nardin, C., & Szilagyi, I. (2016). Ion specific effects
501 on the stability of layered double hydroxide colloids. Soft Matter, 12(17), 4024-4033.
502 [45] Montes Ruiz-Cabello, F. J., Trefalt, G., Maroni, P., & Borkovec, M. (2014). Accurate predictions
503 of forces in the presence of multivalent Ions by Poisson–Boltzmann theory. Langmuir, 30(16),
504 4551-4555.
505 [46] Huang, Y., Yamaguchi, A., Pham, T. D., & Kobayashi, M. (2018). Charging and aggregation
506 behavior of silica particles in the presence of lysozymes. Colloid and Polymer Science, 296(1),
507 145-155.
508 [47] Montes Ruiz-Cabello, F. J., Trefalt, G., Csendes, Z., Sinha, P., Oncsik, T., Szilagyi, I., ... &
509 Borkovec, M. (2013). Predicting aggregation rates of colloidal particles from direct force
510 measurements. The Journal of Physical Chemistry B, 117(39), 11853-11862.
511 [48] Schenkel, J. H., & Kitchener, J. A. (1960). A test of the Derjaguin-Verwey-Overbeek theory with a
512 colloidal suspension. Transactions of the Faraday Society, 56, 161-173.
513 [49] Ohshima, H., & Furusawa, K. (Eds.). (1998). Electrical phenomena at interfaces: fundamentals:
514 measurements, and applications (Vol. 76). CRC Press.
515 [50] Russel, W. B., Saville, D. A., & Schowalter, W. R. (1991). Colloidal dispersions. Cambridge
516 university press.
517 [51] Trefalt, G., Szilagyi, I., & Borkovec, M. (2013). Poisson–Boltzmann description of interaction
518 forces and aggregation rates involving charged colloidal particles in asymmetric electrolytes.
519 Journal of colloid and interface science, 406, 111-120.
520 [52] Adachi, Y., Feng, L., & Kobayashi, M. (2015). Kinetics of flocculation of polystyrene latex
521 particles in the mixing flow induced with high charge density polycation near the isoelectric point.
522 Colloids and Surfaces A: Physicochemical and Engineering Aspects, 471, 38-44.
523 [53] Szilagyi, I., Trefalt, G., Tiraferri, A., Maroni, P., & Borkovec, M. (2014). Polyelectrolyte
524 adsorption, interparticle forces, and colloidal aggregation. Soft Matter, 10(15), 2479-2502.
525 [54] Cao, T., Trefalt, G., & Borkovec, M. (2018). Aggregation of colloidal particles in the presence of
526 hydrophobic anions: Importance of attractive non-dlvo forces. Langmuir, 34(47), 14368-14377.
527 [55] Gotoh, A., Uchida, H., Ishizaki, M., Satoh, T., Kaga, S., Okamoto, S., ... & Tokumoto, M. (2007).
528 Simple synthesis of three primary colour nanoparticle inks of Prussian blue and its analogues.
529 Nanotechnology, 18(34), 345609.
530 [56] Alsharif, N. B., Samu, G. F., Sáringer, S., Muráth, S., & Szilagyi, I. (2020). A colloid approach to
531 decorate latex particles with Prussian blue nanozymes. Journal of Molecular Liquids, 113066.
532 [57] Behrens, S. H., Christl, D. I., Emmerzael, R., Schurtenberger, P., & Borkovec, M. (2000).
533 Charging and aggregation properties of carboxyl latex particles: Experiments versus DLVO theory.
534 Langmuir, 16(6), 2566-2575.
535 [58] Bevan, M. A., & Prieve, D. C. (1999). Direct measurement of retarded van der Waals
536 attraction. Langmuir, 15(23), 7925-7936.
537 [59] Trefalt, G., Behrens, S. H., & Borkovec, M. (2016). Charge regulation in the electrical double
538 layer: ion adsorption and surface interactions. Langmuir, 32(2), 380-400.
539 [60] Sugimoto, T., & Kobayashi, M. (2020). Critical coagulation ionic strengths for heteroaggregation
540 in the presence of multivalent ions. Colloids and Surfaces A: Physicochemical and Engineering
541 Aspects, 603, 125234.

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Figure 1. Electrophoretic mobility of allophane as a function of salt (KCl, K2SO4, K3[Fe(CN)6]
and K4[Fe(CN)6]) concentration.
Figure 2. Hydrodynamic diameter of allophane aggregate as a function of time with different
KCl concentration.
Figure 3. Stability ratio of allophane in the presence of potassium salts with different
multivalent anions (KCl, K2SO4, K3[Fe(CN)6] and K4[Fe(CN)6]).
Figure 4. The relative (first) critical coagulation concentration (relative first CCC) against the
counter-ion valence.
Figure 5. The critical coagulation ionic strength against surface charge density (a) in the case
of different monovalent counter-ions (I-, Br-, BrO3-, Cl-, IO3- and F-, Takeshita et al., 2019), and
first CCIS of multivalent counter-ions, (b) in the case of multivalent counter-ions including
second and third CCIS. The symbols are experimental data. The solid and dashed lines are the
DLVO predictions with and without considering the effect of κa, which with Hamaker constant
of 3.5×10-20 J for allophane in water.
GRAPHICAL ABSTRACT: