Research article
Synthesis and characterization of a molecularly imprinted polymer for
the isolation of the 16 US-EPA priority polycyclic aromatic
hydrocarbons (PAHs) in solution
Somandla Ncube
a
, Phumlile Kunene
a
, Nikita T. Tavengwa
a, b
, Hlanganani Tutu
a
,
Heidi Richards
a
, Ewa Cukrowska
a
, Luke Chimuka
a, *
a
Molecular Sciences Institute, School of Chemistry, University of Witwatersrand, Private Bag X3, Johannesburg, 2050, South Africa
b
Department of Chemistry, University of Venda, Private Bag X5050, Thohoyandou, 0950, South Africa
article info
Article history:
Received 31 March 2017
Received in revised form
9 May 2017
Accepted 13 May 2017
Keywords:
Polycyclic aromatic hydrocarbons
Molecular imprinting technology
Molecularly imprinted polymers
Benzo[k]fluoranthene
Indeno[1 2 3-cd]pyrene
abstract
A smart sorbent consisting of benzo[k]fluoranthene-imprinted and indeno[1 2 3-cd]pyrene-imprinted
polymers mixed at 1:1 (w/w) was successfully screened from several cavity-tuning experiments and
used in the isolation of polycyclic aromatic hydrocarbons from spiked solution. The polymer mixture
showed high cross selectivity and affinity towards all the 16 US-EPA priority polycyclic aromatic hy-
drocarbons. The average extraction efficiency from a cyclohexane solution was 65 ± 13.3% (n ¼ 16, SD).
Batch adsorption and kinetic studies confirmed that the binding of polycyclic aromatic hydrocarbons
onto the polymer particles resulted in formation of a monolayer and that the binding process was the
rate limiting step. The imprinted polymer performance studies confirmed that the synthesized polymer
had an imprinting efficiency of 103.9 ± 3.91% (n ¼ 3, SD). A comparison of the theoretical number of
cavities and the experimental binding capacity showed that the overall extent of occupation of the
imprinted cavities in the presence of excess polycyclic aromatic hydrocarbons was 128 ± 6.45% (n ¼ 3,
SD). The loss of selectivity was estimated at 2.9% with every elution cycle indicating that the polymer can
be re-used several times with limited loss of selectivity and sensitivity. The polymer combination has
shown to be an effective adsorbent that can be used to isolate all the 16 US-EPA priority polycyclic ar-
omatic hydrocarbons in solution.
© 2017 Elsevier Ltd. All rights reserved.
1. Literature review
Polycyclic aromatic hydrocarbons (PAHs) belong to an impor-
tant class of persistent organic pollutants that are commonly found
in the environment at low concentrations. In urban areas, the
source of PAHs includes household human and chemical waste,
automobile exhaust products, storm water run-off from both
impervious and pervious areas like roads, parking areas and con-
struction sites, industrial effluents from the manufacture of
chemicals and carbonaceous waste incineration. They then enter
the wastewater treatment plants through the sewerage (Zorpas
et al., 2011; Cai et al., 2007; Singh and Agrawal, 2008). The gen-
eral adverse effects of PAHs to the environment and humans is
widely documented (Abdel-Shafy and Mansour, 2015;
Maliszewska-Kordybach, 1999; Dean and Suess, 1985). Environ-
mental and potential carcinogenic health concerns of PAHs have
necessitated their inclusion in lists of priority pollutants by several
regulatory agencies such as the US Environmental Protection
Agency (US-EPA), European Union Environmental Protection
Agency, and Environment Canada. The US-EPA has identified 16
unsubstituted PAHs as priority pollutants, some of which are
considered possible or probable human carcinogens (Shailaja and
D'Silva, 2003).
Most of the techniques used in the extraction of PAHs are fol-
lowed by a clean-up step in which the PAHs are isolated from the
matrix effects and finally pre-concentrated for detectability in
chromatographic instruments (Rawa-Adkonis et al., 2006). This
step is almost always through solid phase extraction (SPE) or gel
permeation chromatography (GPC) with various adsorbent phases
such as octadecyl (C
18
) and molecularly imprinted polymers (MIPs)
while membrane-based extractions like membrane assisted solid
extraction and liquid phase micro extractions have been used
* Corresponding author.
E-mail address: luke.chimuka@wits.ac.za (L. Chimuka).
Contents lists available at ScienceDirect
Journal of Environmental Management
journal homepage: www.elsevier.com/locate/jenvman
http://dx.doi.org/10.1016/j.jenvman.2017.05.041
0301-4797/© 2017 Elsevier Ltd. All rights reserved.
Journal of Environmental Management 199 (2017) 192e200