Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-022-19737-3

REVIEW ARTICLE

Degradation features of pesticides: a review on (metallo)

porphyrin‑mediated catalytic processes
Dayse Carvalho da Silva Martins1 · Iasmin Tavares Resende1 · Bruno José Rocha da Silva1

Received: 12 November 2021 / Accepted: 11 March 2022

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
Pesticides have been used to kill pests such as insects, fungi, rodents, and unwanted plants. Since these compounds are poten-
tially toxic to the target organisms, they could also be harmful to human health and the environment. Several chronic adverse
effects have been identified even after months or years of exposure. A few pesticide degradation processes have been studied
including adsorption, homogeneous and heterogeneous (photo)catalytic oxidation, and biological methods. Although these
methods have been playing a significant part in the pesticide’s degradation, there are still gaps in many aspects. Here, we
review the catalytic degradation of these pollutants by (metallo)porphyrins. To evaluate the P450 cytochrome’s biomimetic
behavior of these catalysts, various synthesized porphyrins have been used since 1999 and their activities were summarized
in this manuscript. The porphyrins appear to act as good catalysts for the degradation of pesticides; in fact, they also have
been shown as a useful tool for the elucidation of their degradation products. Achieving pesticide mineralization without
intermediate products is still challenging, although the ability of this kind of catalysts to conduct the formation of some
lower toxic products comparing their precursors has been verified.

Keywords  Catalysis · Biomimetic systems · Metabolites · P450 cytochromes · Pesticides · Environment

Introduction producing less harmful pesticides, given that research is very

The constant growth of industrialization and the world popu-
lation has led to a great demand for agricultural processes for
the development of food production. As a result, large-scale
use of various types of pesticides can be observed and, from
an environmental point of view, there is a growing investiga-
tion into the behavior of these substances and their harmful
effects on the ecosystem (Lushchak et al. 2018; Nagy et al.
2020; Shefali et al. 2021).
Some studies have shown that pesticides had a benefit-
cost ratio highly overestimated, while others pointed out that
less than 5% of the applied pesticide arrives at the target
(Zadoks and Waibel 2000). In addition, for the time being,
there seems to be low interest by the agriculture industry in
Responsible Editor: Santiago V. Luis
* Dayse Carvalho da Silva Martins
daysequimica@ufmg.br
1
Departamento de Química, Instituto de Ciências Exatas,
Universidade Federal de Minas Gerais, Belo Horizonte,
MG 31270‑901, Brazil
expensive (150 million Euro per new compound) (Zadoks
and Waibel 2000); moreover, since there is a huge monopoly
of the seeds used in agriculture, crops are becoming resist-
ant to pesticides, which increases the need of this product
for the same results, making a “chemically dependent agri-
culture” (Hayes and Hansen 2017). Furthermore, certain
plague species have also developed pesticide resistance (in
fact, by 1980, more than 400 insects and arthropods species
were already known to be resistant to pesticides (Hayes and
Hansen 2017)), as well as the use of these chemicals, had
led to the elimination of beneficial species that previously
established mutualistic relationships with the crop, which
could induce other opportunistic species to become “second-
ary pests,” regaining the problem.
Environmental contamination occurs mainly in soil and
water since the problems arising from the use of pesticides
are constantly linked to agricultural practice. These sub-
stances are often dissolved in water or adsorbed onto parti-
cles and, through erosion or surface runoff, are destined for
surface and groundwater (Stuart et al. 2012; Gavrilescu et al.
2015; Lushchak et al. 2018). In addition, pesticides with
high lipophilicity are prone to bioaccumulation, and thus

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contamination can extend to an entire ecosystem and result
in toxicological problems.
Bioaccumulation makes aquatic organisms the main
targets of these substances and can occur through direct
absorption of water, absorption of suspended particles, or
consumption of contaminated food (Lushchak et al. 2018).
Thus, many studies point out the various toxic effects of
pesticides, and among them, we can highlight endocrine
disturbances (Hayes et al. 2002), changes in liver metabo-
lism (Xing et al. 2014), and genotoxic effects (Özgür 2019)
mainly in fish and frogs, although these risks extend to
several other organisms such as algae, mollusks, reptiles,
amphibians, and between others (Singh et al. 2018). Besides,
contaminations such as these can extend to other animals
in the food chain, namely birds, which can cause embryo-
toxic and immunotoxic damage (Buck et al. 2020), as well
as mammals, which can cause carcinogenic, teratogenic,
and genotoxic effects (Lushchak et al. 2018). In humans,
studies report the association of exposure to pesticides with
different categories of diseases such as carcinogenicity, neu-
rotoxicity, pulmonary toxicity, reproductive toxicity, devel-
opmental toxicity, and metabolic toxicity indicating several
mechanisms and induction pathways for the development of
diseases (Mostafalou and Abdollahi 2013, 2017).
Pesticides can often be even more toxic in their commer-
cial formulations, due to synergistic effects of the formula-
tion, than the active ingredient alone (Nagy et al. 2020) and
although many of these substances are persistent, their deg-
radation products must also receive attention, since they are
found in the ecosystem together with the original products
and may have similar toxicity (Kolpin et al. 1998).
Thus, a handful number of studies reported chemicals
that have been verified as pesticide degradants. The main
methods for removing pesticides from water and soil are
photocatalytic degradation (Cui et al. 2021; Kaur and Kaur
2021), photo-Fenton (Chiron et al. 2000), biological oxida-
tion (Singhal et al. 2021), advanced oxidation process (Jatoi
et al. 2021), electrochemical (Trellu et al. 2021), ozonation
(Ikehata and El-Din 2005a, b), and adsorption (Andrunik
and Bajda 2021), each having their own up- and shortcom-
ings in economic, efficiency, and scalability aspects. In this
context, it could be highlighted (metallo)porphyrin com-
pounds which have been showing promising degradation
yields for several pesticides, such as atrazine (ATZ), atra-
ton, and mecoprop, alongside being faithfully biomimetic
systems.
A porphyrin is a ring composed of four pyrrole groups
as in Fig.  1, and in the absence of any metal ion, this
chemical compound is called a “free base porphyrin.” A
transition metal ion (in the concern of pesticide degrada-
tion, mostly Fe or Mn) can also be placed in the porphy-
rin core, as well as meso- and β-substituents, changing
their physical-chemical and catalytic properties. In nature,
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Environmental Science and Pollution Research
porphyrins can be found as the reactive centers of pro-
teins responsible for oxygen transportation (erythrocytes),
electron transport chain (cytochromes), and substrates’
oxidation (oxygenases), thus explaining their potential
application as biomimetic synthetic systems. As known,
reproducing in vivo structures can be chemically hard, and
a lot of studies with synthetic porphyrins have been shown
that these compounds could be used to mimic these com-
plex systems to degrade some pollutants such as drugs and
pesticides (Zanatta et al. 2016).
The utilization of metalloporphyrin-based materials on
the degradation reactions of many pollutants has demon-
strated to be a very convenient tool to elucidate the contami-
nant transformation (Bernadou and Meunier 2004; Lohmann
and Karst 2008; Zanatta et al. 2016). Many studies have been
carried out to describe the degradation of different pharma-
ceuticals and pesticides mediated by metalloporphyrins. The
use of these catalysts as biomimetic models in degradative
metabolism studies presents some advantages over standard
in vitro methods (Lohmann and Karst, 2008; Hubin et al.
2000; Chorghade et al. 1996, Vidal et al. 1993; Bernadou
et al. 1991; Komuro et al. 1996; Melo et al. 2005; Bernadou
and Meunier 2004; Mansuy 2007): it has been possible to
allow the obtaining of certain metabolites/products in suffi-
cient amounts and with sufficient purity to permit characteri-
zation and further pharmacological and toxicological tests
(Mansuy 2007) (see Fig. 1), and those biomimetic studies
can minimize the problems associated with the use of a large
number of living animals in experimental research (Berna-
dou and Meunier 2004). The potentiality of bioinspired syn-
thetic porphyrins to catalyze pollutant degradation, such as
pesticides, under mild experimental conditions (standard
pressure, room temperature, using some environmental-
friendly oxidant), could be more investigated.
Study design
This is a review designed to investigate all the studies that
attempted to degrade pesticides using porphyrinic catalysts.
All available databases were searched for peer-reviewed
research journal articles. Review articles, letters to the edi-
tor, and book chapters were excluded from the search. Fif-
teen eligible articles were obtained, and we performed a
data abstraction to collect selected information from them.
This information included the biomimetic behavior, the for-
mation of different products from metabolites, the capacity
of mineralization, the porphyrin type (free base or metal-
lated), and catalysis type (homogeneous or heterogenized).
Data extraction was performed using an online spreadsheet
(Google). A comprehensive literature analysis was per-
formed to overview the detailed classification of pesticides
Environmental Science and Pollution Research
Fig. 1  Schematic diagram to clearly show the principle of porphy-
rin-mediated pesticide degradation. A free base porphyrin can be
obtained by replacing “M” with two hydrogen atoms; by substituting
studied, as summarized in Table 1. The following sections
and subsections were designed and examined with proper
pesticides as a core of this review.
Pesticide degradation by (metallo)
porphyrins
Although the first studies on the degradation of pesticides
date to the end of the 1960s (Chacko et al. 1966; Casida
and Fukunaga 1968; Li and Bradley 1969), to the best of
our knowledge, the first report of a study on degradation
of these kinds of contaminants by porphyrin catalysts has
not more than 25 years old. Keserü and coworkers (Keserü
et al. 1999) started studies in this area, introducing some
important questions which could be the start point to the
development of this field of research. Their research was
motivated by three questions “(1) Can chemical models be
used to mimic the CP450-catalyzed oxidative metabolism
of carbamate insecticides? (2) Can metabolically sensitive
functional groups be identified in this way? (3) Do these
model systems adequately reproduce experimental meta-
bolic profiles?” (literal copying from Keserü and cowork-
ers (Keserü et al. 1999), p. 762). These issues can be seen
as the fundamental pillars that support the research that
followed and that will be discussed in this review. After
the publication of these articles since Keserü’s first work,
we hope that we could have a better vision of how these
“M” with a transition metal ion, a metalloporphyrin will be created.
­R1 and ­R2 designated positions that could be replaced to form differ-
ent porphyrin catalysts
questions can be answered and this survey could help all
the porphyrinic community to think about the next steps
of this kind of work.
In total, 20 pesticides have been attempted to be
removed by porphyrin-mediated degradation (Table 1) in
fifteen manuscripts (Fig. 2). The most studied compound
was atrazine, which is an active ingredient for herbicides
and has been recorded in 47% of our records. As we
already said, pesticides have been classified into differ-
ent categories, and we separated them according to the
chemical type as described in the WHO Recommended
Classification of Pesticides by Hazard and Guidelines to
Classification (WHO 2019) and including the organochlo-
rine compounds as a category. According to these crite-
ria, we are going to discuss the pesticides in five groups,
namely: (a) carbamates; (b) organophosphorus compound;
(c) triazine derivative (with emphasis on atrazine, the most
studied pesticide so far); (d) organochlorine compounds;
and (e) others (non-categorized by the WHO).
Carbamates
Carbamates are ester compounds derived from carbamic
acids, and they have been extensively used in agriculture,
household, and for industrial purposes as insecticides,
aphicides, herbicides, fungicides, nematicides, mollus-
cicides, and acaricides. Despite some carbamates being
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Table 1  Classification overview of pesticide degraded by (metallo)porphyrins

Toxicity Chemical
Main use/
according classification
Identification
Pesticide Chemical structure to WHO according to
(CAS
(WHO WHO (WHO
number)
2019) 2019)

Moderately
Insecticide /
Carbaryl hazardous Carbamate
63-25-2
(Class II)

Highly
Insecticide /
Carbofuran hazardous Carbamate
1563-66-2
(Class Ib)

Moderately
Aphicide /
Pirimicarb hazardous Carbamate
23103-98-2
(Class II)

Slightly
Herbicide /
Atrazine hazardous Triazine derivative
1912-24-9
(Class III)

Pesticides
unlikely to
Herbicide / present
Simazine Triazine derivative
122-34-9 acute hazard
in normal
use

Moderately
Herbicide /
Ametryn hazardous Triazine derivative
834-12-8
(Class II)

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Table 1  (continued)

Moderately
Herbicide /
Metribuzin hazardous a
21087-64-9
(Class II)

Active
ingredients
believed to
be obsolete
Atraton 1610-17-9 or a
discontinued
for use as
pesticides

Moderately
Herbicide / Organophosphorus
Butamifos hazardous
36335-67-8 compound
(Class II)

Moderately
Insecticide / Organophosphorus
Cyanophos hazardous
2636-26-2 compound
(Class II)

Pesticides
unlikely to
Fungicide
Tolclofos- present
applied to soil b
Methyl acute hazard
/ 57018-04-9
in normal
use

Highly
Nematocide / Organophosphorus
Fenamiphos hazardous
22224-92-6 compound
(Class Ib)

Insecticide, Moderately
Organophosphorus
Fenthion larvicide / 55- hazardous
compound
38-9 (Class II)

Moderately
Insecticide / Organophosphorus
Fenitrothion hazardous
122-14-5 compound
(Class II)

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Table 1  (continued)
Active
ingredients
believed to
Insecticide / be obsolete
Dieldrin c
60-57-1 or
discontinued
for use as
pesticides
Pesticides
unlikely to
Insecticide / present
Pyriproxyfen d
95737-68-1 acute hazard
in normal
use

Moderately
Herbicide /
Mecoprop hazardous d
7085-19-0
(Class II)

Slightly
Diuron Herbicide /
hazardous d
(Direx) 330-54-1
(Class III)

2,3,5-
697-82-5 - d
trimethylphenol

2,4,6-
trimethylphenol 527-60-6 - d
(Mesitol)

a
 Pesticides discussed at the triazine’s group; bpesticides discussed at the organophosphorus compounds’ group; cpesticides discussed at the
organochlorine compounds’ group; and dpesticides discussed at “Other pesticides” group.

easier to break down, with also having low bioaccumu-
lation, and less persistence, it has been shown that the
adverse effects caused by these pesticides include hepatic,
immune, neurological, reproductive renal, and metabolic
functions in humans and animals (Dias et al. 2015).
The three studied carbamates were carbaryl, car-
bofuran, and pirimicarb (Table  1), and they present
moderately a highly hazardous according to the WHO.
Keserü and coworkers (Keserü et al. 1999) developed a
homogeneous system with an iron porphyrin, the meso-
tetrakis(2,6-dichlorophenyl)porphyrin iron(III) chloride
(Supplementary material), associated with three dif-
ferent oxygen donors ­( H 2O 2, NaOCl, and m-CPBA) to
degrade these carbamates. The reactions were performed
for 30 min and, although it did not lead to contaminant
mineralization (and < 50% of carbamates degradation),
it caused its degradation with the formation of known
metabolism products, as can be seen in Fig. 3. It is impor-
tant to highlight that the catalytic system was capable to
mimic the already known P450 reactions such as N-dem-
ethylation, hydroxylation, and oxidation. In addition, the
porphyrin catalyst was able to lead to the formation of

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Fig. 2  Timeline of published
studies on pesticide degradation
mediated by porphyrins and
metalloporphyrins
not expected products for the metabolism of the studied
compounds (as can be seen in Fig. 3 for pirimicarb in the
dotted arrow) through reactions also known to be per-
formed by P450 cytochromes and mimicked by synthetic
porphyrin catalysts.
These authors (Keserü et al. 1999), responsible for the
only work involving the degradation of carbamates medi-
ated by porphyrin catalysts, are the rocket scientists that
opened the doors to the development of a research field of
porphyrin-mediated pesticide degradation as could be veri-
fied in this review.
Organophosphorus compounds
The organophosphorus compounds are used worldwide,
exhibiting acute and potential chronic toxicity to humans
and the environment. Most of the studied pesticides were
organophosphorus (six) although we have only two studies
in the literature describing the degradation of these com-
pounds by porphyrin catalysts (Fujisawa and Katagi 2005;
Silva et al. 2010).
Fujisawa and Katagi (Fujisawa and Katagi 2005) per-
formed the first porphyrin-mediated organophosphorus
degradation. They carried out the homogenous catalysis for
five pesticides (butamifos, cyanophos, fenitrothion, fenthion,
and tolclofos-methyl; Fig. 4) by hydrogen peroxide and three
iron metalloporphyrins: meso-tetrakis(pentafluorophenyl)
porphyrin iron(III) chloride, meso-tetrakis(2,6-dichloro-
phenyl)porphyrin iron(III) chloride, and meso-tetrakis(2,6-
dichlorophenyl)-β-octabromoporphyrin iron (III) chloride
(Supplementary material).
The authors performed a very elegant study in which they
followed the catalytic performance of the catalysts through
reactions carried out in homogeneous systems monitoring
their rate constants and theoretical analysis. According to
the authors, the degradation profiles were common to feni-
trothion, cyanophos, tolclofos-methyl, and butamifos not
taking porphyrins used into account. Moreover, two degra-
dation pathways were predominant for these organophospho-
rus compounds: oxidative cleavage of the P–O-aryl bond and
oxidative desulfuration (Fig. 4). The degradation profile for
fenthion was much different for the others, in which the pes-
ticide suffered oxidation of the thiomethyl group followed
by an oxidative desulfuration, followed by cleavage of the
P–O-aryl linkage (Fig. 4).
As previously noted for carbamates, the iron porphyrin
mediated did not lead to contaminant mineralization in all
systems, it caused high degradation levels of them (60–100%
of organophosphorus compounds’ degradation) associated
with metabolic products’ formation. The authors said, at the
end of their manuscript that “Although our system could not
fully demonstrate the metabolic oxidation catalyzed by P450,
it was found to be very useful for estimating the primary oxida-
tion reaction of an organophosphorus pesticide by the simple
in vitro method” (literal copying from Fujisawa and Katagi
(Fujisawa and Katagi 2005), p. 109). It is important to highlight
that these models are relevant not only for mimicking the P450
system but to predict the formation of unexpected products, as
could be seen for the next organophosphorus compound.
The sixth compound studied was the fenamiphos (Fig. 4),
by Silva and coworkers (Silva et al. 2010) which performed
the photocatalysis of three pesticides (two of them will be
discussed in the “Others” group). The carried out reac-
tions using meso-tetrakis(2-fluorophenyl)porphyrin, meso-
tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP), and their
copper complexes (Supplementary material) immobilized
within MCM-41 mesoporous molecular sieve to be evaluated
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Table 2  Summary of representative catalytic porphyrin systems and their performance at the pesticides’ degradation

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Table 2  (continued)

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Table 2  (continued)

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Table 2  (continued)
a
 Chemical structure representation for all (metallo)porphyrins are presented in the supplementary material. bHO homogenous system, HE het-
erogeneous system. cMaximum degree of degradation . dNon cytotoxic product. e Product distribution only.
as photocatalysts. They monitored the disappearance of the
substrate and formation of the products and observed the
dependence of fenamiphos’ photodegradation on the oxygen
concentration. They achieved up to 60% of fenamiphos’ deg-
radation and observed two products (Fig. 4) that are still not
recognized as its metabolites. As mentioned above (at literal
copying from Fujisawa and Katagi (Fujisawa and Katagi
2005), p. 109), the results are extremely relevant in the sense
of being predictors by a simple in vitro procedure.
Triazine derivatives
Triazines are a set of six-membered conjugated car-
bon–nitrogen atom cyclic rings that presented a lot of phar-
macological properties. The 1,3,5-triazines, such as the
pesticides described here (atraton, ametryn, simazine, and
atrazine; Figs. 5 and 6), are one of the most studied among
the isomeric forms of triazine. When applied to the soil,
these compounds can be absorbed through roots, thus inhib-
iting photosynthesis once the plant has emerged (Jepson
2001). Although these triazines are classified as slightly or
moderately hazardous (except atraton that was considered as
obsolete or discontinued for use as pesticides by the WHO)
and present low acute toxicity in most animal species, the
chronic exposures to them are animal carcinogens (Horsak
et al. 1964). There is another herbicide, the metribuzin, a
1,2,4-triazine (Fig. 5), which is not classified as a triazine
by the WHO but clearly could be incorporated in this group
as also being moderately hazardous.
Atrazine is the most studied triazine in this group of pes-
ticides, being presented in seven manuscripts (Héquet et al.
2000; Gotardo et al. 2006; Granados-Oliveros et al. 2009;
Nelkenbaum et al. 2009; Rebelo et al. 2007, 2009; Almeida
Lage et al. 2019), and it was the first triazine to be degraded
by (metallo)porphyrin catalysts. Despite that, we will leave
its discussion to the end of this section.
The degradation of ametryn was studied by Rebelo et al.
through two different systems: (a) the first one was carried
out in the presence of 5,10,15,20-tetrakis(2,6-dichloro-3-sul-
fophenyl)porphyrin or 5,10,15,20-tetrakis(4-sulfophenyl)
porphyrin complexes (Supplementary material) as photo-
catalyst (Rebelo et al. 2007) and (b) the second was carried
out with Fe(TPFPP)Cl and Mn(TDCPP)Cl complexes (Sup-
plementary material) in the presence of hydrogen peroxide
(Rebelo et al. 2009). The photocatalytic degradation of ame-
tryn was performed in neutral water solution, during 120 h
of irradiation at 350 nm, and the catalysts led to 40 and 60%
of the pesticide degradation possibly through two different
mechanisms. Experiments using the singlet oxygen scav-
engers ­NaN3 could show that the 5,10,15,20-tetrakis(2,6-
dichloro-3-sulfophenyl)porphyrin act through a mechanism
involving singlet oxygen, and this porphyrin was less self-
degraded in the reaction medium than the other catalyst
(42% of porphyrin degradation versus a full degradation).
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Fig. 3  Metabolites and products produced from carbamates catalyzed by porphyrins under synthetic models (solid dark arrow, plant and/or ani-
mal metabolism; broken gray arrow, porphyrin-catalyzed degradation) (Keserü et al. 1999)

The catalytic systems employing metalloporphyrins have
shown to be more efficient than those without the catalysts.
Reactions achieved the complete conversion of ametryn at
3 or 12 h, and some systems were selective for only one
product. None of the observed products for both studies were
known as ametryn metabolites (Fig. 5).
Atraton was also studied by Rebelo and coworkers (Rebelo
et al. 2009), using the same manganese catalyst cited in the
previous paragraph. They could observe 98% of degradation
of this triazine at 9 h associated with high selectivity to one
of three products. In the absence of the catalyst, only 4%
of atraton conversion was observed which highlighted the
importance of the use of this kind of catalyst. For this tria-
zine, none of the observed products are known as metabolites.
The herbicide simazine degradation was carried out
in the presence of six different metalloporphyrins—
5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin metal(III)
chloride; 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin
metal(III) chloride; and 5,10,15,20-tetrakis(pentafluoroph
enyl)porphyrin metal(III) chloride (metal: Fe or Mn) (Sup-
plementary material)—and three oxygen donors ­(H2O2,
m-CPBA, and PhIO). Santos and coworkers (Santos et al.
2011) performed this study associating each catalyst to each
oxygen donor, varying the catalyst:oxidant:simazine molar

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Fig. 4  Metabolites and products produced from organophosphorus compounds catalyzed by porphyrins under synthetic models (solid dark
arrow, plant and/or animal metabolism; broken gray arrow, porphyrin-catalyzed degradation) (Fujisawa and Katagi 2005; Silva et al. 2010)
ratio, and evaluating the axial ligand effect as co-catalyst.
They could achieve up to 49% of simazine degradation
and the observed seven products of which five are known
metabolites (Fig. 5).
The biomimetic degradation of metribuzin with hydro-
gen peroxide was performed catalyzed by 5,10,15,20-tetr
aarylporphyrinatoiron(III) chloride (Supplementary mate-
rial), under various reaction conditions. Chauhan and
Kumari (Chauhan and Kumari 2007) studied the effect of
time, catalyst:oxidant:metribuzin molar ratio, the presence
of a co-catalyst, and the solvent effect. They observed the
formation of four metabolites and the reactions achieved up
to 62% of degradation in 1 h.
While most of the pesticides had been studied at one or
two systems, atrazine’s degradation by (metallo)porphy-
rin had been described in seven different papers (Héquet
et  al. 2000; Gotardo et  al. 2006; Granados-Oliveros
et al. 2009; Nelkenbaum et al. 2009; Rebelo et al., 2007,
2009; Almeida Lage et al. 2019), achieving its total degra-
dation. This pesticide has been degraded in some distinct
ways. The first study of atrazine degradation mediated by
porphyrins was reported by Héquet and coworkers (Héquet
et al. 2000) that used hemin (an iron porphyrin) supported
on Amberlite resin. The photocatalytic degradation of
atrazine under visible (and simulated solar) light by the
heterogenized catalyst was compared to that observed for
­TiO2; the porphyrinic catalyst has shown better perfor-
mance and they could identify eight products, including
some metabolites. This was not the only photocatalytic
study for degrade atrazine. Rebelo and coworkers (Rebelo
et al. 2007) and Granados-Oliveros and coworkers (Gra-
nados-Oliveros et al. 2009) have studied water-soluble
porphyrins and metalloporphyrins supported on ­TiO 2,
respectively. They first employed free base porphyrins,
and they proposed that the mechanism could involve the
formation of a superoxide radical anion, and, although it
depends on the oxygen presence, there is no formation of
oxygen singlet. The latter study has presented the photo-
degradation by iron, copper, zinc, and free base porphyrins
supported on titanium dioxide which have a mechanism
mediated by superoxide radical anion and hydroxyl radi-
cal. The porphyrins adsorbed on the ­TiO2 surface kept a
good photocatalytic activity even after six reaction runs.
Nelkenbaum and coworkers (Nelkenbaum et al. 2009)
performed a different way to degrade atrazine. They have
used nickel and cobalt porphyrins in a dechlorination reac-
tion system. Besides the dehalogenation of atrazine, the
authors could verify a migration of a methyl group from the
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Fig. 5  Metabolites and products

produced from triazine deriva-
tives catalyzed by porphyrins
under synthetic models (solid
dark arrow, plant and/or animal
metabolism; broken gray arrow,
porphyrin-catalyzed degrada-
tion) (Chauhan and Kumari
2007; Rebelo et al. 2007, 2009;
Santos et al. 2011)

isopropyl chain to the chlorine atom place to form selec-
tively a symmetric molecule.
The other studies were performed through a more biomi-
metic model, by using manganese and iron porphyrins and
the already known oxygen donors (iodosylbenzene, meta-
chloroperbenzoic acid, hydrogen peroxide, iodobenzene
diacetate, Oxone®, and tert-butyl hydroperoxide). Gotardo
and coworkers (Gotardo et al. 2006) have shown that atrazine
degradation could not be performed in methanol since this
solvent competes with the pesticide, and it oxidated to yield
formaldehyde; they also could show the product distribution
is dependent on the reaction conditions such as the solvent.
Rebelo and coworkers (Rebelo et al. 2009) have shown that
the correct choice of the reaction conditions could orientate
the results to a great agreement with the invivo and invitro
reports. Lage and coworkers (Lage et al. 2019) performed
a reaction in acetonitrile medium, verifying good degrada-
tion levels; they also performed atrazine degradation in a
real water effluent, and the catalyst performances were better
than those observed for acetonitrile systems. These authors
analyzed the toxicity of the degradation products, and they
could observe that the studied systems were not cytotoxic
under the evaluated conditions.
The majority of the studies on atrazine degradation (not
only those with porphyrins) report its metabolism associated
with the N-dealkylation (partial or total), but some of these
seven different papers (Héquet et al. 2000; Gotardo et al.
2006; Granados-Oliveros et al. 2009; Nelkenbaum et al.
2009; Rebelo et al.2007, 2009; Almeida Lage et al. 2019)
could show distinct products (Fig. 6), including molecules
which had been observed as atrazine’s metabolites (Rob-
erts et al. 1998; Aizawa 2001).
Organochlorine compound
Although the WHO Recommended Classification of Pes-
ticides by Hazard and Guidelines to Classification does
not present a group for chlorinated pesticides, dieldrin is
discussed in this section since it represents a kind of typi-
cal and highly toxic pesticide pollutant.

13
Environmental Science and Pollution Research
Fig. 6  Metabolites and prod-
ucts produced from atrazine
catalyzed by porphyrins under
synthetic models (Héquet et al.
2000; Gotardo et al. 2006;
Granados-Oliveros et al. 2009;
Nelkenbaum et al. 2009; Rebelo
et al. 2007, 2009; Almeida Lage
et al. 2019)
In the same way as the atraton, dieldrin is considered
obsolete or discontinued for use as pesticides since 2003
by the WHO. According to the WHO Recommended Clas-
sification of Pesticides by Hazard and Guidelines to Clas-
sification (WHO 2019), its use and production are prohib-
ited or severely restricted by the Stockholm Convention
on persistent organic pollutants. When Hino and Dolphin
(Hino and Dolphin 1999) carried out its degradation medi-
ated by polyhalogenated metalloporphyrins, this restric-
tion had not yet been imposed. They used iron and manga-
nese porphyrin (Supplementary material) to degrade this
pesticide using different solvents and oxygen donors. Their
catalytic systems surpass even the Fenton process, and
they could observe the formation of two metabolites and
one different product (Fig. 7).
Although the pesticides mecoprop and diuron (Table 1)
could be grouped in this category for having chlorine in
their chemical structure, in the literature these compounds
have been classified according to their chemical nature
at the phenyl amide and the phenoxyalkonate group,
respectively. Because of that, they are discussed in the
“Other pesticides” section.
Other pesticides
This last group comprises the compounds that are not chemi-
cally classified according to the WHO: mecoprop, diuron
(Direx), pyriproxyfen, 2,3,5-trimethylphenol, and 2,4,6-tri-
methylphenol (mesitol). Despite this, some of them could
be classified as organochlorine compounds (dieldrin, meco-
prop, diuron) or phenoxyacetic acid derivatives (mecocrop).
The herbicide diuron (classified according to its chemical
nature at the phenyl amide group; Jayaraj et al. 2016), slightly
hazardous, was studied by Silva and coworkers (Silva et al.
2010) by using porphyrins immobilized within MCM-41
mesoporous molecular sieve (Supplementary material) to be
evaluated as photocatalysts as already mentioned for fenami-
phos. Although the study has been more detailed for the other
pesticides, the results for diuron were preliminary, and the
authors noted the formation of products/metabolites previously
13

Fig. 7  Metabolites and products produced from dieldrin catalyzed
by porphyrins under synthetic models (solid dark arrow, plant and/or
animal metabolism; broken gray arrow, porphyrin-catalyzed degrada-
tion) (Hino and Dolphin 1999)
described for this pesticide (Fig. 8) as well as the possibility of
reusing the catalyst in more than one catalytic cycle.
The degradation of the moderately hazardous chlorophe-
noxy propionic acid herbicide, mecoprop (classified accord-
ing to their chemical nature at the phenoxyalkonate group;
Jayaraj et al. 2016), was performed through a photocatalytic
system employing 5,10,15,20-tetrakis-(2-fluorophenyl)por-
phyrin immobilized into MCM-41 (Supplementary mate-
rial). The authors observed a formation of several products
associated with conversions about 50% after 90 min (Silva
et al. 2009). In a homogenous system in the presence of
Mn(TDCPP)Cl or Fe(TPFPP)Cl (Supplementary material)
and hydrogen peroxide, Rebelo and coworkers (Rebelo et al.
2009) could achieve up to 100% of mecocrop degradation
producing at least four different identified products, with
only one of them known as a metabolite (Fig. 8).
Pyriproxyfen degradation was performed in a homogeneous
system mediated by 5,10,15,20-tetrakis(pentafluorophenyl)-
21H,23H-porphine iron(III) chloride (Supplementary mate-
rial) and hydrogen peroxide for 10 min. Concomitantly, the
metabolism of the pesticide was evaluated using tomato seed-
lings. Fukushima, Fujisawa, and Katagi (Fukushima et al.
2005) intended to compare those systems to check the viabil-
ity of using metalloporphyrins as a biomimetic model to well
reproduce the primary metabolites detected in the metabolism
of this pesticide (Fig. 8). They observed that the porphyrin-
catalyzed oxidation reproduced some metabolites and could
be used as a tool to predict the metabolites of pesticides.
The two last compounds, 2,3,5-trimethylphenol and
2,4,6-trimethylphenol (Mesitol), have not been described
13
Environmental Science and Pollution Research
as a pesticide at the WHO Recommended Classification of
Pesticides by Hazard and Guidelines to Classification (WHO
2019). The photodegradation of the pesticide 2,3,5-tri-
methylphenol (Table  1) was performed using catalyst
5,10,15,20-tetrakis-(2-fluorophenyl)porphyrin encapsulated
in mesoporous MCM-41 material. The authors observed up
to 50% of pesticide conversions after 90 min. 2,4,6-trimeth-
ylphenol (Table 1) was used as a model substrate for Silva
and coworkers (Silva et al. 2010) for kinetical studies, and
they observed that the degradation rate depends on the struc-
ture of the catalyst (meso-tetrakis(2-fluorophenyl)porphyrin,
meso-tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP), and
their copper complexes (Supplementary material), immobi-
lized within MCM-41 mesoporous molecular sieve). They
could suggest a mechanism singlet oxygen-independent.
Porphyrins’ use for catalytic degradation
of pesticides and perspectives
It has been demonstrated that the synthetic (metallo)por-
phyrins can be used as biomimetic catalysts bioinspired
in P450 cytochromes (Bernadou and Meunier 2004; Man-
suy 2007; Oszajca et al. 2016; Zanatta et al. 2016) by
performing known reactions such as alkane oxidation,
olefin epoxidation, aromatic hydroxylation, S-oxidation,
N-oxidation, and carbon-carbon bond cleavages. In com-
parison to studies concerning the reactivity of porphyrins
and their metallic complexes as catalysts to function-
alization of organic compounds, the porphyrin-mediated
pollutants’ degradation such as that related to pesticides
remains a less explored topic. In this way, the already
presented studies could serve as a strong inspiration for
the development of new systems for the degradation of
this type of environmental contaminant, associated with
the study of the toxicity of the observed products.
Different kinds of porphyrin have been studied and used
as homogenous or heterogenized catalysts for pesticide deg-
radation in aqueous solution, non-aqueous medium under,
buffer solution, or in a mixture of solvents. As could be veri-
fied in Table 2 and Supplementary material (Table S1), the
majority of studied porphyrins belong to the second genera-
tion of catalysts (23 catalysts versus six of the third genera-
tion, and three of the first generation).
Although most of the studied systems did not achieve pes-
ticide mineralization, it could be observed its complete con-
version into known metabolites and other products. The for-
mation of pesticides metabolites emphasizes that (metallo)
porphyrin can be used as convenient models of cytochrome
P450 for metabolic studies of new or known pesticides. They
can also be very helpful to predict the possible behavior of
these compounds in the environment. Knowing the possible
Environmental Science and Pollution Research

products from pesticides to be formed in the environment
and studying their toxicity is convenient.
In this sense, it is possible to observe the versatility of
(metallo)porphyrins to degrade pesticides belonging to differ-
ent classes, according to the WHO (2019). For example, two
of the studied porphyrins (PorfA and PorfF in Table 2 and
Table S1, Supplementary Material) have been used for differ-
ent pesticides, performing nonidentical chemical reactions.
Although heterogeneous catalysis based on porphyrins
has been developed for a long time, there are only a few stud-
ies regarding their use for pesticide degradation. To design
a heterogenized catalysis strategy for pesticide degradation
by using porphyrin molecules, some studies were performed
by supporting them in amberlite, T ­ iO2, MCM-41, and NaY
(Héquet et al. 2000; Granados-Oliveros et al. 2009; Silva
et al. 2009, 2010). In these studies, the authors had used
iron, copper, zinc, and metal-free porphyrins, and they could
show that these materials presented a better performance
when compared to the support alone. Associated with the
maintaining of the photocatalytic activity after reuses, the
heterogenized catalysts had presented insignificant decom-
position/leaching which highlighted the possibility of using
porphyrin-based materials in environmental decontamina-
tion systems.

Fig. 8  Metabolites and products

produced from other pesticides
(non-categorized by the WHO)
catalyzed by porphyrins under
synthetic models (solid dark
arrow, plant and/or animal
metabolism; broken gray arrow,
porphyrin-catalyzed degrada-
tion) (Fukushima et al. 2005;
Silva et al. 2009, 2010)

13

Over time, porphyrins have emerged as versatile cata-
lysts for pollutant degradation under mild and sustainable
reaction conditions. Although some progress has been
made, the development of catalytic systems for pesticides
degradation incorporating synthetic (metallo)porphyrins is
still in a relatively early stage. Besides the necessity of the
development of new low-cost, efficient, stable, and robust
(metallo)porphyrin catalysts, the following challenges
need to be addressed to allow in carrying out further
research in this mentioned area: to perform the toxicity
essay for the reaction’ products, to use renewable sources
of energy such as sunlight (natural and unlimited energy)
for photocatalysis, to use eco-friendly oxidizing agents
and reagents as benign approach, to produce heterogenized
porphyrin catalysts from waste materials (as support), to
rationalize the design of surface-functionalized nano-sized
materials to operate cost-effectively and environmentally
safe pesticides’ degradation, to investigate polluted sites
containing multiples pollutants at the same time to check
the activity and the efficiency of the entire system. Finally,
we hope these (metallo)porphyrin-mediated catalytic pro-
cesses could serve as powerful (photo)catalysts for the
green environmental pesticides’ degradation in associa-
tion with the current wastewater treatments.
Supplementary Information  The online version contains supplemen-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 11356-0​ 22-1​ 9737-3.
Acknowledgements  This study was partially financed by Coordenação
de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)—Finance
Code 001, Brazil; Fundação de Amparo à Pesquisa do Estado de Minas
Gerais (FAPEMIG), Minas Gerais, Brazil; Financiadora de Inovação
e Pesquisa (FINEP), Brazil; and by Conselho Nacional de Desenvolvi-
mento Científico e Tecnológico (CNPq), Brazil. The authors thank
anonymous reviewers for their helpful comments that improved the
manuscript.
Author contribution  DCSM had the idea for the article; DCSM,
ITR, and BJRS performed the literature search and data analysis; and
DCSM, ITR, and BJRS drafted and critically revised the work.
Funding  This study was partially financed by Coordenação de Aper-
feiçoamento de Pessoal de Nível Superior (CAPES)—Finance Code
001, Brazil; Fundação de Amparo à Pesquisa do Estado de Minas Ger-
ais (FAPEMIG), Minas Gerais, Brazil; Financiadora de Inovação e
Pesquisa (FINEP), Brazil; and Conselho Nacional de Desenvolvimento
Científico e Tecnológico (CNPq), Brazil.
Data availability  Not applicable.
Declarations  as biomimetic models for cytochrome P-450 in the oxidation of
Ethics approval and consent to participate  Not applicable.
Consent for publication  Not applicable.
Competing interests  The authors declare no competing interests.
13
Environmental Science and Pollution Research
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