Biogenic platinum and palladium nanoparticles as new catalysts for
the removal of pharmaceutical compounds
M
onica Martins
a, *
, Cl
audia Mourato
a
, Sandra Sanches
b
, Jo
~
ao Paulo Noronha
c
,
M.T. Barreto Crespo
a, b
, In
^
es A.C. Pereira
a, **
a
ITQB NOVA, Instituto de Tecnologia Química e Biol ogica Ant onio Xavier/ Universidade Nova de Lisboa, Av. da Republica-EAN, 2780-157 Oeiras, Portugal
b
iBET, Instituto de Biologia Experimental e Tecnol ogica, Apartado 12, 2780-901 Oeiras, Portugal
c
LAQV, REQUIMTE, Departamento de Química, Faculdade de Ci^ encias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
article info
Article history:
Received 26 July 2016
Received in revised form
25 October 2016
Accepted 27 October 2016
Available online xxx
Keywords:
Pharmaceutical compounds
Biogenic nanoparticles
Platinum
Desulfovibrio
Reductive catalysis
abstract
Pharmaceutical products (PhP) are one of the most alarming emergent pollutants in the environment.
Therefore, it is of extreme importance to investigate efficient PhP removal processes. Biologic synthesis of
platinum nanoparticles (Bio-Pt) has been reported, but their catalytic activity was never investigated. In
this work, we explored the potential of cell-supported platinum (Bio-Pt) and palladium (Bio-Pd) nano-
particles synthesized with Desulfovibrio vulgaris as biocatalysts for removal of four PhP: ciprofloxacin,
sulfamethoxazole, ibuprofen and 17b-estradiol. The catalytic activity of the biological nanoparticles was
compared with the PhP removal efficiency of D. vulgaris whole-cells. In contrast with Bio-Pd, Bio-Pt has a
high catalytic activity in PhP removal, with 94, 85 and 70% removal of 17b-estradiol, sulfamethoxazole
and ciprofloxacin, respectively. In addition, the estrogenic activity of 17b-estradiol was strongly reduced
after the reaction with Bio-Pt, showing that this biocatalyst produces less toxic effluents. Bio-Pt or Bio-Pd
did not act on ibuprofen, but this could be completely removed by D. vulgaris whole-cells, demonstrating
that sulfate-reducing bacteria are among the microorganisms capable of biotransformation of ibuprofen
in anaerobic environments. This study demonstrates for the first time that Bio-Pt has a high catalytic
activity, and is a promising catalyst to be used in water treatment processes for the removal of antibiotics
and endocrine disrupting compounds, the most problematic PhP.
© 2016 Elsevier Ltd. All rights reserved.
1. Introduction
The widespread occurrence of pharmaceutical products (PhP) in
the environment has become a worldwide issue (Gavrilescu et al.,
2015; Luo et al., 2014; Stuart et al., 2012). Globally, thousands of
different active compounds are used in human and veterinary
medicine and most of them are excreted in unaltered form or as
active metabolites (Petrie et al., 2015). Due to their inefficient
removal in wastewater treatment plants (WWTP) and improper
disposal of industrial wastewaters, PhP are continuously intro-
duced in the environment (Gavrilescu et al., 2015; Petrie et al.,
2015). These pollutants are not only detected in wastewaters but
also in surface waters, in sea and groundwater and even in drinking
water in several countries (Gavrilescu et al., 2015; Luo et al., 2014;
Stuart et al., 2012). Despite the low concentrations in which they
are usually detected, their accumulation and persistence in the
environment can lead to harmful effects on human and animal
health and on the ecosystems (Gavrilescu et al., 2015; Luo et al.,
2014; Stuart et al., 2012).
The most problematic PhP are non-steroidal anti-inflammatory
drugs, estrogens and antibiotics (Fischer et al., 2012; Santos et al.,
2010). Estrogens are commonly found in aquatic systems, and
there is strong evidence that they affect the fertility and develop-
ment of fish, reptiles and aquatic vertebrates (Boxall, 2004; Santos
et al., 2010). Antibiotics are also a severe environmental problem
because even at vestigial levels they can induce resistance in bac-
terial populations (Gavrilescu et al., 2015).
To prevent environmental contamination by PhP and their
possible adverse effects, it is essential to develop new strategies to
remove these pollutants from wastewaters. Advanced oxidation
processes, such as UV/H
2
O
2
, UV/O
3
, and UV/TiO
2
, have been the
most studied processes for PhP degradation (Homem and Santos,
* Corresponding author.
** Corresponding author.
E-mail addresses: msmartins@itqb.unl.pt (M. Martins), ipereira@itqb.unl.pt
(I.A.C. Pereira).
Contents lists available at ScienceDirect
Water Research
journal homepage: www.elsevier.com/locate/watres
http://dx.doi.org/10.1016/j.watres.2016.10.071
0043-1354/© 2016 Elsevier Ltd. All rights reserved.
Water Research xxx (2016) 1e9
Please cite this article in press as: Martins, M., et al., Biogenic platinum and palladium nanoparticles as new catalysts for the removal of
pharmaceutical compounds, Water Research (2016), http://dx.doi.org/10.1016/j.watres.2016.10.071