Version of Record: https://www.sciencedirect.

com/science/article/pii/S0048969716319842
Manuscript_672c93658fbed65446be0c9ec5cf8633

Effect of surfactants on the aggregation and stability of TiO2

nanomaterial in environmental aqueous matrices

Xuankun Li*, Minoru Yoneda, Yoko Shimada, Yasuto Matsui

Department of Environmental Engineering, Graduate School of Engineering, Kyoto University, Katsura,

Nishikyo-ku, 615-8540, Kyoto, Japan

HIGHLIGHTS

●To better simulate the dynamic natural water environment, the aggregation of TiO2

nanoparticles was studied not by the widely applied static experimental method, but by a

batch experiment conducted in a shaker.

●Both ionic sodium dodecyl sulfate (SDS) and non-ionic nonylphenol ethoxylate (NPEO)

surfactants can remarkably reduce the aggregation of nano-TiO2 and stabilize the aggregate

when the surfactant concentration exceeds 0.015% (w:v).

●The aggregation and sedimentation of nano-TiO2 are more remarkable in environmental

aqueous matrices than in Milli-Q water, but surfactants are effective in reducing the

aggregation and retarding the sedimentation of TiO2.

Keywords: Nano-TiO2; Surfactant; Aggregation; Sedimentation; Environmental aqueous matrices

ABSTRACT

The high likelihood of the coexistence of surfactants and engineered nano-materials (ENMs)

in aqueous environments redoubles the need to study the effects of surfactants on the

© 2016 published by Elsevier. This manuscript is made available under the Elsevier user license
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behavior and transport of nano-materials. In this study, we chose anionic sodium dodecyl

sulfate (SDS) and nonionic nonylphenol ethoxylate (NPEO, Tergitol NP-9) to study the

effect of surfactants on the behaviors of a typical TiO2 ENM in water environment. An

adsorption isotherm and zeta potential study showed that both surfactants could be

adsorbed onto the surface of nano-TiO2 but that only SDS can significantly decrease the

zeta potential of TiO2. For a better simulation of the dynamic natural water environment,

we conducted a 24-h batch experiment to study the aggregation behaviors of nano-TiO2 in

the presence of SDS or NP-9 surfactants and recorded the sedimentation of the aggregates

in solutions containing the surfactants over a 24 h-period. SDS and NP-9 both reduced the

growth of the TiO2 aggregates and retarded the aggregate sedimentation at surfactant

concentrations ≥ 0.015% (w:v). The aggregation of TiO2 was far more remarkable in six

environmental water matrices from different natural origins than in Milli-Q water, mainly

because of the relatively high ionic strength of the former. The introduction of surfactants,

however, still retarded the aggregation and sedimentation of TiO2 in the six environmental

water matrices. SDS exerted a stronger reductive effect than NP-9. This study reveals that

the presence of surfactants may increase the bioavailability and environmental risk of

nanomaterial contaminants by retarding the aggregation and promoting the transport of

nanomaterials in natural aqueous environments.

1. Introduction

With the development of nano-technology, engineered nanomaterials (ENMs) have been

applied to various industries and consumer products. However, there are concerns that the

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large-scale application of ENMs will inevitably result in the release of these ENMs and

possibly cause harmful effects on the environment (Gardea-Torresdey et al., 2014;

Rathnayake et al., 2014; Van Koetsem et al., 2015; Zhang et al., 2008). Thus, studies of the

fate and behaviors of ENMs have been attracting increasing attention in recent years. As

one of the most frequently used ENMs, the titanium dioxide nanomaterial is widely applied

in consumer products such as sunscreen, cosmetics, paints, pigments, coatings, foods, and

pharmaceuticals (Godinez and Darnault, 2011; Sygouni and Chrysikopoulos, 2015).

Because of their large specific area, photo-catalytic activity, and other physico-chemical

characteristics, TiO2 ENMs are also widely used in environmental remediation works for

the decontamination of toxic organic matter-polluted water (Henderson, 2011; Kanakaraju

et al., 2015; Li et al., 2015; Yang et al., 2008; Zhang et al., 2011). Therefore, the diverse

application of TiO2 ENMs will greatly increase the risk of their release into municipal

wastewater treatment plants and ultimately into the natural water environments (Fan et al.,

2011; Kiser et al., 2009; Majedi et al., 2014). Considering the reported toxicity of TiO2

ENMs to aquatic organisms such as Daphnia magna, cladocerans, algae, rotifers, and

plants(Clément et al., 2013; Ji et al., 2011; Metzler et al., 2011; Wiench et al., 2009), the

fate and behaviors of TiO2 ENMs in the natural aqueous matrices are necessary to be

studied.

Surfactants are widely used in industries and households and can often be detected in

wastewater in high concentration. Detergents in industrial wastewater have been reported to

have concentration ranging from a few hundred to thousands of ppm (Narkis and Ben-

David, 1985; Sun et al., 2015). The presence of surfactants in ENM suspensions can

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tremendously affect the aggregation and sedimentation of ENMs, thereby altering their

behavior and fate and ultimately their bioavailability and eco-toxicity in aqueous

environments (Keller et al., 2010; Liu et al., 2015). At pH 7.0, Triton X-100 and sodium

dodecyl benzene sulfonate (SDBS) have been found to increase steric repulsive forces and

inhibit the uncontrollable aggregation of nano-TiO2. At pH 9.0, increasing surfactant’s

concentrations led to concomitant increase in the transport distance of nano-TiO2 in a

porous medium column (Godinez and Darnault, 2011). Another study found the surfactants

SDBS and cetyl trimethyl ammonium bromide (CTAB) to be effective in dispersing and

stabilizing graphene ENMs even at low concentrations of 0.004% (w:v). The surfactant

concentration also proved to have a significant impact on the retention and transport of

graphene in saturated porous medium (Liu et al., 2015). In addition, surfactant CTAB was

also reported to increase the stability of Al2O3 nanoparticles in suspension (Yang et al.,

2011).

Most of the studies published thus far have focused only on the behaviors and transport of

ENMs in laboratory-used ultrapure water or artificial solutions. The pH value and ionic

strength of the solutions are reported to highly affect the aggregation and sedimentation of

nano-TiO2 (Erhayem and Sohn, 2014; French et al., 2009). Considering the differences and

complexities of physico-chemical properties of natural waters, we can obtain significant

information by studying the environmental behaviors of ENMs in natural waters.

In this study, we investigated the effects of surfactants on the behaviors and fate of TiO2

ENMs in both laboratory-used Milli-Q water and environmental aqueous matrices. A

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widely applied TiO2 ENM was selected as a model ENM. Among the available surfactants,

we selected anionic sodium dodecyl sulfate (SDS) and nonionic nonylphenol ethoxylate

(NPEO, Tergitol NP-9), which are the two common types of surfactants used in very large

quantities in the industry. The mechanisms by which ionic SDS and non-ionic NPEO

surfactants affect the environmental behaviors of nano-TiO2 were elucidated. Instead of

traditional static experiment, the aggregate size and sedimentation behavior of TiO2

aggregate were studied after a 24-h batch experiment in a shaker, which was designed to

better simulate the actual dynamic aquatic environment. We used six water samples from

different origins to study the effect of surfactants on the behaviors of nano-TiO2 in real

environmental waters.

2. Materials and methods

2.1 Chemicals

Aeroxide P25 TiO2 (718467, ≥99.5% trace metals basis ) with a primary particle size of 21

nm (TEM) and surface area (BET) of 35–65 m2 g -1

was purchased from Sigma-Aldrich.

The point of zero charge (PZC) of this TiO2 is reported to be approximately 6.2 (Jiang et al.,

2008; Kosmulski, 2009; Suttiponparnit et al., 2010). A nano-TiO2 stock solution was

prepared by adding 0.5 g of nano-TiO2 powder into 1 L of ultrapure water (Milli-Q) with

30 min sonification. The working solutions were prepared by diluting the nano-TiO2 stock

solution to 50 mg L -1. SDS (436143, ACS reagent, ≥99.0%) and NPEO (521078, Tergitol

NP-9, >97%) surfactants were also obtained from Sigma-Aldrich, and the corresponding

0.1% (w:v) stock solutions were prepared and stored at room temperature before use. The

5
total organic carbon (TOC) values of the SDS and NP-9 stock solutions are 537.34 and

616.84 mg/L, respectively.

2.2 Experimental water samples

Water samples from six different origins were collected to study the effects of the

surfactants on the environmental behaviors of nano-TiO2. The first two water samples were

collected from the Yangtze River (Wuhan, China) and Xiangjiang River (Changsha, China),

two of the most important water sources in China. The next two samples were collected

from Lake Biwa (Otsu, Japan) and Katsuragawa River (Kyoto, Japan), which are important

water sources in the Kansai area of Japan. The last two samples were tap water (Kyoto

University, Japan) and water discharged from a municipal wastewater treatment plant

(MWTP; Kyoto Toba MWTP, Japan). All the water samples were filtered through a 0.2 µm

Millipore hydrophilic polytetrafluoroethylene (PFTE) membrane and stored at 4o C before

the experiments.

The pH levels of the water samples were measured using a pH meter (Horiba, D51). The

TOC was measured using a TOC-V analyzer (Shimadzu Corporation). The F -, Cl -, NO3 -,

SO4 2-, HCO3 -, Na+, K+, NH4+, Ca2+, and Mg2+ ions in the water were determined using an

ion chromatograph (Shimadzu Corporation).

2.3 Adsorption study

To study the adsorption behaviors of surfactants on the surface of nano-TiO2, the

adsorption isotherms were obtained on the basis of a batch equilibration experiment at 25o

C. Briefly, 50 mg of nano-TiO2 powder and 50 mL of SDS or NP-9 surfactant solutions

6
 -1
with concentrations ranging from 0 to 80 mg L were added into 100-mL vials. After

equilibrating at 140 rpm for 24 h in a shaker, the suspensions were centrifuged at 10,000

rpm for 20 min, and the supernatants were collected for TOC analysis.

2.4 Effect of surfactants on the aggregation and sedimentation of nano-TiO2

The effects of SDS and NP-9 surfactants on the aggregation of nano-TiO2 in solution were

studied after a 24-h batch experiment. In general, nano-TiO2 and surfactant stock solutions

were diluted to form 50-mL mixed suspensions containing 50 mg L -1 TiO2 and 0-0.03%

surfactants. After preparing all the suspensions, the zeta potential of the nano-TiO2 in each

suspension was measured by a dynamic light scattering (DLS) analyzer (ELSZ-2plus,

Otsuka Electronics). Next, the suspensions were placed in a shaker and shaken at 140 rpm

at 25o C. After 24 h of reaction, 2.5 mL of the above suspensions were added to disposable

cuvettes. The average hydrodynamic particle sizes of TiO2 aggregate in SDS and NP-9

solutions were measured by DLS. In addition, a scanning electron microscope (SEM, JSM-

5600T, JEOL) was used to observe the aggregate size of nano-TiO2 to better confirm how

the surfactants affected the aggregation of nano-TiO2.

To predict the effect of surfactants on the environmental transport and fate of nano-TiO2,

sedimentation experiment was carried out using an ultraviolet–visible (UV-Vis)

spectrophotometer. After the 24-h batch experiment in the shaker, 2.5 mL of TiO2

suspensions containing different concentrations of surfactants were transferred into 3-mL

cuvettes. The suspensions were measured at a wavelength of 378 nm, and the UV

absorbencies were recorded at different time intervals for 24 h. The sedimentation of TiO2

7
aggregate is expressed by Ct/C0, where C0 is the initial absorbency and Ct is the absorbency

recorded at different intervals during the sedimentation process.

Finally, we studied the aggregation and sedimentation of TiO2 nanoparticles in

environmental aqueous matrices to better simulate and understand how the surfactants

affected the behaviors and transport of TiO2 ENMs in a natural water environment as

opposed to the remarkably different aqueous environment of the ultra-pure Milli-Q water

generally used in laboratories. All the above-mentioned experiments were conducted in

duplicate.

3. Results and discussion

3.1 Adsorption of surfactants by nano-TiO2

Fig.1 Adsorption isotherms of SDS and NP-9 surfactants by nano-TiO2

Figure 1 plots the adsorption isotherms of SDS and NP-9 surfactants by nano-TiO2. As

shown in the figure, the nano-TiO2 adsorbs both SDS and NP-9, with higher adsorption of

8
NP-9. The Langmuir isotherm model applied to fit the adsorption data is expressed in Eq. 1

as follows:

= bC /(1 + bC ), Eq.1

where (mg/g) is the amount of solute adsorbed per unit weight of nano-TiO2 at

equilibrium, is the maximum adsorption capacity, (mg/L) is the equilibrium

concentration of solute in the liquid phase, and b (L/mg) is the constant related to the molar

heat of adsorption. The fitted values of SDS and NP-9 calculated by the equation

were 13.05 mg/g with an r2 value of 0.969 and 15.20 mg/L with an r2 of 0.993, respectively.

The fitted regression coefficients show that the Langmuir isotherm model can be well fitted

to the adsorption of SDS and NP-9 surfactants by nano-TiO2, and that NP-9 has higher

maximum adsorption capacity than SDS.

3.2 Effects of the surfactants on the zeta potential, aggregation, and sedimentation of

nano-TiO2

Fig.2 Effect of surfactants on the zeta potential (A) and average particle size (B) of nano-TiO2

9
The adsorption of surfactants exerted different effects on the zeta potential of nano-TiO2 in

aqueous solutions. As shown in Figure 2 (A), the zeta potential of nano-TiO2 decreased

from 14.72 to - 42.67 mV with the increase in the SDS concentration from 0% to 0.030%.

In contrast, the zeta potential remained unchanged, showing only small fluctuations, with

the increase in the NP-9 concentrations. The existence of surfactants also significantly

affected the average particle size of TiO2 aggregates in solutions after shaking for 24 h. The

increase in the particle size of nano-TiO2 to 1250.2 nm in Milli-Q water showed the 24-h

continuous shaking process remarkably facilitated the aggregation of nano-TiO2 particles.

With the introduction of SDS, in contrast, the particle size of the TiO2 aggregates increased

sharply at the outset and continued to reach a peak size of 3268.7 nm at an SDS

concentration of 0.005%. However, despite the further increase in the SDS concentration,

the particle size rapidly decreased. After the SDS concentration reached 0.015%, the

particle size of the TiO2 aggregates remained far below that measured in bare Milli-Q water.

At an SDS concentration of 0.030% after the 24-h batch experiment, an aggregate as small

as 241.7 nm was recorded. For NP-9, the increasing surfactant concentration in the solution

reduced the particle size of the TiO2 aggregates relatively smoothly. When the NP-9

concentration reached 0.030%, a TiO2 aggregate of 676.0 nm, a diameter 45.9% smaller

than that observed in Milli-Q water, was detected.

The SEM images further confirmed that the presence of surfactant could remarkably affect

the particle size of the TiO2 aggregate. As shown in Figure 3, most of the TiO2 aggregates

formed in Milli-Q water after 24-h shaking were apparently beyond the micrometer grade.

In comparison, the TiO2 aggregate remained within the 100-nm range in the presence of

10
both 0.030% SDS and 0.030% NP-9. The above findings confirm the high capacity of the

surfactants to affect the aggregate size of TiO2 in aqueous solutions.

Fig.3 SEM images of TiO2 aggregates after shaking for 24 h

It is reported that nanoparticles tend to aggregate as the zeta potential approaches zero;

when absolute zeta potential value is higher than 20 mV, particles tend to repel each other

and remain stable in the suspension (Hasani Bijarbooneh et al., 2013). With the

introduction of a low concentration of SDS, the absolute value of the zeta potential of TiO2

initially decreased in response to the SDS-induced compression of the diffuse layer of

nanoparticles, which later reduced the repulsive force between the nanoparticles. The TiO2

nanoparticles tended to aggregate more as a result, leading to a much larger aggregate after

the 24-h batch experiment. As the SDS concentration increased further, the zeta potential

followed a consistently negative trajectory, whereas the absolute value of the zeta potential

increased. The repulsive force between the nanoparticles accordingly increased, which

reasonably explained the decrease in the aggregate size. In contrast, the introduction of NP-

9 clearly reduced the size of the TiO2 aggregate without exerting any obvious effect on the

11
zeta potential. This can be explained by the adsorption of non-ionic NP-9 surfactant on the

surfaces of the TiO2 primary particles, a process that reduced the aggregation of TiO2

through steric inhibition during the batch experiment.

Fig.4 Effect of surfactants on the sedimentation of TiO2 aggregates

The sedimentation of TiO2 aggregates after 24 h of continuous shaking was observed using

a UV-spectrophotometer at the wavelength of 378 nm (Keller et al., 2010). Before

measuring the TiO2 suspension, SDS or NP-9 background solutions were measured at the

same wavelength and no absorbency was recorded. As shown in Figure 4 (A), the TiO2

aggregates clearly settled in the Milli-Q water, leaving only 44.6% remaining in the

suspension after 24 h. The sedimentation of TiO2 aggregate significantly accelerated in the

presence of SDS at 0.005% and 0.010% concentrations, leaving only 4.49% and 8.80% of

the aggregate in the above suspensions after 24 h, respectively. The rate of TiO2

sedimentation retarded remarkably, however, at SDS concentrations higher than 0.015%.

At an SDS concentration of 0.020%, over 95% of the TiO2 was still suspended after 24 h.

The effect of SDS on the sedimentation of TiO2 correlated well with that on the particle

12
size. At SDS concentration above 0.015%, the repulsive force generated by the surface-

attached anionic surfactant retarded the aggregation of nano-TiO2 particles during the batch

experiment and prevented the quick sedimentation of nano-TiO2 particles. Figure 4 (B)

shows the effect of NP-9 surfactant on TiO2 sedimentation. The figure clearly shows the

effect of NP-9 in retarding the sedimentation of TiO2: as the concentration of NP-9

increased, the stability of TiO2 in the suspension generally increased in parallel during the

experimental period. In the presence of NP-9 at the concentration of 0.030%, as high as

83.65% of the TiO2 remained in the suspension after 24 h.

From the results of the above experiments, SDS and NP-9 surfactants remarkably changed

the aggregate size and sedimentation speed of TiO2 aggregates. We can therefore

reasonably assume that surfactants increase the environmental risk of TiO2 nano-materials

by changing their transport behavior and fate in aqueous environments.

3.3 Characterizations of experimental aqueous matrices

To further understand how surfactants affect the behaviors and fate of nano-TiO2 in natural

water environments, we also need to study the aggregation and sedimentation of the

nanomaterial in actual environmental aqueous matrices. Table 1 lists the chemical

compositions and physico-chemical properties of all the water samples used for the

experiments, as determined in preliminary analyses. Although collected from different

locations, all the water samples used for the experiments had similar pH values in the range

from 6.65 to 6.99. The highest TOC and ionic strength were detected in wastewater, and the

lowest values were detected in tap water. The Yangtze River sample had the highest

concentration of multivalent ions.

13
 Table.1 Chemical composition and physico-chemical properties of water samples
Yangtze Xiangjiang Lake Katsuragawa Tap Waste

River River Biwa River Water Water

Ionic composition (mg L −1)

F− 0.26 0.28 0.18 0.13 0.09 0.19
Cl − 20.08 19.83 10.98 6.33 11.09 46.46
NO3 − 7.18 10.36 1.94 2.82 0.93 17.53
SO4 2- 26.18 24.51 19.95 16.91 11.90 28.84
HCO3 − 133.21 112.55 95.24 89.18 37.15 148.33
Na+ 23.10 22.23 13.26 18.36 14.29 25.53
K+ 2.26 3.04 2.75 2.12 1.69 8.14
NH4+ 1.67 1.51 0.49 0.20 0.12 31.24
Mg2+ 9.79 5.39 3.09 2.53 1.79 3.18
Ca2+ 45.23 39.17 12.86 12.91 7.31 16.36
pH 6.65 6.70 6.93 6.99 6.89 6.83
TOC (mg L −1) 1.20 1.09 1.40 1.27 0.67 2.54
Conductivity at 25° C (µS) 390 330 132 139 86 330
Ionic strength (mM) 5.57 4.71 2.59 2.47 1.56 4.35

3.4 Effect of surfactants on the behaviors of nano TiO2 particles in natural aqueous

matrices

Fig.5 Effect of surfactants on the size ratios of TiO2 aggregates in natural waters

Figure 5 shows the size ratio of TiO2 aggregates after 24 h batch experiment with and

without surfactants in natural aqueous matrices, where Ds and D0 are the TiO2 aggregate

14
sizes with and without surfactants, respectively. In different aqueous matrices, the

introduction of both SDS and NP-9 surfactants clearly reduced the size of the TiO2

aggregates. In the MWTP discharged water, for example, the presence of 0.015% and 0.030%

SDS reduced the TiO2 aggregate sizes by 42.72% and 50.98%, respectively. In comparison,

the presence of 0.015% and 0.030% NP-9 reduced the aggregate size by 36.18% and

46.99%, respectively. Two findings were commonly found in all the aqueous matrices

tested: higher surfactant concentrations reduced the TiO2 aggregate size more and the ionic

SDS surfactant retarded the aggregation of TiO2 nanoparticles more than the non-ionic NP-

9 surfactant.

Fig.6 Effect of surfactants on the sedimentation of TiO2 aggregates in natural aqueous matrices

Figure 6 shows the effects of surfactants on the sedimentation of TiO2 aggregates in six

experimental aqueous matrices. The presence of surfactants retarded the sedimentation of

15
TiO2 aggregates in all six matrices. The effects of surfactants in retarding the TiO2

sedimentation, however, were much weaker in the natural aqueous matrices than in Milli-Q

water. In the presence of SDS or NP-9 at 0.030% concentration in tap water, for instance,

52.97% and 39.58% of the TiO2 remained in the suspension after 24 h, respectively. In

comparison, the corresponding values in Milli-Q water were 96.01% and 83.65%. Many

studies have shown that factors such as pH, natural organic matters (NOMs), and ionic

strength can affect the behaviors of nano-materials in aqueous solutions (Badawy et al.,

2010; Godinez et al., 2013; Mohd Omar et al., 2014; Philippe and Schaumann, 2014; Shih

et al., 2012). However, in the present study, only minor difference in pH values was found

between Milli-Q water and natural water samples. In addition, the TOC of all the water

samples ranges from 0.67 to 2.54 mg L −1 according to Table 1, suggesting that the

concentrations of NOMs were much lower than surfactants in our suspension; hence

sorption competition between NOMs and surfactants was very weak. Although interactions

between surfactants and components in natural waters may exist, it does not change the fact

that surfactants effectively stabilize TiO2 nano-materials in natural waters.

The discrepant values of aggregate sizes and sedimentation efficiencies are thought to result

from the relatively high ionic strength in the environmental aqueous matrices. At low ionic

strength, Dickson et al. reported that an increase in ionic strength to 10 mM NaCl resulted

in rapid aggregation and sedimentation of hematite nanoparticles in dispersion within 8 h

(Dickson et al., 2012). At 0.01 mM ionic strength of KCl and CaCl2, it was reported that the

sedimentation efficiencies of TiO2 nanoparticles were about 20% and 25%, respectively,

after 4 h (He et al., 2015). In general, an increase in ionic strength leads to stronger

16
compression of the double layer of nanoparticles, thus reducing the repulsive force between

nanoparticles and increasing the size of the aggregates and speed of the sedimentation. In

experiments conducted by French et al., a 5-min mixing of NaCl solutions (ionic strength

0.0165 M) with a stable 50-60 nm nano-TiO2 aggregate suspension increased the mean

aggregate size to 150 nm(French et al., 2009). A comparison of seawater and freshwater

from several different natural aqueous matrices shows that the former generally had an

ionic strength of 1 or 2 orders of magnitude higher, a larger aggregate size, and a much

higher sedimentation speed (Keller et al., 2010). At an ionic strength of 0.11 M, Godinez et

al. found that the size of TiO2 aggregate increased by more than five-fold after 145-min

aggregation. They concluded that the increase in ionic strength led to faster aggregation and

sedimentation by shielding the surface charge of the nano aggregates (Godinez et al., 2013).

Among all the cations listed in Table 1, the divalent Ca2+ contributed most to the total ionic

strength in all the water samples. It is reported that even if ionic strength is kept the same,

Ca2+ had a much higher activity than Na+ in decreasing the absolute zeta potential value and

stability of nanoparticles. Additionally, for carboxyl groups and humic acid-modified

nanoparticles, the bridging effect of Ca2+ is also an important contributor of the reduced

stability of nanoparticles (Badawy et al., 2010). Our experimental results indicate that the

effects of the SDS and NP-9 surfactants in reducing the aggregate size and sedimentation

speed of TiO2 can be generally ranked as follows: 0.030% SDS > 0.015% SDS > 0.030%

NP-9 > 0.015% NP-9. When only nonionic NP-9 was used, the TiO2 nanoparticles cannot

be stabilized with additional repulsive force. Besides, the pH values of all the

environmental water samples were higher than the PZC value (6.2), indicating the negative

17
charge on the surface of TiO2 nanoparticles. Therefore, the intermolecular bridging through

Ca2+ and Mg2+ weakened the steric inhibition effect of NP-9. With regard to SDS surfactant,

although surface-covered SDS anions exerted strong repulsive forces between the TiO2

nanoparticles, cations were also attracted by the negative surface charge. Finally, with the

suppression of the double layer, the repulsive force between TiO2 nanoparticles decreased.

These effects, in turn, remarkably increased the chances for nanoparticle collision in natural

aqueous matrices during the batch experiments, promoting aggregation and sedimentation

in both SDS and NP-9 suspensions.

4. Conclusions

This study found that SDS and NP-9 surfactants could be adsorbed onto the surface of TiO2

nanoparticles. When the concentration of either surfactant exceeded 0.015%, the growth of

the TiO2 aggregate size was significantly hindered after the 24-h batch experiment, and the

sedimentation speed of the aggregate was sharply retarded. While a relatively high ionic

strength compressed the double layer and weakened the repulsion between TiO2

nanoparticles, the presence of surfactants in natural water matrices still conferred

pronounced effects in reducing the growth of the aggregates and retarding the

sedimentation. The effects of SDS were more pronounced than those of NP-9. This study

indicates that surfactants reduce the aggregation and increase the stability of TiO2 nano-

materials in natural waters, thereby possibly increasing their risk levels in aqueous

environments.

18
Acknowledgments

This study was supported by the Environmental Risk Engineering Laboratory of Kyoto

University. The author would like to thank Professor Minoru Yoneda for his kind guidance

on this research. The author is also grateful to the China Scholarship Council for offering

financial support for his studies in Japan.

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