Journal of Environmental Chemical Engineering 9 (2021) 104558

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Endocrine-disrupting compounds: Occurrence, detection methods, effects

and promising treatment pathways—A critical review
Wedja Timóteo Vieira, Marina Barbosa de Farias, Marcela Pires Spaolonzi,
Meuris Gurgel Carlos da Silva, Melissa Gurgel Adeodato Vieira *
Department of Processes and Products Design, School of Chemical Engineering, University of Campinas (UNICAMP), Albert Einstein Avenue, 500, 13083-852 Campinas,
São Paulo, Brazil

A R T I C L E I N F O A B S T R A C T

Editor: G.L. Dotto The increase in the anthropogenic impact has induced a constant discharge of new substances into the envi­
ronment. Endocrine-disrupting compounds (EDCs) belong to this group of emerging contaminants that began to
Keywords: be widely detected in various water matrices and has drawn attention due to their toxicity. The presence of EDCs
Water and wastewater in water and wastewater has become a global concern because of the health problems that this class of con­
Detection
taminants could cause in the endocrine system of animals and humans; and the uncertainty around their fate and
Hormones
longlasting effects. Recently, novel advanced analytical technologies have allowed the identification of these
Removal
Degradation compounds and their structures, and therefore the proposition of suitable treatment processes. Here, we review
Endocrine system the classification, incidence and impact of EDCs detected in water and wastewater. We also review the detection
methods and which treatments processes have been studied by the major publications of the last decade and their
future perspectives.

1. Introduction products, pesticides and herbicides and compounds present in personal

Hormones are essential substances for the proper functioning of
human and animal metabolism. They are produced and distributed
throughout the body by glands, regulating the activity of organs and
some cells [1]. The concern with the overexposure to these substances,
or to compounds that can mimic or interfere with the hormone activity
and disrupt the functioning of the endocrine system, is not recent. These
substances, or group of elements, are called endocrine-disrupting com­
pounds (EDCs) and are defined by the United States Environmental
Protection Agency (US EPA) (1998) as “exogenous agents that interfere
with the production, release, transport, metabolism, binding, action, or
elimination of the natural hormones in the body responsible for the
maintenance of homeostasis and the regulation of developmental pro­
cesses”. Substances identified as EDCs can act as a substitute for the
natural hormones in the body of humans and animals, inhibiting or
imitating their effects, thus being able to deregulate their levels and
affect the health of those contaminated [2,3]. These contaminants are
usually classified according to their sources and or function. As common
examples, there are natural and synthetic hormones, pharmaceutical
care products and food packaging. [4,5].
Although it is not possible to establish an absolute cause-effect
relation, the current research data associates a wide range of long­
lasting health problems to human and wildlife exposure to EDCs [6].
Disturbances in the male and female reproductive systems,
hormone-related cancers, neurological problems, obesity, immune dis­
orders, and development, and growth abnormalities are some of the
diseases related to the EDCs [7]. The effects of these hazardous com­
pounds on wildlife are well-reported and clear; they include impaired
reproductive, immune, and nervous systems, as in humans. However,
there are also signs of a decrease in population, behaviour changes and
modified anatomy as well [8].
As there are several types of compounds classified as EDCs, there are
also numerous sources of contamination of rivers, seas and lakes, and
drinking water. One of the biggest sources of contamination is the
sewage and wastewater treatment plants, where agro-industrial efflu­
ents and substances which do not undergo total metabolism in the body
are excreted via urine and feces [9,10]. Due to the low concentrations in
which they are found in the environment (ng/L and μg/L), suitable

* Corresponding author.
E-mail addresses: wedja.tvieira@gmail.com (W.T. Vieira), mar.bfarias@gmail.com (M.B. de Farias), marcela_spaolonzi@hotmail.com (M.P. Spaolonzi), meuris@
feq.unicamp.br (M.G.C. da Silva), melissagav@feq.unicamp.br (M.G. Adeodato Vieira).

https://doi.org/10.1016/j.jece.2020.104558
Received 27 August 2020; Received in revised form 23 September 2020; Accepted 26 September 2020
Available online 2 October 2020
2213-3437/© 2020 Elsevier Ltd. All rights reserved.
W.T. Vieira et al.
analytical detection and preparation methods are necessary for the
identification of such EDCs. Some conventional methods, used for
detection in different matrices such as blood and urine, have been suc­
cessfully adapted for environmental purposes. Besides the traditional
methods such as
High-Performance Liquid Chromatography with Mass Spectroscopy
(HPLC-MS), Gas Chromatography with Mass Spectroscopy (GC–MS),
and Solid Phase Extraction (SPE); biosensors, a novel technology based
on the biological effect of the EDCs have also been studied [11–16].
These EDCs can be hazardous even at low concentrations, therefore,
efficient water and wastewater treatments are key for adequate removal
of these compounds. Conventional treatments currently present at the
water and wastewater treatment plants are designed for the removal of
organic matter and do not promote effective removal of EDCs. Thus,
non-conventional alternative treatments have been developed and
thoroughly studied to enhance the removal of these compounds. The
most promising methods are the advanced oxidative processes and
biodegradation, which are based on the degradation of the micro con­
taminants; and adsorption and membrane filtration, which are phase-
changing methods [17–20]. Advanced oxidative processes exhibit
great potential for the treatment of EDCs present in waters due to its
property of degrading the contaminant and not only removing them
[21–23]. Biological processes are effective for lowering the concentra­
tion of biodegradable contaminants; active sludge, membrane biore­
actor, and biofiltration are examples of feasible techniques [24].
Adsorption is a promising method due to its high efficiency, simplicity,
and cost-effectiveness. Activated carbon and unconventional adsorbents
can remove a wide range of emerging contaminants [25–28]. Mem­
branes are effective barriers for the selective filtration and rejection of
contaminants, notably the ones employed in nanofiltration and reverse
osmosis [29].
This review aims to summarize the latest data on the occurrence of
EDCs on the environment; risks and effects of these compounds on
human and wildlife health; detection and sample preparation methods
and promising treatment pathways of the most common EDCs found and
studied throughout the last decade.
2. Endocrine system
Humans and animals have an endocrine system that consists of a
series of hormone-producing glands. These glands act as a bridge to
integrate the endocrine system with physiological systems through a
complex system of chemical signals, which communicate with the or­
ganism through the circulatory system, reaching the receptors of the
target cells and releasing the signals necessary to keep the body func­
tioning. There are a variety of glands, some producing multiple types of
hormones while others produce only simpler hormones, however, they
all are indispensable for life, whether for growth, reproduction, sexual
differentiation, development and other physiological functions of the
human and animal organism [30–32]. In humans, hormones are pro­
duced in various parts of the body. In both men and women, they are
produced in the brain, hypothalamus, pituitary, thyroid, parathyroid,
adipose tissue, bones, adrenal, cardiovascular system, and pancreas.
Mammary glands, uterus, oviduct, and ovary are responsible for the
production of hormones in women, whereas, prostate and testis have
this function in men [33,34].
Hormones are primarily responsible for maintaining the healthy
functioning of human and animal bodies. Their release from the glands
into the bloodstream depends on many factors, including metabolism
and target cells, and are usually found in low concentrations in the
circulation system to keep the cycle constant [30,33]. Therefore, hor­
mones must always be kept within the optimal range, as levels far above
or below the ideal levels can cause disease in both humans and animals
[32].
Endocrine disruptors can act as hormone substitutes and end up
acting as blockers, producing an antagonistic effect, or they can act as a
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Journal of Environmental Chemical Engineering 9 (2021) 104558
hormone mimic, causing an agonist effect. Besides, they are also able to
deregulate the ideal levels of natural hormones of the body, causing
disorders that can lead to diseases such as cancer, obesity, diabetes,
heart disease, among others [3,35,36].
The first evidence of the influence of endocrine disruptors was
exposed in 1950/1960, with studies on the impacts of pesticides, espe­
cially DDT (Dichloro-Diphenyl-Trichloroethane), on the environment,
more specifically on wildlife, made by Rachel Carson and published in
her book ‘Silent Spring’ (1962). Rachel concluded that pesticides accu­
mulated in the organisms of animals (fish and birds) could affect their
endocrine system, deregulating the level of sex hormone and prosta­
glandin. She also noted that human health could be affected by food
contaminated with DDT as well. After a wide repercussion of the book,
the use of DDT was restricted in many countries in 1970 [9,32].
However, it was only in 1996, through the book ‘Our Stolen Future:
Are We Threatening Our Fertility, Intelligence, and Survival? A Scien­
tific Detective Story’, by Theo Colborn, Dianne Dumanoski, and John
Myers that the concern with chemicals in the environment became more
evident. In the book, the authors highlighted the alarming results of
chemical compounds that acted as natural hormones of humans and
animals and disrupted their natural processes of development and
reproduction. Over the years, a multitude of research and studies were
conducted on these compounds that later were called endocrine dis­
ruptors [37–41].
Nowadays, endocrine disruptors are defined by several international
organizations. According to Endocrine Society [42] (one of the largest
international organizations in this field of research), endocrine dis­
ruptors are “an exogenous chemical or mixture of chemicals, that can
interfere with any aspect of hormone action”. For the European Com­
mission, EDCs “are chemicals that may interfere with the hormonal
system and, as a result of that, produce harmful effects in both humans
and wildlife”. The United States Environmental Protection Agency (US
EPA) defined EDCs, in 1998, as “exogenous agents that interfere with the
production, release, transport, metabolism, binding, action, or elimi­
nation of the natural hormones in the body responsible for the mainte­
nance of homeostasis and the regulation of developmental processes”. In
2002, the International Program on Chemical Safety (IPCS) of United
Nations Environment Program (UNEP) and World Health Organization
(WHO), defined chemical endocrine disruptors and potential chemical
endocrine disruptors, respectively, as “an exogenous substance or
mixture that alters function(s) of the endocrine system and consequently
causes adverse health effects in an intact organism, or its progeny, or
(sub)populations” and “an exogenous substance or mixture that pos­
sesses properties that might be expected to lead to endocrine disruption
in an intact organism, or its progeny, or (sub)populations”. Although
slightly different, all definitions include disturbances or interference in
the endocrine system of humans or animals that may cause adverse
health outcomes.
3. Classification of EDCs
Despite being chemical substances, endocrine disrupting compounds
do not have a similar chemical structure or nature to be classified in this
way [39]. Therefore, they are divided into synthetic substances, or
xenoestrogens, and natural substances, known as hormones [43,44].
Besides, they can still be divided into different groups according to their
origin: drugs with hormonal side effects (metoprolol, naproxen, etc);
industrial and household chemicals (fire retardants, bisphenol A,
phthalates, polychlorinated biphenyls, etc); side products of industrial
and household processes (dioxins, pentachlorobenzene, etc); agricul­
tural chemicals (pesticides, herbicides, etc); and artificial and natural
hormones (ingredients of contraceptive pills, testosterone, 3-omegafatty
acids, etc) [44–46]. Or, they can also be divided according to their use, as
can be seen in Table 1.
The increased daily production and consumption of new synthetic
substances by industries and people has caused a growth in the levels of
W.T. Vieira et al.
Table 1
Most common synthetics EDCs, divided by their use.
Most common EDCs Uses References
DDT, Atrazine, 2,4D; Glyphosate; Pesticides, Herbicides, [5,46,49,
Chlorpyrifos; Pyraclostrobin Fungicides 51]
Lead, Cadmium, Phthalates Children’s products [49,52]
Phenol, BPA, phthalates Food contact materials [43,53]
Phthalates, Parabens, cyclosiloxanes, Personal care and [46,53,54]
Triclosan, DEET cosmetics
EE2, Dexamethasone, Rosiglitazone, Pharmaceutical agents [5,46,48]
Levonorgestrel
Perfluorochemicals Textile clothing’s [43,55]
PCBs, Brominate flame retardants Electronic and building [56,57]
materials
2,4D: 2,4-dichlorophenoxyacetic acid; BPA: bisphenol A; DEET: N,N-diethyl-m-
toluamide; EE2: 17α-ethinylestradiol; PCBs: polychlorinated biphenyls.
potential EDCs, turning them to be ubiquitous in the environment. These
substances end up in sewage or water bodies and their effects on the
environment and ecosystem are still unknown [47]. Some of the
well-known synthetic EDCs classes are mainly present in pesticides,
children’s products, food contact materials, electronic and building
materials, personal care and cosmetics, pharmaceutical agents, and
textile clothing. The natural hormones classified as endocrine disruptors
are estrone (E1), 17β-estradiol (E2), and estriol (E3) [48–50].
The naturals hormones E1 and E2 and the synthetic hormone EE2
have a similar chemical structure, with one aromatic ring (A), two
cyclohexane rings (B and C) and one cyclopentane ring (D) [58], which
can be seen in Fig. 1.
EE2, which is a synthetic derivative of the natural hormone E2 with
high estrogenic activity, is commonly used in oral contraceptives and
general medication. Although E2 and EE2 have similar structures, EE2 is
more resistant to biodegradation, therefore its accumulation in the
environment is easier [43,59].
Pesticides are the largest class of endocrine disruptors. They are used
in agriculture, and traces of their use can be found in some foods and
drinking water [43,49]. The DDT, a common example of pesticide, was
largely used after World War II, but its use was banned in the’ 70 s in
many countries due to their effects on human and wildlife health. Some
underdeveloped countries still use DDT against malaria [60,61].
Polychlorinated biphenyls (PCBs) are no longer used nowadays,
however, they have been largely used in heat transfer and electrical
equipment, transformers, capacitors, and plastics. It can still be found in
older installations or electronic materials as well as in thermal insulation
and oil used in motors [35,62,63].
Phthalates are used as an additive in PVC (polyvinyl chloride) pro­
duction and therefore are present in children’s products and packaging
materials. They can also be used in cosmetics, medical devices, food and
building materials. The three most common phthalates used are di-2-
ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and dibutyl
phthalate (DBP) [64]. DEHP, DBP, BBP (benzyl butyl phthalate) and
DIBP (diisobutyl phthalate) cannot be used as additives in PVC or other
plastics in the manufacture of toys and childcare articles if they have a
concentration equal to or greater than 0.1 % by weight material [65]. In
California, in the United States, there is also a ban on the use of DBP and
DEHP in the formulation of cosmetics [66].
Fig. 1. Chemical structure of natural and synthetic hormones. E1: estrone; E2:
17β-estradiol; EE2: 17α-ethinylestradiol.
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Journal of Environmental Chemical Engineering 9 (2021) 104558
Bisphenol A is another substance widely synthesized by the industry
of plastics and it is mainly present in polycarbonates and epoxy resins.
Therefore, it is part of daily used products as food packaging, thermal
papers, CDs and DVDs, pipes, car panels, dental sealants, medical de­
vices, among others [49,67]. The use of BPA in the manufacture of
polycarbonate baby bottles has been banned in Europe since 2011.
However, it is allowed to be used as a monomer in the production of
other plastics for food packaging, with a specific migration limit of 0.05
mg/kg of food, according to European Plastics Regulation (EU) No.
10/2011, in its current consolidated version of 2019 [68]. In the United
States, the use of BPA is prohibited, under FDA (Food and Drugs
Administration) regulations, in the production of baby bottles, sippy
cups and infant formula packaging [69,70].
Parabens are compounds used in cosmetics as preservatives, some
types are also used in food, pharmaceuticals, and personal care products
[71]. Methylparaben is the most common paraben used, but ethyl­
paraben, butylparaben, and other parabens are also found in cosmetics,
food, and personal care products [72]. In Europe, parabens under the
denomination of 4-hydroxybenzoic acid and its salts and esters have a
maximum allowed concentration of 0.4 % (as acid) for single ester and
0.8 % (as acid) for mixtures of esters to be able to be used in cosmetics
[73]. In 2014, Europe banned the use of isobutylparaben, phenyl­
paraben, benzylparaben and pentylparaben in cosmetics [74]. In Cali­
fornia, there is a ban on the use of isobutylparaben and
isopropylparaben in cosmetics [66].
Another group of elements that can be classified as endocrine dis­
ruptors is heavy metals, like cadmium (Cd), arsenic (As), lead (Pb), and
mercury (Hg). These metals can mimic the biological functions of some
hormones in the organism, preventing the functioning of certain en­
zymes, and this can deregulate the endocrine system of humans and
animals, causing diseases in them [49,75]. Cadmium is used in the
production of batteries, in pigments and coatings, in electroplating, and
as a stabilizer for plastic and non-ferrous alloys [76,77]. Lead is one of
the oldest metals used by mankind, and it is frequently found in com­
binations with other substances than in its natural form. It can be used in
the production of plastics, glass, batteries, ceramic enamels, and welding
of metal alloys [78,79]. Mercury can be used, in its inorganic form, in
the production of pigments, or its elementary form, in production of
hydrochloric gas and caustic soda. Mercury is also used in thermometers
and manometers, or even in dental products, and in the production of
intermediate chemical compounds [79]. In some parts of the world, the
use of these metals is restricted. In Europe, for example, there is the
Registration, Evaluation, Authorization and Restriction of Chemical
(REACH), which aims to lessen the impact that chemicals can cause on
human health or the environment. In Annex XVII, there is a list with all
substances, group of substances or a mixture and their conditions of
restriction, within the scope of REACH and the Directive 76/769/EEC.
The cadmium concentration must be less than 0.01 % by weight of the
material for the production of mixtures and articles made from plastic
and to be able to be used in some paints. Since 2014, mercury cannot be
used in barometers, hygrometers, manometer, tensiometers and others.
Lead cannot be used in jewellery if its concentration exceeds 0.05 % by
weight [65]. In the United States, the use of mercury compounds in the
production of cosmetics is regulated by the FDA, and it is limited to 65
ppm of mercury in products for the eye area, and it is restricted to cases
when it is not possible to use any other safer preservative [80].
4. Detection of EDCs
Point sources such as industrial effluents and wastewater, as well as
diffuse sources such as septic tanks and soil polluted with agricultural
substances, are two of the ways in which EDCs can reach and contam­
inate rivers, bays and underground water, and, therefore humans and
wildlife [9].
According to a research carried out by Chang et al. [81], more than
60 % of hormones (mainly E1, E2 and EE2) found in 45 urban rivers in
W.T. Vieira et al.
China are coming from freshly discharged untreated sewage. This
pattern of detection is due to the excretion of natural and synthetics
hormones, that are not completely metabolized by the body, through
urine and feces [82].
The EDCs are found in low concentrations levels in the environment,
in the order of ng/L and μg/L. Several analytical methods, developed for
detecting the presence of those compounds in blood, tissue and urine
matrices, were adapted for environmental matrices [43,79]. Solid Phase
Extraction (SPE) [53], solid-phase microextraction [83], Derivatization
[84], Gas Chromatography with Mass Spectroscopy (GC–MS) [85] and
High-Performance Liquid Chromatography with Mass Spectroscopy
(HPLC-MS) [5] are some of the analytical methods most frequently
employed for this purpose. Biological methods have also been used to
detect EDCs in water matrices, the most common one being the
Enzyme-Linked Immuno-Sorbent Assay (ELISA) [86].
Solid-phase extraction is a sample preparation method that was first
used in 1976 to complement and enhance the liquid-liquid extraction
(LLE) method, which has some disadvantages and is still widely used
today [11,87]. As a very versatile analysis, it can be used in several
research areas, such as organic compounds, food and drug analysis, and
biological and environmental samples, like drinking water and waste­
water [11,87,88]. This analysis can be used for the extraction and
concentration of a particular compound for the evaluation or the
cleanup of a sample [11,89,90]. The operation mechanism of the SPE
method is like that of LLE. The difference between these two processes
lies in the sample partition, in SPE it is divided into liquid and solid
phases [91]. This partition is due to the affinity of the analyte with the
solid phase sorbent, and the choice of this sorbent is what controls the
selectivity and the extraction capacity [89,92]. The analytes in the solid
phase are washed out with solvent to obtain only the substance of in­
terest [93]. SPE pipette tip, disks, disks in syringe cartridge and 96-well
microtiter plate are the most commons formats of sorbent available [91,
94]. In addition to other sorbent formats, there have been several
modifications to this method over the years, resulting in similar methods
with more automation or at smaller scales, such as solid-phase micro-­
extraction (SPME), micro-extraction by packed sorbent (MEPs) or
solid-phase dynamic extraction (SPDE) [88]. One of the advantages of
this method is its easy applicability, however the use of, generally, toxic
solvents can be a disadvantage [93].
The derivatization is another example of a sample preparation
method that is suitable for the detection in complex samples. It indicates
the presence of organic compounds and therefore is widely used in
environmental and forensic chemistry [12,95]. Derivatization is a
chemical reaction necessary to provide thermal stability and volatility to
some compounds, especially the ones with polar functional groups.
These enhanced properties achieved with derivatization are funda­
mental for chromatographic analysis [12,96,97]. Silylation, alkylation
or acylation are commonly used reactions to substitute the polar group
of the molecule [95,98]. Silylation is the most used of those, in this re­
action the most unstable hydrogen is replaced by the trimethylsilyl
group. Whereas in alkylation, the unstable hydrogen is replaced by the
aliphatic group, and in acylation, the hydrogen is replaced by a car­
boxylic acid group [95,97,99]. One of the advantages of derivatization is
the higher sensitivity and separation, but this results in a longer
analytical process [100]. The problem concerning the time necessary for
the analysis was overcome by adding a reagent to the liquid sample. The
choice of reagent will influence the response of the analysis and the
stability of the sample, therefore the reagent must be carefully chosen,
and must be specific to the analyte of interest and its functional groups
[12,101].
Gas Chromatography with Mass Spectroscopy is a qualitative and
quantitative detection method for volatile or semi-volatile organic
compounds [14,102]. Coupled GC–MS equipment started to be
commercialized from 1970 but it was already in use since the’ 50 s [102,
103]. The two techniques are quite compatible to be combined since the
components analyzed in both techniques follow the same “rules” and use
4
Journal of Environmental Chemical Engineering 9 (2021) 104558
the same operation phase. The only difference is the pressure adopted in
each method, the GC column comes out with atmospheric pressure
whereas the ionization chambers of MS must be between 10− 5 and
10− 6 Torr [102,104]. However, this issue can be solved by using an
efficient vacuum pump and, in the GC, using capillary columns con­
nected directly to the MS ionization chamber [104,105]. There are
several methods of ionization, the most applied for CG-MS are the
electron impact ionization (EI) and the chemical ionization (CI) [105,
106]. EI is the most common method; it transmits a high level of energy,
in addition to producing almost 100 % of positively charged ions,
neutral atoms and fragmented ions. CI transfers less ionization energy,
which results in the production of more molecular ions and less frag­
mentation [107]. GC with MS has the advantage of having its detection
limit quite low, in addition to being able to measure complex samples
with greater sensitivity and selectivity and, therefore, it is used for
several purposes, such as forensic and criminal cases, environmental
monitoring, medicine and pharmaceutical applications, biological and
pesticides detections and industrial applications [104,108].
High-Performance Liquid Chromatography with Mass Spectroscopy
is a detection method that is also used to identify the purity of the
compound [109]. The combination of these two methods took a little
longer to become available due to the difficulty in obtaining an ioniza­
tion source that would contain a liquid stream with low volatility and
temperature-sensitive compounds [103,105]. There are three main
ionization sources employed for HPLC: Electrospray Ionization (ESI),
Atmospheric Pressure Chemical Ionization (APCI) and Atmospheric
Pressure Photoionization (APPI). ESI is the most used among these [106,
109,110]. ESI can be used for highly polar compounds that are ionizable
in solutions, in addition to temperature-sensitive compounds and com­
pounds with large molar mass, since the ionization sources act directly
on the solution [103,105,110]. Moreover, ESI releases ions in their un­
excited and very stable state [111]. Unlike ESI, APCI is used for
nonpolar, volatile, and thermally stable compounds, as it occurs in the
gas phase [103,105]. Even though APCI is a source of soft ionization, it
generates a degree of fragmentation in ions [112]. APPI is a source of
ionization complementary to the other two aforementioned methods.
Some compounds with low polarity or nonpolar ones can only be
analyzed from APPI, although a large majority of compounds may be
analyzed with both APCI and APPI. An example of compounds that are
only analyzed by APPI is polycyclic aromatic hydrocarbons [105,113].
The ions produced by this ionization source are usually single charge,
which is only positive or only negative, and the compound is analyzed
through chemical photoionization reactions [103,110].
The bioassays are also an approach that can be adopted for the
identification of EDCs. The biological methods can quantify the toxic
potential and the cumulative effect of complex mixtures through their
biological response in vitro and in vivo [114]. Enzyme-Linked Immu­
no-Sorbent Assay (ELISA) is a qualitative and/or quantitative
biochemical method, that was developed by Peter Perlmann and Eva
Engvall at Stockholm University, Sweden, in 1972 for detecting hor­
mones, antibodies, peptides, etc. [115–117]. The ELISA method is
derived from the radioimmunoassay (RIA) technique and its working
principle is like that of enzyme immunoassay (EIA), another method
derived from RIA [118]. ELISA is based on the interaction of antigens
and antibodies, using an enzyme as a catalytic agent. The antibodies
coupled to the enzyme bind to their respective antigens (substrates)
present in a colorless sample, forming a colored product, and the amount
of antigen is measured spectrophotometrically [119–121]. There are
several types of ELISA, the indirect, sandwich and competitive methods
are the most used ones [13]. The indirect method has the non-specific
immobilization of the antigen as a disadvantage, but this problem can
be overcome by using the sandwich method, which is simpler, more
sensitive and specific, and both methods can detect antigens or anti­
bodies in low concentrations. The competitive ELISA can be used in
complex mixtures of antigens, as it can detect differences in their com­
positions with high sensitivity [118,122]. A disadvantage of the ELISA
W.T. Vieira et al.
method is the need to generate a known antibody or antigen to detect
specific antibodies or antigens [118].
There are more specific bioassays that measure the events that affect
the binding to the receptor (or report gene assays). Tests of this nature
are capable of detecting lower concentrations of substances such as
EDCs that can be analyzed based on human cell lines such as the CALUX
(Chemically activated luciferase gene expression) assay or yeast cells
employing screening [123,124]. In CALUX assays, a receptor induces
gene expression that provides information on the biological response in
humans that would be caused by EDCs, such as agonic and antagonistic
effects, for example [124]. CALUX bioassays are responsive to andro­
gens and estrogens, however, they have also been conducted to study the
activation of receptors of individual compounds or complex mixtures.
The evaluation of the endocrine combination of real samples was carried
out in a water treatment plant containing a complex mixture of chem­
icals. From this study, it was realized that the masking effect is relevant
for complex samples and it is recommended to perform tests of antag­
onistic and agonistic effects with different cellular systems [123].
Considerable progress has been observed concerning bioassays in vitro,
but they still do not have the strength to ensure water quality alone, but
they are a way to embrace the analytical techniques for identifying EDCs
[114].
Biosensors are another type of biological method used for the
detection of EDCs. They are cheaper and simpler techniques to make this
kind of detection and its analysis can be done with minimal amounts of
complex matrix samples [125,126]. According to the International
Union of Pure and Applied Chemistry (IUPAC), biosensors are in­
struments (equipment) for transforming chemical information into
specific quantitative analytical information, through a biochemical
mechanism and a physical-chemical transducer [127]. The transducer
can transform the received biological signal into an electrical signal,
which is transformed into analytical responses that can be analyzed
[128]. Some authors classify biosensors based on the transduction
element or the bioelement used [15,129,130]. However, they can also
be divided based on the type of analyte they detect [16]. The biosensors
based in the transduction element can be classified as electrochemical
(potentiometric, amperometric, conductimetric and impedimetric), op­
tical (surface plasmon resonance, fiber optics, absorption etc) or
mass-based (piezoelectric or thermal). Those based on their bioelement
can be classified as enzymatic, immunochemical, DNA biosensors,
whole-cell, antibody/immunosensors, protein receptors among others
[15,56,129–131]. Due to their higher sensitivity and better stability,
biosensors can be used in several areas, such as in food and agricultural
industry, medical and biomedical field, environmental monitoring,
marine and military sector, among others [16,132,133]. Table 2 shows
the levels of some EDCs, found in surface and wastewaters in several
countries, detected through the aforementioned methods. Table 3 ex­
hibits a comparison between classic methods and biosensors.
5. Toxicological effects of EDCs
The overexposure to endocrine disruptors may cause a multitude of
effects in humans and wildlife. Infants and children are the most sus­
ceptible to the threats of EDCs when exposed to them, because it is at this
stage that the most critical development of their physiological systems
occurs, and any hormonal imbalance can cause problems in the future,
triggering diseases such as breast and prostate cancer, fertility, preg­
nancy and thyroid problems in humans, and in animals, there may be a
decrease in egg hatching and problems in the reproductive and immune
systems [9,43].
5.1. Effects in human health
Concern about the effects of prolonged exposure to endocrine dis­
ruptors in human health is not recent. Between the’ 40 s and’ 70 s,
pregnant women widely used DES (diethylstilbestrol), as prevention of
5
Journal of Environmental Chemical Engineering 9 (2021) 104558
abortion. It was later discovered that its long-lasting effects could pass to
the fetus, affecting its adult life, with possible development of cancer in
their reproductive system [35,151]. Besides, exposure to DES can cause
problems for adult women as well, such as problems with ovulation and
vaginal cancer [39,152].
Currently, several studies associate many EDCs with diseases in the
reproductive, endocrine or nervous system, as well as with brain or
pulmonary and cardiovascular diseases, such as obesity, diabetes, hy­
pothyroidism, respiratory problems, cancer, Alzheimer, learning dis­
abilities, etc [151,153,154].
Obesity is one of the diseases that are in continuous growth, espe­
cially in children and adolescents, and has become a worldwide public
health concern. Since EDCs are substances that mostly behave as fat-
soluble, they have great ease to accumulate in adipose tissue. This
accumulation can directly affect the metabolism of human beings,
interfering with the energy balance of the body [155,156]. The EDCs
bind to the nuclear receptors of hormones, disrupting adipocyte differ­
entiation and interfering with hormone transport. Studies have associ­
ated the exposure to phthalates and their metabolites, and BPA with
obesity [151,157]. According to a study conducted by Choi and col­
laborators [158], obese children have 1.37 times more MEP (monoethyl
phthalates) in their urine than non-obese children. Children whose
mothers may have been exposed to DDT pesticide may suffer from
obesity due to epigenetic heritage [159,160]. Diabetes is one exponen­
tially growing disease that can occur as a consequence of obesity. There
are two types of diabetes, and type 2 diabetes is the one that is associated
with obesity and may be related to exposure to PCBs, BPA and pesticides
like DDT [160–162]. These EDCs can block the function of insulin,
causing normal body enzyme functions to be incomplete, triggering the
disease [163].
Some studies suggest that Alzheimer’s disease (AD) may be associ­
ated with type 2 diabetes, due to impaired insulin levels, especially in
people who already have a genetic predisposition to AD [164,165]. APP
and p-tau protein, considered pathological proteins and associated with
AD, may suffer an increase in their levels, due to the presence of BPA,
thus causing the triggering of AD [148]. Exposure to Pb and Hg can also
generate an increase in other pathological proteins related to AD, thus
provoking its onset. Other endocrine substances are also being studied as
causes of AD or other neurological diseases, such as brominated flame
retardants (BFRs), phthalates and pesticides [153,166,167].
Cancer has been a great cause of death for men and women world­
wide for many years. Prostate cancer is one that most affects men and
one of the types of cancer that kills the most [168]. This type of cancer
may be related to the exposure of men to endocrine substances, such as
pesticides, BPA, PCBs, phthalates, cadmium, arsenic and others
[169–172]. These compounds can modify reproductive activities and
activate the carcinogens to act on the human body [168,173]. Breast
cancer can also be developed because of EDCs, affecting the mammary
glands, changing their sensitivity and protection against carcinogens.
Some endocrine disruptors that may be related to breast cancer are
diethylstilbestrol (DES), BPA, phthalates and DDT [174–177].
5.2. Effects in wildlife
Regarding the wildlife, studies indicate that EDCs may be associated
with hormonal and other health problems [178]. As these compounds
reach different water matrices in the environment directly, without
previous suitable treatment, the effects on the health of animals are
usually due to the interaction of those EDCs rather than only as a result
of an isolated substance [179,180]. In wildlife, the effects of EDCs are
measured using biomarkers, tissue, and individual organism [180].
Some of the most striking effects of EDCs on wildlife are the changes that
occur in their reproductive anatomy, fertility, eggshell thinning, hor­
monal activity, hatchability, plasma vitellogenin (VTG) levels, and
viability of the offspring [181–183].
Besides the publication of Rachel Carson’s Silent Spring in 1962, the
W.T. Vieira et al. Journal of Environmental Chemical Engineering 9 (2021) 104558

Table 2
Concentration of some endocrine disruptors found in the wastewater and surface water.
Concentration (ng/L)
EDC Limit of detection (ng/L) Country Reference
wastewater surface water

E1 79 US [134]
(13.1–104) 1.8 [84]
Canada
20 0.5 [135]
566 (ND - 3050) 35.38 [136]
Brazil
870 [137]
71.2 (18.8–170) France [138]
(ND - 65) [134]
China
(0.7–75) 0.2 [139]
E2 147 US [134]
(24.7–66.9) 24.3 [84]
Canada
30 0.5 [135]
143 (ND - 776) 11.28 [136]
Brazil
1330 [137]
20.4 (5.1–37.9) France [138]
(ND - 2) [134]
China
(0.7–7.5) 0.3 [139]
E3 1661 US [134]
297 (26.8–658) France [138]
(ND - 1) China [134]
(ND - 3600) Indonesia [53]
EE2 230 US [134]
(0.5–5.7) 0.5 Canada [84]
421 (ND - 3180) 60.43 [136]
Brazil
840 [137]
(ND - 1) China [134]
BPA 2550 US [134]
84,110 Brazil [137]
(192–215) Germany [134]
(6–881) [134]
China
(2.2–1030) 0.7 [139]
27 (6.9–59)
Korea [140]
62 (11–120)
(ND - 37,000) Indonesia [53]
TRICLOSAN 53 (ND - 9.8) [134]
US
(4700*) (1130*) [141]
(ND - 415) 0.4 Brazil [142]
(0.001–6.87) Germany [143]
39.8 (2–118) Spain [134]
(35–1023) [134]
China
(0.6–347) 0.2 [139]
17 (1–29) [140]
Korea
55 (16–82)
ATRAZINE 19 (5–49) Brazil [5]
36 (756*) [134]
Spain
1.24 (1.74*) 0.02 [144]
0.34 (<0.25− 0.61) 0.49 (<0.25 - 1.2) Korea [140]
2,4D 88.5 (442*) 0.11 Spain [144]
(5.6–6.2) 0.2 China [139]
MePB (15.9–204) 0.5 US [145]
(72–91) 0.5 Canada [145]
(ND - 2875) 1.7 Brazil [142]
(5.1–26.2) 0.5 Spain [145]
(274–517) 0.5 China [145]
(ND - 5.75) Indonesia [53]
EtPB (<0.6 - 2.6) 0.2 US [145]
(<6.4*) 0.2 Canada [145]
(ND - 1485) 1.4 Brazil [142]
(<1.1*) 0.2 Spain [145]
(1.14–6.8) 0.2 China [145]
PHENOL (ND - 140) 10 e 70 South Africa [85]
PCB 133.2 (89–186.6) [146]
9.4 (2.4–15.2) US
5.7 (3.1–7.9)
201 [147]
246 France
179
8.42 (ND - 34.84) 0.006− 0.02 China [148]
5.84 (2.49–7.56) 0.006− 0.03
PBC 16.91 (5.51–40.28) 0.01− 0.07 China [149]
DEHP 2270 (330–97800) 30 Germany [54]
(220–3860) 10 France [147]
DBP 500 (120–8800) 20 Germany [54]
(5160–20760) 10 France [147]

ND: not detected; main (min - max); *max.

6
W.T. Vieira et al.
Table 3
Comparison between biosensors and conventional methods.
Biosensors Conventional
Small sample volume High sample volume
Real-time monitoring Long analysis time
Determination of the biological effect Determination of the chemical structure
Minimal waste generation Generation of toxic solvents waste
Most prototypes Most commercially available
Source: [131,150].
first evidence of the impacts of EDCs on wildlife was found in Florid in
the mid-1980s. It was observed that young male alligators had lower
testosterone concentrations and reduced phallus size, while female al­
ligators showed changes in their ovaries, in addition to plasma con­
centration higher than normal. The main cause of these anomalies is the
exposure to the metabolite DDE, from the pesticide DDT [31,184].
Over the years, other pieces of evidence of the danger of exposure to
EDCs have emerged. Natural and synthetic hormones (E1, E2, and EE2)
are associated with the change in the level of VTG in the blood of species
of fish, turtles and mussels [43,185]. Problems in the reproductive and
immune systems of some species of seals may be associated with
contamination of their food chain, mainly by PCBs and DDT and their
metabolites. Polar bears have been observed with masculinization in
females and low testosterone concentration in males from exposure to
PCBs and DDE (a metabolite of DDT) [186,187]. Eggshell thinning may
be also be associated [188]. The feminization of male fishes and
masculinization of female fishes, and other reproductive problems, are
commonly related to estrogens E1, E2 and EE2, phthalates, and BPA
[186]. As the effects of EDCs on animals are clearer and based on more
extensive literature, it is possible to draw lessons about the mechanism
of action and the possible consequences of those compounds for human
health. [189].
6. Treatment process for EDCs removal
The EDCs have multiple physical-chemical and structural properties
that give these compounds low or moderate natural biodegradability,
causing a cumulative effect in the environment [190]. Conventional
wastewater treatment processes were believed to be inefficient in
removing these contaminants. However, the activated sludge system has
been widely used, pointing out that the biodegradation stage is a
mechanism able to remove EDCs [191]. Tertiary processes such as
adsorption, reverse osmosis, nanofiltration and advanced oxidative
processes have also shown efficiency in removing this type of
compound.
Through a scan of the literature regarding endocrine disruptors
Fig. 2. Number of documents published per year from the last decade for the treatment of effluents contaminated with endocrine disruptors.
7
Journal of Environmental Chemical Engineering 9 (2021) 104558
compounds in wastewater and the removal processes as means of
minimizing the impacts caused by these contaminants, it was possible to
evaluate the tendentious scenario of the technologies concerning ad­
vances and innovations. For this, a search was carried out in the Scopus
scientific documents base, using the strings Endocrine-disrupting AND
wastewater AND removal OR treatment, in titles, abstracts and key­
words. Documents from the last decade (2010− 2020) were considered
such as articles, reviews, conference papers and book chapters. Refine­
ment was carried out about areas of interest limited to the fields of
Environmental Science, Chemistry, Engineering, Chemical Engineering
and Science, Agricultural and Biological Sciences, Pharmacology,
Toxicology and Pharmaceutics and Material Science. For the established
search strategy, 896 documents were returned. However, a detailed
analysis of the documents was carried out, and only the works that
addressed treatment processes for removal or degradation of EDCs were
considered, resulting in 453 documents. The methods of treatment, as
well as the number of documents published per year, are shown in Fig. 2.
The treatments using advanced oxidative processes had expressive
participation in the last decade as an alternative for removal of EDCs
with 32.01 % followed by the processes using methods of adsorption
(20.75 %), biodegradation (16.56 %), membrane filtration (11.26 %)
and mixed processes (5.74 %). The works about AOPs emerged, bringing
approaches such as Photolysis processes associated with Fenton’s re­
actions [192]; the use of different catalysts at photocatalysis processes as
TiO2 [193], SiO2 e WO3 [194], MnO2 [195], fibrous catalysts based on
fibrous silica-titania [196]. The improvement of photocatalysis pro­
cesses was also achieved through the combination of processes such as
photocatalysis and photolysis using UV-A, UV-C and UV–vis light [197].
Overall, the adsorption processes evaluated the efficiency of
different adsorbent materials such as biological activated carbon [198],
activated carbon (in powder [199], synthesized xerogel, lignin, com­
mercial C400 [200], carbon nanotubes [201], chitosan [202], nano­
adsorbers [203], residual biomass [204], cyclodextrin hydrogels [205]
and cellulose-based materials [206].
The publications concerning the application of biodegradation pro­
cesses to remove EDCs showed the use of different types of the reactors
(aerobic, anaerobic [207], membrane bioreactors [208], activated
sludge process (ASP) and sequencing batch reactor (SBR)) with micro­
organisms such bacteria [209], yeast [210], algae, fungi [211], as well
as enzymatic methods using immobilized enzymes [212,213]. Processes
using membranes have been also studied focusing on the microfiltration
membrane technology [214], reverse osmosis [214,215] and direct
osmosis [216], as well as the improvement of the characteristics of the
membrane, with the incorporation of hydrophilic metal-organic struc­
tures in a polyamide layer, as an example [217]. The main character­
istics of these aforementioned processes are presented below.
W.T. Vieira et al.
6.1. Advanced oxidative processes
Advanced oxidative processes (AOPs) generate highly oxidizing
species in situ such as the hydroxyl radical, which is non-selective and
has an oxidation potential of 2.80 V. This non-selectivity allows this
radical to attack a variety of organic compounds that are reduced to less
harmful intermediate products or to mineralize the molecule to CO2 and
H2O, which are more stable [218,219]. The success of AOPs is associated
with the appropriate operating conditions and the process applied
[220]. These processes are efficient to remove EDCs that cannot be
treated through conventional physicochemical and biological methods.
The performance of some of the most common advanced oxidative
processes is shown in Table 4.
The advanced oxidative processes presented in Table 4 were applied
to remove EDCs in water and wastewater. In the photolysis process,
studies were more focused on the use of the ultraviolet light due to its
low cost when compared to other systems. Whereas the photocatalysis
has explored many materials for use as a catalyst and supports [226,240]
or the improvement on the performance of TiO2 [197,227]. It was
observed that the authors used the combination of more advanced
oxidative processes achieving excellent kinetic rates and better degra­
dation efficiencies.
The use of ozone (O3) in ozonation processes has shown relative
efficiency. However, when it acts synergistically with other oxidants
such as hydrogen peroxide (H2O2) or associated with a physical mean of
degradation such as the use of UV radiation, the capacity for destruction
of EDCs is enhanced [241,242]. The disadvantage of processes that use
UV is in the cost associated with energy consumption, which according
to Basile et al. [243], can exceed by 30 mJ.cm− 2 the amount of energy
needed to degrade steroids. Thus, UV catalyzed processes have been
widely used for the notorious efficiency of degrading pollutants of any
nature without generating secondary waste [244]. Catalysts oxides base
(TiO2, ZnO, Al2O3, CeO2) [23,245,246] have been widely studied and
their efficiency is improving as the quality and functionality of the
equipment and development of supports with a high surface area, such
as silica [247], zeolites [248], clay [249] and activated carbon [250],
allows a better performance of the catalyst. Although they are costly
processes, they are environmental-friendly, as they are not only
phasing-transfer processes [251].
Some advanced oxidative processes are not able to full mineralize
EDCs resulting in transformation products. Studies have been conducted
to identify and evaluate the concentration, and the estrogenic and
antimicrobial activities of these compounds [252,253]. Even with
negligible concentrations detected, additional processes such as filtra­
tion with membrane or other materials can be considered to improve the
results achieved with AOPs.
6.2. Adsorption
One of the most relevant non-conventional processes for removing
EDCs is adsorption. Adsorption is a surface phenomenon in which a
certain component accumulates at the interface of two phases through
mass transfer mechanism. The substance that has its concentration
increased on the surface is the adsorbate and the adsorbing surface is the
adsorbent [254,255]. This process can be influenced by many factors
such as temperature, nature and concentration of the adsorbate, the
presence of other contaminants, the nature of the adsorbent, and
experimental conditions such as pH, time of contact, and surface area of
the adsorbent.
The selection of adsorbents is an essential aspect of the process since
the efficiency and the cost-benefit of the adsorption are strongly related
to their characteristics, prices, and availability. One of the most widely
used adsorbents worldwide is the activated carbon, due to its high ef­
ficiency and suitability for the removal of different types of contami­
nants. However, its elevated costs of production and regeneration
intensify the search for non-conventional adsorbents of similar
8
Journal of Environmental Chemical Engineering 9 (2021) 104558
efficiency [256–258].
There are a plethora of materials being studied as alternatives to
activated carbon, such as clay, zeolites, industrial and agricultural
waste, and by-products, biochar and activated biochar, silica-based
materials, metal-organic frameworks, polymers and bio adsorbents
[259–265]. Table 5 shows some promising adsorbent materials that
have been recently employed for the removal of endocrine disruptors
from aqueous solutions.
Most of the non-conventional adsorbents are naturally available,
plentiful, and economical materials with favorable adsorption capacity.
Even though different adsorbents show good removal capacity, as can be
seen from Table 5, it is tough to compare their adsorptive performance.
This comparison is difficult due to the higher selectivity of those mate­
rials when compared to commercial activated carbon, which means
specific results for each adsorbent-adsorbate system [283]. This
discrepancy can be noticed through the analysis of the removal
bisphenol A from aqueous solutions, the adsorption capacity varies from
9.68 to 263.7 mg.g− 1 [272,277], depending on the adsorbent. This
pattern can also be observed through the use of the same adsorbent,
Krupadam et al. [278] reported that a chitin adsorbent had an adsorp­
tive capacity of 64.6 and 84 mg.g− 1 for bisphenol A and benzo[a]pyrene,
respectively (Table 5).
In general, adsorption has several advantages when compared to
other removal processes. It is an essentially physical process, it has a
simple structure and operating system and it does not generate un­
wanted or potentially toxic by-products. Furthermore, the use of non-
conventional adsorbents enhances the cost-effectiveness of the process
[265,284].
6.3. Membrane filtration processes
Membrane processes are promising methods for the removal of
endocrine disruptors due to their broad applicability, no insertion or
fabrication of by-products and metabolites, and high removal efficiency.
Membrane filtration processes use different membranes as physical
barriers for rejecting or reducing the concentration of contaminants
present in solutions. The removal of compounds may occur throughout
one or the combination of three mechanisms: physical sieving, physi­
cochemical interaction, and charge repulsion [285–287].
The membranes are usually composed of two layers, one of a porous
material that serves as support, and one of a denser material as a top
layer. They allow a selective filtration of specific compounds depending
on a multitude of factors such as their physicochemical properties, the
nature of the contaminant, the operational conditions under which the
process is carried out, type of water matrix and membrane fouling [285,
288].
The types of membrane processes are usually classified based on the
driving force and the pore size of the membrane. Pressure-driven
membrane filtration such as microfiltration, ultrafiltration, nano­
filtration, and reverse osmosis are the main process employed for the
removal of micro-contaminants as endocrine disruptors (Table 6). For­
ward osmosis and membrane bioreactor are also effective techniques for
the removal of these compounds [92,289].
Microfiltration membranes operate at low pressures which widen
their applicability. However, they have relatively large pore sizes
(0.1–10 μm) that prevent their employment for the efficient removal of
EDCs [301,302]. Ultrafiltration is undertaken at low pressures as well,
but the smaller pore size (0.01–0.1 μm) of these membranes allows them
to reduce the concentration of EDCs, especially polar and water-soluble
compounds such as E1, E2, EE2 and diclofenac [286,303]. Micro­
filtration and ultrafiltration operate mainly by size exclusions and are
more efficient when applied as pre or post-treatment [304].
Nanofiltration and reverse osmosis are undertaken at high pressure
and are the most employed for the separation process due to the small
size of their pores. They can reject numerous EDCs not only through
sieving but with the aid of adsorption and charge effects. Nanofiltration
W.T. Vieira et al.
Table 4
Advanced oxidative process for degradation of disruptors endocrines present in water.
Process Compound
4-nonylphenol (NP)
Photolysis
17β-Estradiol (E2)
17β-Estradiol (E2) 17α-
ethinylestradiol (EE2) Estrone
(E1) Estriol (E3) Progesterone
Photolysis (PG)
Nonylphenol (NP) Nonylphenol
monoethoxylate (NP1EO)
Nonylphenol
diethoxylate (NP2EO)
Bisphenol A (BPA) Triclosan
(TCS)
Photocatalysis
Nonylphenol diethoxylate
(NP2EO)
Photocatalysis Bisphenol A (BPA)
Triclosan (TCS)
Perfluorooctanoic acid (PFOA)
Photocatalysis
Methylparaben (MPB)
Ozonolysis Methylparaben (MPB)
Atrazine (ATZ) Alachlor (ALA)
Ozonolysis Carbamazepine (CBZ) 17-
α-ethinylestradiol (EE2)
Pentachlorophenol (PCP)
Testosterone
Ozonolysis Methylparaben (MP)
Ethylparaben (EP)
Propylparaben (PP)
Butylparaben (BUP)
Benzylparaben (BZP)
Ozonolysis
Diethyl phthalate (DEP)
Sonolysis 17β-Estradiol (E2)
Sonolysis
Journal of Environmental Chemical Engineering 9 (2021) 104558
Class Degradation (%) Other parameters References
2 − 1
k = 0.0326 × 10 min (UV-C) k =
0.0078 × 102 min− 1 (UV-A) k =
0.0082 × 102 min− 1 (UVA/PS) k =
Phenol – 0.050 × 102 min− 1 (UVC/PS) k = [221]
0.048 × 102 min− 1(UVA/PS/Fe2+) k =
0.018 × 102 min− 1 UVC/PS/Fe2+)
UV - A and UV-C
k =0.1304 h− 1 t(half-life) =5.32 h
Hormones 72.0 kinetic model = pseudo-first-order [222]
300-W xenon lam
k = 2.0 × 103 (E2) k = 1.3 × 103 (EE2)
k = 24.5 × 103 (E1) k = 1.9 × 103 (E3)
51.0− 46.0 (E2, EE2, E3)
k = 34.7 × 103 (PG) kinetic model =
Hormones [223]
pseudo-first-order
Low pressure (LP)/UV direct
>93 (E1, PG)
photolysis
70.0 (NP)| HA 16.0 (NP1EO)|HA
Alkylphenol 18.0 (NP2EO)|HA 75.0 (TCS)|HA kinetic model = pseudo-first-order [224]
58.0 (BPA)|HA
52.0 (NP)| NO3− 16.0 (NP1EO)|
NO3− <5.0 (NP2EO)| NO3− [224]
98.0 (TCS)| NO3− 30.0 (BPA)| NO3−
− 1
t = 120 min [ZnO] =1 g.L pH = 8
Kinetic model = pseudo-first-order
Phenol 95.0 [225]
Activated carbon| zirconium oxide
(ZrO)| UV–vis
k = 0.0097 (VZ); DT90* = 237 min k =
0.0023 (FR); DT90 = 1001 min k =
0.0092 (QP); DT90 = 250 min k =
Diphenol until 92.0 0.0872 (MT); DT90 = 26 min k = [226]
0.0082 (FT); DT90 = 28 min k =
0.0297(DT) DT90 = 78 min
ZnO|Na2S2O8|UV–vis
Kinetic model = pseudo-first-order
Antimicrobial 90.0 [196]
Fibrous silica-titania (FST)
83.0 %| pH = 3.0| t = 4 h) 100 %| pH
Surfactant 83.0–100 = 3 |t=2.5 h| T = 75 ◦ C [227]
Graphene oxide|TiO2 nanotubes
kapp* = 0.0505 min− 1 Ki* = 1.5641
mg L.min− 1 kinetic model =
Paraben 88–98 % [197]
Langmuir-Hinshelwood
UV-A, UV-C, UV–vis TiO2
t = 15 min [MEP] = 30 mg.L− 1 [O3] =
Paraben 100 [228]
30 mg.L− 1
pH = 9 (MEP) T = 20 ◦ C (O3)
<5.0 ATZ|O3 <10.0 ATZ|(O3| H2O2) [O3] = 0.5 mg.L− 1 [H2O2] =0.5 mM
ATZ - herbicide ALA - 68.0 ATZ|(O3| H2O2|UV) 68 ALA| [EDC] = 200 μg. L− 1 pH = 7 t = 30 min
herbicide CBZ - O3 70.0 ALA|(O3| H2O2) 80.0 ALA|
pharmaceutical EE2 - (O3| H2O2|UV) 88.0 CBZ| O3 90.0 [229]
Comparison of processes ozone|H2O2|
hormone PCP - fungicide, CBZ|(O3| H2O2) 92.0 CBZ|(O3|
UV
insecticide, bactericide H2O2|UV) 60.0 EE2|O3 68.0 EE2|
(O3| H2O2) 70.0 EE2|(O3| H2O2|UV)
62.0 PCP|O3 60.0 PCP|(O3| H2O2)
[229]
64.0 PCP|(O3| H2O2|UV)
1 1
kO3 = 0.58 s− (5 ◦ C) k O3 = 1.76 s−
Hormone > 97.0 [230]
(35 ◦ C)
21.0 MP| O3 34.5 MP| (O3|UV) 98.0
MP| (O3|UV|ZnO) 20.0 EP| O3 40.5
Paraben EP| (O3|UV) 97.0 EP| (O3|UV|ZnO) – [231]
20.0 PP| O3 38.0 PP| (O3|UV) 97.0
PP| (O3|UV|ZnO)
18.0 BUP| O3 38.0 BUP| (O3|UV)
96.0 BUP| (O3|UV|ZnO) 18.0 BZP|
[231]
O3 37.0 BZP| (O3|UV) 96.0 BZP|
(O3|UV|ZnO)
87.0 | O3 99.0 |(O3|Al2O3) 97.0 | pH = 11| O3 pH = 9 |(O3|Al2O3) pH =
Ester (O3|AC) 87.0 | (O3|H2O2|Fe2+) 85.0 11 |(O3|AC) pH = 7| (O3|H2O2|Fe2+) [232]
|(O3|H2O2) 81.0 |(O3|TiO2) pH = 9|(O3|H2O2) pH = 11|(O3|TiO2)
k = 0.326 min− 1 (Deionized water)
Hormone – [233]
k = 0.319 min− 1 (River water)
k = 0.325 min− 1 (Ground water) k =
0.312 min− 1 (Effluent) [233]
Ultrasonic density up to 840 W/L
Pharmaceuticals ~100 [234]
(continued on next page)
9
W.T. Vieira et al. Journal of Environmental Chemical Engineering 9 (2021) 104558

Table 4 (continued )
Process Compound Class Degradation (%) Other parameters References

Diclofenac (DCF)
Carbamazepine (CBZ)
Amoxicillin (AMX)
Naphthol blue black (NBB)
propylparaben (PPB)
Fenton Bisphenol A (BPA)
Methylparaben (MP)
Ethylparaben (EP)
Fenton Bezonphenone 1 (BP1)
Bezonphenone 2 (BP2)
Bezonphenone 3 (BP3)
Bisphenol A
Bisphenol (BPA)
Fenton
Sulfamethoxazole (SMX)
Ciprofloxacin (CPX) Ibuprofen
(IBP)
Dietil ftalato (DEP)
Paraben
Synthetic organic compound
MP - Paraben EP - Paraben
BP1 - Bezonphenone BP2 -
Bezonphenone BP3 -
Bezonphenone
Synthetic organic compound
BPA - diphenol Other
pharmaceuticals
Plasticizer
65.6–100 (NBB|sea water)
53.6–94.4 (NBB)|deionised water)
33.7− 97.8 (PPB|sea water)
37.0–96.0 (PPB)|deionised water)
80.0− 100
39.7–75.4 |MP 31.2–58.6 |EP
40.9–68.5 |BP1 39.8–70.4 |BP2
33.8–55.9| BP3
> 95.0
87.6
100
Membrane/ ultrassound/activated
carbon
Variable frequencies (300–1700 kHz) [235]
[Fe2+] = 0− 16μM (40− 80 % removal) [236]
[H2O2] = 0− 1000μM (28− 100 %
removal)
[BPA] = 250− 2000 μM (50− 100 %
removal) t = 30 min
– [192]
pH = 5 [BPA] =20 ppm [Catalyst] =5
[237]
g.L− 1
[H2O2] =100 ppm Kinetic model =
second-order
Heterogeneous Fenton-like with [237]
modified magnetic nanoparticles with
sodium alginate
A catalyst consisting of dandelion-like
copper-aluminium-silica nanospheres [238]
(DCAS Ns)
[DEP] = 200 mg.L− 1 [O3] = 45 g.m-3
[H2O2] 0 = 2.5 × 10-2 mol.L− 1 [Fe2+)] [239]
0 = 5 × 10-3 mol.L− 1 t = 50 min

DT90* The time required for 90 % degradation.

HA* Humic acid.
kapp* Apparent reaction rate constant.
ki Initial reaction rate.

Table 5
Examples of alternative adsorbents applied for the removal of endocrine disruptors.
Adsorbent Adsorbate Adsorption capacity Additional information References

Bisphenol A 20 mg.g− 1 Organo-montmorillonite [266]

Clay Atrazine 3.492 mg.g− 1 Organophilic clay [267]
2,4 - D 50.36 mg.g− 1 Organophilic clay [268,267]
Carbamazepine 11.57 mg.g− 1 Natural clay Na-montmorillonite [269]
17β-Estradiol 26.91 mg.g− 1 Rice straw-derived biochar [270]
Biochar Sulfamethoxazole 212.8 mg.g− 1 Biochar-supported magnetic CuZnFe2O4 composite [271]
Bisphenol A 9.68 mg.g− 1 Ulva prolifera biochar [272]
Estriol 117.72 mg.g− 1 – [273]
Metal-organic framework
Carbamazepine 101.12 mg.g− 1 Flexible MIL-53(Cr) [274]
Estrone 2.698 mg.g− 1 Rice husk [275]
17β-Estradiol 1.649 mg.g− 1 Rice husk [275]
Agro-industrial waste and by-products Bisphenol A 18.35 mg.g− 1 Black tea leaves [276]
Sulfamethoxazole 295.06 mg.g− 1 Functionalized sawdust [277]
Bisphenol A 263.7 mg.g− 1 Functionalized sawdust [277]
Bisphenol A 64.6 mg.g− 1 Chitin [278]
Biosorbent
Benzo[a]pyrene 84 mg.g− 1 Chitin [278]
Bisphenol A 15.46 mg.g− 1 Chitosan‒polyvinyl alcohol-carbon fibers [279]
Biosorbent
17α-ethinylestradiol 24.50 mg.g− 1 Yeast biomass [280]
17β-Estradiol 8.24 mg.g− 1 Y type zeolite [281]
Zeolite
Bisphenol S 25.64 mg.g− 1 Nanozeolite NaY [282]

is usually more cost-effective than reverse osmosis because they have
similar removal efficiency, however, nanofiltration requires less energy
[305,306]. Forward osmosis has a similar operation and efficiency to
these of nanofiltration and reverse osmosis, however, it applies the
gradient at the osmotic pressure as driving force [307]. Coupling
different techniques such as membrane and biodegradation have shown
promising results for rejection of EDCs, in particular those that are
recalcitrant to biodegradation processes [308].
Membrane filtration process has high removal efficiency, but there
are some drawbacks associated with them, mainly the high cost of the
membrane, the membrane fouling and the generation of great volumes
of concentrate. Most membranes require regular changes due to the
fouling effect, which makes the process less cost-effective. The other
disadvantage comprises the challenges of treatment and discharge of the
contaminants accumulated during the process. It is essential to deter­
mine environmentally friendly ways to manage this potentially

10
W.T. Vieira et al. Journal of Environmental Chemical Engineering 9 (2021) 104558

Table 6 isoenzymes have different activities considering the intrinsic charac­

Exhibits some membrane process used for the removal of the most commonly teristics of the substrate and the process, such as temperature and pH
found endocrine-disrupting compounds. [309].
Process Compound % Additional References The decomposition can occur through aerobic, anaerobic, or hybrid
Removal information processes. Aerobic processes have a fast decomposition rate and the
Microfiltration Bisphenol A 24 Initial [290] removal of contaminants may happen through biosorption, bio-
concentration of chemical degradation, vaporization, and photo-transformation. The
0.7 ± 0.29 mg.L− 1 main aerobic process employed for the treatment of EDCs is the acti­
Estrone [291]
<20 –
vated sludge. Anaerobic processes such as upflow sludge blanket,
Ultrafiltration Bisphenol A 64− 76 Initial [292]
concentration of 1 anaerobic filters, and anaerobic lagoons, are less expensive, however, it
mg.L− 1 requires longer operational times and it has inferior efficiency. The
Initial removal efficiency of biological processes depends on several factors:
17β-estradiol 24− 63 concentration of 1 [292] characteristics and behavior of the organisms; type of contaminant,
mg.L− 1
Membrane
operational conditions and type of water matrix [311–313].
17α- Commonly, the biological treatment is the most cost-effective tech­
94− 96.6 coupled with [293]
ethinylestradiol
Ultrafiltration carbon nanotubes nique for the removal of EDCs from water and wastewater, however,
Membrane some compounds are non-biodegradable and therefore are recalcitrant
Bisphenol A 73.6− 78.9 coupled with [293]
to those treatments. Additionally, some toxic substances cannot be
carbon nanotubes
17α- biologically treated. In these circumstances, adsorption, membrane
42− 53 – [294] filtration, and advanced oxidative processes are feasible for the removal
ethinylestradiol
Nonpolyamide and rejection of EDCs [218,314].
membrane using
Ethylparaben 93.1 [295]
green tannic acid-
iron complexes 7. Conclusions and future perspectives
Nonpolyamide

Benzylparaben 99.7
membrane using
[295] This present review addressed several classes of endocrine-
green tannic acid- disrupting compounds evaluated in the last decade and their potential
iron complexes
Initial
hazard to human and animal health due to their presence in water
Nanofiltration bodies. These substances are increasingly growing in the environment,
Bisphenol A 100 concentration of [290]
0.3 ± 0.29 mg.L− 1 and depending on the level of exposure, they can cause hormonal
Initial problems, which can lead to more serious diseases, such as cancer or
Bisphenol A 72 concentration of [290]
infertility. Although EDCs are found in low concentrations, there are
0.7 ± 0.29 mg.L− 1
NF90 membrane – already effective methods for detecting these compounds, such as
Sulfamethoxazole 96 [296]
pH10 chromatographic and extraction methods, bioassays and biosensors. It
Carbamazepine 88
NF90 membrane –
[296] was observed that it is still necessary to develop advanced detection
pH10 methods that can cover different substances and their effects at lower
Three polyamide-
Bisphenol A ≥ 98
based membrane
[297] levels of concentration and to further improve the biosensors.
Bisphenol A 99.51 [298] The removal of EDCs from water and effluents is a challenge due to
Reverse
XLE membrane – the complexity of structures and particularities of each process. The
osmosis Sulfamethoxazole ≥ 98 [296]
pH10 conventional processes present in water and wastewater treatment
XLE membrane –
Carbamazepine ≥ 96 [296] plants are inefficient for completely removing or degrading EDCs, then it
pH10
17α- has been observed that the use of alternative treatments, as adsorption,
87.5− 91.5 [298]
Forward ethinylestradiol
–
advanced oxidative processes and biodegradation, showed high per­
osmosis
Carbamazepine 99.8
Coupled with
[298]
centages of removal. The combined processes can be a solution, as
reverse osmosis promising results were obtained, for example, with AOPs coupled with
Based on an
Estrone 77 anaerobic-anoxic- [299]
membrane filtration to remove EDCs from aqueous solutions. Another
Membrane example of combined processes that have been discussed in the litera­
oxic process
bioreactor
Coupled with ture and have shown efficient removal for EDCs is the combination of
Carbamazepine 82.1− 93.1 [300]
reverse osmosis microfiltration with enzyme immobilization. Overall, regarding EDCs,
new detailed legislation, and improved strategies for monitoring and
controlling should be developed. It is also important to study the feasi­
bility and the cost-benefit of the scale-up of alternative removal pro­
hazardous waste [285]. cesses at the water and effluent treatment stations as a complementary
step to ensure the quality of the outgoing product and consumer safety.
6.4. Biodegradation
Availability of data and material
Biological treatments are based on the use of living organisms,
mainly bacteria [209], fungi [211], yeast [210] and immobilized en­ Not applicable.
zymes [212,213] for the degradation of contaminants into nontoxic
compounds. Within the scope of organisms not alive, there was a Code availability
growing interest in the horseradish peroxidase enzyme (HRP) of the
oxidase family, due to its high oxidative conversion capacity of several Not applicable.
EDCs, such as estrone (E1), 17β-estradiol (E2), estriol (E3), and
17α-ethinylestradiol (EE2). The aforementioned EDCs were evaluated
both separately [212,309] and mixed in a sample [310]. Analogous to Declaration of Competing Interest
most peroxidases, HRP has heme protein group and acts as a catalyst in
the reduction of peroxides such as H2O2. It is worth mentioning that HRP The authors report no declarations of interest.

11
W.T. Vieira et al.
Acknowledgements
The authors thank for the financial support from Research Support­
ing Foundation of the State of São Paulo(FAPESP, proposal nº. 2017/
18236-1,2019/11353-8), Brazilian National Research Council (CNPq,
proposal nº. 406193/2018-5 and 308046/2019-6), and Coordination for
the Improvement of Higher Education Personnel (CAPES, Financial code
– 001).
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