Aggregation and disaggregation of ZnO nanoparticles: Influence of pH
and adsorption of Suwannee River humic acid
Fatehah Mohd Omar
a
, Hamidi Abdul Aziz
b
, Serge Stoll
a,
⁎
a
F.-A. Forel Institute, University of Geneva, 10 route de Suisse, 1209 Versoix, Switzerland
b
School of Civil Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
HIGHLIGHTS
• ZnO nanoparticle aggregation and dis-
aggregation behavior is pH dependent.
• SRHA environmental concentrations in-
duce disaggregation of ZnO NPs.
• Electrostatic repulsions and steric stabi-
lization control ZnO disaggregation.
GRAPHICAL ABSTRACT
ZnO
Nanoparticles
and
Aggregates
SRHA
?
Aggregation
Disaggregation
pH, [SRHA]
abstract article info
Article history:
Received 12 July 2013
Received in revised form 14 August 2013
Accepted 14 August 2013
Available online 9 September 2013
Editor: Damia Barcelo
Keywords:
ZnO nanoparticles
Suwannee River humic acid
Zeta potential
Aggregation
Disaggregation
The surface charge and average size of manufactured ZnO nanoparticles (NPs) were studied as a function of pH to
understand the aggregation behavior and importance of the electrostatic interactions in solution. The interac-
tions between ZnO and Suwannee River humic acid (SRHA) were then investigated under a range of environ-
mentally relevant conditions with the ZnO nanoparticles pH
PZC
as the point of reference. The anionic charges
carried by aquatic humic substances were found to play a major role in the aggregation and disaggregation of
ZnO nanoparticles. At low concentrations of SRHA (b 0.05 mg/L) and below the pH
PZC
, anionic SRHA was rapidly
adsorbed onto the positively charged ZnO NPs hence promoting aggregation. With similar SHRA concentrations,
at pH
PZC
, SRHA was able to control the suspension behavior of the ZnO and promote partial disaggregation in
small volumes. This was more distinguishable when the pH was greater than pH
PZC
as SRHA formed a surface
coating on the ZnO nanoparticles and enhanced stability via electrostatic and steric interactions. In most cases,
the NP coating by SRHA induced disaggregation behavior in the ZnO nanoparticles and decreased the aggregate
size in parallel to increasing SRHA concentrations. Results also suggest that environmental aquatic concentration
ranges of humic acids largely modify the stability of aggregated or dispersed ZnO nanoparticles.
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
Zinc oxide nanoparticles (NPs) have emerged as one of the most wide-
ly used nanomaterials in commercial products with applications such as
in catalysis, dye-sensitized solar cells, sensors, sunscreens, cosmetics,
Science of the Total Environment 468–469 (2014) 195–201
⁎ Corresponding author. Tel.: +41 22 379 0333; fax: +41 22 379 03 29.
E-mail addresses: mohdoma9@etu.unige.ch (F. Mohd Omar), cehamidi@usm.eng.my
(H. Abdul Aziz), serge.stoll@unige.ch (S. Stoll).
0048-9697/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.scitotenv.2013.08.044
Contents lists available at ScienceDirect
Science of the Total Environment
journal homepage: www.elsevier.com/locate/scitotenv