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Cite this: RSC Adv., 2014, 4, 63650

Received 29th October 2014

Accepted 18th November 2014

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A photocatalytic process for the eradication of

dengue through cOH generation in the presence of
sunlight and iron oxide
G. V. Pereira, V. A. Freitas, H. S. Oliveira, L. C. A. Oliveira* and J. C. Belchior

DOI: 10.1039/c4ra13435d
www.rsc.org/advances

Iron oxide was dispersed in a oating matrix based on autoclaved

porous brick. Under an incidence of solar radiation cOH radicals are
generated by the photocatalytic process, completely oxidizing the
organic matter. This procedure makes the proliferation of dengue
larva unfeasible. Additionally, cOH radicals have a remarkable deleterious eect on hatching of A aegypti eggs. The predominant iron phase
was hematite (a-Fe2O3), as indicated by the Mossbauer spectroscopy.
The formation of cOH species was demonstrated by typical m/z values
obtained via ESI-MS.

Dengue is a disease that occurs mainly in tropical and

subtropical areas of the world. It is caused by an arbovirus
producing infected individuals that can develop a high fever,
headaches, pain behind the eyes and back, drowsiness and
generalized body ache, nausea and vomiting. Reddish spots
may appear throughout the body.1,2 The disease transmission
occurs in all cases through the bite of the Aedes aegypti
mosquito. This species reached South America via slave ships
from Africa in the colonial period (16th to 19th centuries).3,4
Dengue is a particularly serious concern to public health in
several tropical countries.5 From 2009 to 2011, the Department
of Health Surveillance of the Ministry of Health in Brazil
reported incidences of 205.5, 530.3 and 400.5 per 100 000
persons, respectively.6 Globally, about 100 million cases of
dengue and about 500 000 cases of dengue hemorrhagic fever
occur annually.7,8 Therefore, ecient technological processes
than can contribute to reduce the incidence of dengue in
infected areas are highly needed.
The present study discloses a new use of a catalyst
comprising iron oxide supported on an array of autoclaved
aerated concrete. The density, porosity and mechanical strength
of the support material make it well suited to be used in the
Department of Chemistry, Federal University of Minas Gerais, BH-MG, Av. Antonio
Carlos 6627, Campus Pampulha, 31270-901-Brazil. E-mail: luizoliveira@qui.ufmg.
br; jadson@ufmg.br; Fax: +55 31 3409 5700; Tel: +55 31 3409 7550
Electronic supplementary
10.1039/c4ra13435d

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available.

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DOI:

degradation process of organic compounds. This support

material can be chemically treated with Fe2O3, which is a low
cost material. The use of this material can aid in avoiding the
proliferation of diseases based vectors, whose initial stage of the
development occurs in aquatic environments.9,10 We report the
use of catalysts consisting of iron oxide supported by an autoclaved aerated concrete array. This material is activated by UV
component of sunlight and can be used for degrading microorganisms, such as bacteria, fungi and plankton that serve as a
basis for feeding the larvae of A aegypti that can cause diseases
such as dengue, or other vectors that can produce diseases such
as yellow fever, malaria, and leishmaniasis. In other words, the
present approach can, in principle, eliminates larvae that are
developed in an aqueous medium.
The catalyst in contact with an aqueous environment under
incidence of sunlight or articial light in the ultraviolet range
produces the hydroxyl radical (cOH) with a standard oxidation
potential of 2.8 eV.11,12 This potential energy is the highest
potential available from a natural source. In a sense, the device
described herein is similar to a Noxer block, in which a porous
cement matrix is adsorbed with TiO2 and then calcinated.13,14 In
addition, this powerful reactant is transformed into water aer
the process, characterizing our approach as a green method and
an in nature process. The (cOH) radical degrades organic
compounds, including the larvae food source or even the larvae
themselves, reaching complete degradation of the organic matter.
In the synthesis of the a-Fe2O3 catalyst, 12 or 25 g of autoclaved aerated concrete was used, treated in 100 mL of a solution of iron(III) nitrate concentration of 1 mol L
1 for 30 min.
The material was thermally treated at 200  C for 2 h and called
PT. The analogue material, without chemical modication, was
called PNT. Scanning electron microscopy (SEM/EDS) was
carried out on a JEOL analyzer. 57Fe M
ossbauer spectra of all
samples were collected in a constant acceleration transmission
mode with a 50 mCi 57Co/Rh source. A spectrometer equipped
with a transducer (CMTE model MA250) controlled by a linear
function-driving unit (CMTE model MR351) was used to obtain
the spectra at 298 K. The data were stored in a 1024 channel-

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MCS memory unit, with the Doppler velocity ranging between

10 mm s
1, calibrated with a metallic iron (a-Fe) foil as
absorber. The absorbers were prepared with a uniform thickness of 10 mg Fe per cm2, admixing sucrose to the samples.
The experimental resonance lines were tted to Lorentzian
functions with the least-square tting statistical procedure of
the NORMOSTM-90 computer program. UV-vis spectroscopy
with diuse reectance geometry was carried out in a Shimadzu
2600 spectrometer from 200 to 800 nm. BaSO4 powder was used
as reference material (100% reectance), and the Kubelka
Munk equation was used to manipulate all data. The actual
chemical compositions of the prepared samples were determined with an inductively Coupled Plasma Mass Spectrometry
(ICP-MS) ELAN DRC II (PerkinElmer Life and Analytical
Sciences, USA). The ICP-MS was operated with Pt sampler and
skimmer cones, both purchased from Perkin Elmer. The plates
containing the Aedes aegypti eggs were submerged in water.
Aer 24 h, the hatching occurred and the catalysts were added
into the medium. The beakers containing the larvae and the
catalysts were placed under solar irradiation (average temperature 20  C, humidity 69% and radiation kJ m2 2000) for
8 hours (http://www.inmet.gov.br/).
The eciency of the catalyst material was compared with the
oxidative activity of commercial sodium hypochlorite (bleach),
which is one of the most commonly compounds used in the
eradication of insect larvae. The experiments were divided as
follows: (i) sucrose (200 mg L
1) was used as nutrient solution;
(ii) sucrose solution + bleach; (iii) sucrose solution + 12 g of
catalyst and (iv) sucrose solution + 25 g of catalyst. Each type of
sample was placed in dierent natural conditions for 8 weeks,
namely: outdoor shade, shade with protection from rainfall and
direct exposure to sunlight. The experiments were monitored
for 1 week with the following experimental conditions:
average temperature 20  C, humidity 69% and radiation
2000 kJ m2 (http://www.inmet.gov.br/).
The formation of iron(III) impregnated in the autoclaved
aerated concrete matrix oxide (PT) was characterized by 57Fe
M
ossbauer spectroscopy at 20 K (spectrum not shown). The PNT
sample has four iron species before impregnation and heat
treatment: Fe3+, a-Fe2O3, Fe7S8 and a-Fe, with the most abundant
species being the superparamagnetic Fe3+ followed by a-Fe2O3
(26%). Aer impregnation and heat treating (200  C/2 h) the
sulde species are converted into hematite (a-Fe2O3), by aerobic
oxidation of sulde to SO2(g). The material continues to show the
superparamagnetic Fe3+ as majority iron specie. This is probably
due to the reduced size of iron oxide particles (<10 nm) dispersed
onto aerated concrete matrix resulting from impregnation.
The determination of total iron in the PNT sample by an
Inductively Coupled Plasma Mass Spectrometry (ICP-MS) presented a content of 1.9 and 3.5% (w/w) before and aer
impregnation, respectively. Through SEM-EDS it is possible to
observe that the impregnation method allows spreading aFe2O3 homogeneously on the whole surface (Fig. 1ac). The PT
sample shows a smooth surface at 50 mm compared to the
roughness of the PNT surface (Fig. 1df). It is also observed and
demonstrated that the iron species dispersion on the PNT
sample is heterogeneous by collecting the EDS signals from

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Fig. 1 Photograph of the PT sample (a), SEM image of its surface (b)
and the EDS spectra of the area (c). PNT sample (d), SEM image of its
surface (e) and the EDS spectra of the area (f).

dierent regions of the sample (spectra not shown here). In the

PNT central region, the SKa signal from Fe7S8 appears while the
FeKa signal from other iron species is very low. By observing the
borderline direction, the FeKa becomes stronger. This suggests
that the iron present in the parent material comes from its
manufacture. However, the amount and chemical speciation of
iron atoms present in the matrix do not provide the eciency
required to perform our new approach. Actually, only the
impregnation process may provide iron photocatalytically
activity that can be used for the catalytic process.
Based on the spectral relative area of the iron species, it is
observed that about 40% of the iron content initially lies in the
form of iron sulde and metallic iron. Another important
feature is that aer the impregnation process, the iron species
are well distributed on the whole surface of the support material. On the other hand, the pre-existing iron is homogeneouslymixed in autoclaved aerated concrete and hence it does not
participate at all in the catalytic process. The UV-vis diuse
reectance spectra of the as-prepared materials are shown in
Fig. S1. The PNT spectrum showed no absorption in the
spectral region surrounding regions of the visible and ultraviolet (red line in Fig. S1). The spectrum of the PT material (black
line), presented absorption in the ultraviolet region and visible
region between 400600 nm, whereas the solar radiation that
reaches the earth surface comprises part of the region where the
iron oxide absorbs (highlighted in the graphic part), which
means that this catalyst can be excited by solar radiation.
Accordingly, the catalyst should exhibit photocatalytic properties
for the generation of electron pair (e
)/holes (h+) when irradiated
with sunlight capable of generating radical species. In order to
prove the formation of hydroxyl radicals (highly oxidizing
species), experiments with an organic dye (methylene blue) were
performed via injection. Some authors (Guimar
aes et al. (2008)15
16
and Oliveira et al. (2007)) have demonstrated that the presence
of hydroxyl radicals is evidenced by the formation of species with
m/z 300, 301, 316 and 318, which are related to the incorporation of the radical into the structure. Hydroxylated species with
m/z 302, 318 and 329 were seen aer 30 min under UV light
irradiation (Fig. 2). Aer 120 min, the molecular ion of the dye
(m/z 284) decreased sharply relative to other hydroxylated
species. Likewise, the PNT material showed hydroxylated species

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aer 30 min of irradiation. However, the presence of these

species was much less pronounced when compared to the PT
material, and aer 120 min. the signal intensity did not signicantly change (Fig. 2). Therefore, the chemical and thermal
treatment on PNT material is actually essential to increase photoactivity and generate the radical species.17
As a preliminary analysis, we studied the ability of the PT
material to eliminate dengue larvae at an advanced stage of its
development. Fig. 3a shows the exposure to 8 h under sunlight
radiation. The larvae did not change aer this long period of
exposition and hence it seems that there was no eect at all.
Similarly, Fig. 3b illustrates the results at the same condition
but in the presence the PT material. As one can see there are no
visible changes for the larvae. Fig. 3c shows an experiment
similar to Fig. 3b but using an articial 15 W UV (l 285 nm)
light source. For these particular results (Fig. 3b and c) one can
verify that due to the radiation and catalytic eects the larvae
did not grow signicantly. Furthermore, we observed that under
sunlight only 20% of larvae survived. However, a very ecient
result was veried considering articial UV light that produced
a signicant result, 100% of larvae died.
In order to validate the general applicability of the catalyst in
the control of mosquito larvae, we carried out eld experiments
simulating natural conditions. These experiments were performed in four dierent sites (occupied houses) with weekly
data collection. The materials were tested during 10 weeks
under solar radiation. The photodegradation of a nutrient
solution composed of sucrose (200 mg L
1) was studied through
the PT material to demonstrate the potential application for
mosquito larvae eradication. The nutrient solution was exposed
for 24 h in a batch reactor under sunlight irradiation with, as
well as without, catalyst. Aer 24 h, the solutions were analyzed
through total organic carbon (TOC), total carbon (TC) and
inorganic carbon (IC). The experiments were carried out in
triplicate in order to evaluate the statistical analysis. It is clearly
seen that aer 24 h the material provided ecient activity
capable of degrading 90% of all organic matter (Fig. 4a). This
makes the aqueous environment a nutrient-scarce medium for

Communication

Experiments of photocatalitic activity (8 h under radiation) for

mosquito larvae eradication. Control experiment with dengue larvae
under sunlight without catalyst (a), dengue larvae under sunlight with
catalyst (12 g) (b), dengue larvae under UV light (285 nm) with catalyst
(12 g) (c) and survival rate at the experiments (d).

Fig. 3

the development of mosquito larvae, leaving, on average, 10%

of organic matter initially present. Certainly, a longer time
exposed to this process will eventually mineralize all organic
materials in solution.
In order to determine the eciency of mosquito larvae
eradication, catalyst material was subjected to a preliminary
test. The latter involves the exposition of the photocatalytic
material in dierent aqueous environments allowing the
proliferation of disease vectors such as dengue, malaria, and
yellow fever. Fig. 4a shows the evolution of weekly average
number of larvae developed for each type of solution. The result
demonstrates the eciency of the catalyst system in inhibiting
the proliferation of insect larvae, probably due to the
consumption of organic matter in the aqueous medium. The

Larvae eradication experiments: (a) prole of larvae death over

a long time period (blank sucrose solution; catalyst 1 bleach +
sucrose solution; catalyst 2 a-Fe2O3 supported (12 g) + sucrose
solution; catalyst 3 a-Fe2O3 supported (25 g) + sucrose solution. (b)
Energy proles for the ionization and decomposition of one and two
isolated water molecules.
Fig. 4

Generation of radical species through catalysts under UV-light

irradiation followed by ESI-MS spectroscopy on positive mode.

Fig. 2

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sample with only sucrose solution showed the highest number

of dengue larvae (see black dots) while no larvae were observed
in the sample containing bleach solution besides sucrose before
7 weeks. Between 7 and 9 weeks, some larvae developed
(Fig. 4a), presumably due to a lower light incidence or the
elapsed presence of rain in this period. However, it is well
known that bleach solution is not environmentally friendly. In
addition, its use can be diluted, in principle, during rainy
seasons or by any other water supply. Accordingly, in the
following weeks (until the time analyzed) one observes a loss of
eciency of the bleach action process due to the appearance of
about 100 larvae. Also, bleach comprised of hypochlorite
(ClO
) and oen NaOH as a stabilizing agent is photolabile
and decomposes relatively fast upon exposure to sunlight for 8 h
and soon losing its oxidative ability. This result can, in principle, address a useful advantage of our photocatalytic system.
In the case of the proposed approach using a-Fe2O3 dispersed
on the support material, one can observe that a total elimination of larvae occurred in both quantities namely 12 and 25 g
employed in the support. Clearly, for both concentrations (blue
and green symbols) total elimination of larvae was observed,
demonstrating a quite ecient method for eradicating Aedes A
aegypti and avoiding possible proliferation.
The general mechanism of this photocatalysis11 requires the
semiconductor excitation with light, followed by the formation
of an electronhole pair on the surface of the catalyst. The
hydroxyl radical cOH is formed by the photocatalytic decomposition of water in the presence of the activating Fe2O3 matrix
or by the reaction with the anion OH. The radical cOH is
extremely strong and non-selective oxidant, which partially or
completely decomposes various organic molecules and this
characteristic can be exploited to aid in the elimination of
vectors such as those of dengue, malaria, yellow fever, West Nile
fever, lariasis, and mosquito-borne encephalitis as well as
chikungunya antilles.
The highly oxidizing radical may act on the eradication of
dengue by three main mechanisms: (i) promoting the oxidation
of organic matter decreasing food for the larvae; (ii) reacting
directly with the larvae or mosquito eggs, attacking cell walls of
these species or even (iii) reducing the possibility of larvae to
access oxygen at the water surface. The ionization of water leads
to its decomposition into OH radicals, since the H2O+ cation
formed at the FrankCondon geometry is unstable (Fig. 4b). On
the other hand, the potential energy of the OH species shows a
minimum both in the anion and radical forms and does not
decompose. Water theoretical decomposition studies have
illustrated the isolate molecule in the gas phase. From the
theoretical point of view, it is interesting to note that an isolated
water molecule would not decompose,18 but rather dissociates
to OH+(X3S) + H(2S). The formation of an H+ ion is only stable in
the presence of another water molecule to accept it.
The catalyst was also eective in preventing the eggs from
hatching. In the presence of the dengue larvae (provided by the
local Brazilian government) and sunlight, but in the absence of
catalyst the experiments show, as expected, the generation of
dengue larvae (see the arrows in Fig. 4a). On the other hand, in
the presence of the catalyst under sunlight (Fig. 4b) there was no

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dengue larvae growth. These results show that the proposed

process completely inhibits the formation of the larvae due to
the in situ generation of hydroxyl radicals through a photocatalytic process. As inferred from M
ossbauer spectroscopy, the
iron species are highly dispersed on the surface of the porous
support matrix resulting in very small sized particles. Moreover,
one should consider the fact that the materials have a lower
density than water, the materials are oating, which means that
the light absorption is maximized facilitating the photocatalytic
process. Evidence of radical action was seen through optical
microscopy in Fig. S2.
For the present study live larvae (le column in Fig. S2) and
larvae killed by the action of the catalyst under sunlight (the two
columns to the right in Fig. S2) were chosen. The images show
that for live larvae, not very obvious spots are observed. On the
other hand, in the images of dead larvae, sharp spots are easily
seen (indicated by arrows), which may be attributed to reactions
with radicals generated by the photocatalytic process. Nene
et al. 2007 (ref. 7) pointed out that mosquito management is
currently the only prevention option for incidence of dengue.
Such an approach may not provide an ecient method to
eradicate it. However, our process may contribute to better solve
this larvae proliferation that produces the Aedes aegypti. Actually, it provides a methodology that causes the death of larvae in
all their stages of development before becoming a mosquito.
Actually, the process described herein parallels one of Mother
Nature's means to control mosquito populations, since the
action of cOH radicals on the decreasing of larvae proliferation
is known and occurs naturally in the Rio Negro, which is an
Amazon River tributary in northern Brazil. It has been shown18
that a large amount of Chromobacterium Violaceum bacteria
(Bacillus violaceus) has photobiological action, generating free
radicals that prevent the proliferation of not only dengue larvae,
but those of yellow fever and malaria. Thus, although the

Hatching tests. (a) Tests under sunlight in the absence of PT

material. (b) The presence of PT.

Fig. 5

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dengue incidence is high in north of Brazil (Amazon), the region

around the Rio Negro does not present a high incidence of the
disease. In this work we imitate nature, which promotes a
controlled and ecient way to generate cOH radicals,19 which
preclude A aegypti eggs from hatching and also kill the
mosquito's larvae (Fig. 5).

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Conclusions
In summary, here we have presented a very eective procedure
to prevent the hatching of dengue larvae and also to kill larvae
already hatched. The generation of hydroxyl radicals by the iron
oxide-based catalyst deposited over a oating autoclaved brick
act on dengue larvae. Similarly, it also prevents the eggs from
hatching by direct attack of the radical cOH. A major advantage
of the present approach is the generation of this radical by
excitation of the iron catalyst by solar radiation and this photocatalytic reaction has the particular advantage of occurring at
the water surface. This makes the whole process a low cost
procedure and hence can be widely used by the population with
a capacity for a large-scale application of it.

Acknowledgements
This work was supported by the CNPq, FAPEMIG, CAPES and
PRPq (UFMG). V
ertica Servios e Tecnologia Eireli.

Notes and references

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