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Wetlands for Micropollutant Removal

This review article discusses the increasing concern over emerging micropollutants (EMPs), particularly endocrine disrupting chemicals (EDCs), in wastewater and their adverse effects on public health and the environment. It highlights the effectiveness of constructed wetlands (CWs) as a cost-effective and eco-friendly method for removing EDCs from contaminated water, while also emphasizing the need for further research on the comparative performance of different CW systems. The findings suggest that integrating CWs with novel technologies can enhance their efficiency in treating wastewater contaminated with various micropollutants.

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0% found this document useful (0 votes)
47 views22 pages

Wetlands for Micropollutant Removal

This review article discusses the increasing concern over emerging micropollutants (EMPs), particularly endocrine disrupting chemicals (EDCs), in wastewater and their adverse effects on public health and the environment. It highlights the effectiveness of constructed wetlands (CWs) as a cost-effective and eco-friendly method for removing EDCs from contaminated water, while also emphasizing the need for further research on the comparative performance of different CW systems. The findings suggest that integrating CWs with novel technologies can enhance their efficiency in treating wastewater contaminated with various micropollutants.

Uploaded by

Pauliina Riico
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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South African Journal of Chemical Engineering 48 (2024) 395–416

Contents lists available at ScienceDirect

South African Journal of Chemical Engineering


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

Applications of constructed wetlands in removing emerging


micropollutants from wastewater: Occurrence, public health concerns, and
removal performances – a review
Shifare Berhe Gebru *, Adhena Ayaliew Werkneh
Department of Environmental Health, School of Public Health, College of Health Sciences, Mekelle University, P.O. Box 1871, Mekelle, Ethiopia

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

Keywords: Emerging micropollutants (EMPs)—which include endocrine disruptors, pharmaceuticals, personal care prod­
Constructed wetlands ucts, pesticides, and industrial chemicals—have recently received global attention due to their detection in the
Endocrine disrupting chemicals environment at trace levels and being labeled as a first-priority environmental and public health concern. EMPs
Emerging micropollutants
are often identified by their nature of toxicity, bioaccumulation potential, and persistence, despite low con­
Environmental and public health concern
Water and wastewater treatment
centrations. Their prevalence in the aquatic environment is closely linked to their difficulty being removed using
conventional water and wastewater treatment techniques. Constructed wetlands (CWs) have drawn more interest
in this field in recent years, largely because of their affordability, ease of use and upkeep, and environmental
friendliness. However, only a small number of researchers have examined and compiled the body of knowledge
regarding the use of CWs to remove endocrine disrupting chemicals (EDCs) and other micropollutants from
various sources. Previously reviewed articles were not focused on the comparative performance of various types
of CWs and their hybrid systems to remove EDCs from various wastewaters. Therefore, the applications and
suitability of different types of CWs and their integrated systems for removing a wide range of emerging
micropollutants from contaminated environments (water and wastewater) were reviewed. The findings from the
review confirmed that integrating CWs with other novel technologies, such as membrane bioreactors (MBR),
electrochemical oxidation, and microbial fuel cells (MFCs), can maximize the specific advantages of constructed
wetland systems in terms of emerging micropollutant removal.

1. Introduction substances like phthalates, pesticides, polychlorinated biphenyls (PCBs),


Pharmaceuticals, personal care products, alkylphenols, bisphenols and
Endocrine-disrupting chemicals (EDCs) are increasingly common steroid estrogens i.e. Natural estrogens (estrone (E1), 17 b-estradiol (E2)
environmental micropollutants that affect the endocrine systems of and estriol (E3)) and synthetic estrogens (17a-ethinyl estradiol (EE2))
humans and animals. Even at very low concentrations, EDCs have been (Luo et al., 2014; Liu et al., 2021). Those emerging contaminants have
linked to cancer, reproductive disorders, mutagenicity, and thyroid been released in larger amounts in the environment for decades, and,
problems in fish (Guo et al., 2020; Werkneh et al., 2022). They are due to their low degradation rate, a significant increase in their back­
emerging exogenous compounds, that have received significant interest ground concentrations has been observed in different environmental
due to their deleterious effects on growth, immunity, neurological sys­ components such as soil and water (Avila et al., 2010). EDCs constitute
tem, and endocrine systems, as well as their interference with hormone pollutants of high interest due to their appearance in several consumer
production and release, which can lead to metabolic issues (Guo et al., and personal-care products, and their toxicological and physicochemical
2020). Moreover, the EPA of the United States defines EDCs as xenobi­ properties (Durcik et al., 2023). Studies have indicated that these
otics that "interfere with the synthesis, secretion, transport, binding, compounds are not sufficiently removed in wastewater treatment plants
action, or elimination of natural hormones in the body that are (WWTPs) and end up as residual concentrations (ng/L or even µg/L) in
responsible for the maintenance of homeostasis, reproduction, devel­ treatment plant effluents, eventually reaching final recipients (Zhang
opment, and/or behavior (Werkneh et al., 2022). EDCs includes a et al., 2014; Avila et al., 2015).

* Corresponding author.
E-mail address: [email protected] (S.B. Gebru).

https://doi.org/10.1016/j.sajce.2024.03.004
Received 13 September 2023; Received in revised form 26 February 2024; Accepted 6 March 2024
Available online 12 March 2024
1026-9185/© 2024 The Author(s). Published by Elsevier B.V. on behalf of South African Institution of Chemical Engineers. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

Several research works have reported EDCs in raw and treated waterways as result of agricultural runoff (Luo et al., 2014; Ioannidou
wastewater and sewage sludge (Pironti et al., 2021; Werkneh et al., and Stefanakis, 2020). Furthermore, veterinary drugs and food additives
2022); sewage effluent (Werkneh et al., 2022); surface water (Wang used in livestock farming are excreted by animals and may reach the
et al., 2018; Pironti et al., 2021); and seawater (Lu et al., 2020). Despite aquatic systems via runoff (Ribeiro et al., 2016; Mooney et al., 2020).
the fact that EDC concentrations are often low in the environment, they Endocrine disrupting chemicals (EDCs) are exogenous substances or
are still of major toxicological concern. Because they are not only mixture that can alter the functions of the endocrine systems and in­
extremely poisonous and estrogenic but also frequently exist as complex fluence physiology and development of aquatic organisms (Ismanto
combinations of chemicals (Durcik et al., 2023). The presence of EDCs et al., 2022; Singh et al., 2024). The presence of EDCs in aquatic envi­
may reduce the biological nutrient removal efficiency in wastewater ronment and their potential public health and environmental impact
treatment (Yi et al., 2017) and inhibit methanogenesis in the anaerobic become a growing concern in recent years (Pessoa et al., 2014). Steroid
fermentation of waste sludge (Hu et al., 2018; Wang et al., 2017). hormones are some of the relevant groups of EDCs which controls many
Several treatment approaches have been proposed to address this functions of endocrine systems and have attracted considerable atten­
problem, such as UV radiation, advanced oxidation, and ozonation, to tion owing to their harmful effects by interfering with the development,
eliminate EDCs (Azizi et al., 2022). Their high operation and mainte­ growth, aging, longevity, survival, and reproduction of aquatic organ­
nance costs render them unsustainable and unfavorable options in isms at nano-gram per liter levels in aquatic environments (Liu et al.,
developing countries. Therefore, low energy demanding, cost effective 2014; Gonsioroski et al., 2020; Macedo et al., 2023). Steroid hormones
and environmentally friendly technologies are recommended to reme­ can be divided into five subgroups based on structural characteristics:
diate EDCs. Constructed wetlands (CWs) are one of them and represent oestrogens, androgens, progestogens, glucocorticoids and mineral cor­
an efficient natural treatment method with low operational and main­ ticoids (Corsini et al., 2018). They are used extensively in our daily life
tenance costs, ease of use, and minimal environmental impact. There are for human medical treatments and in the livestock industry for con­
numerous studies in the literature about the performance and removal trolling animal breeding and promoting growth (Guedes-Alonso et al.,
methods of CWs, which have been effectively investigated for the 2014; Zhang et al., 2015). In the aquatic environment, the estrogens
treatment of a variety of pollutants (Witthayaphirom et al., 2020; Liu have been attributed as a cause of reproductive disturbance in humans
et al., 2020; Lei et al., 2022; Overton et al., 2023). However, to the best and wildlife (Marlatt et al., 2022) and may be responsible for effects
of our knowledge, only a few studies have reviewed and summarized the such as the feminization of male fish (Delbes et al., 2022). Study findings
existing knowledge on the application of CWs to remediate EDCs from confirmed that concentrations of 1–10 ng l− 1 of 17β-estradiol (E2) and
various sources. Previously reviewed articles were not focused on the concentrations of 0.1 ng l− 1 of contraceptive 17α-ethinylestradiol (EE2)
comparative performance of various types of CWs and their hybrid provoking feminization of some male fish species (Zuo et al., 2013;
systems to remove EDCs from various wastewaters. The purpose of this Vymaza et al., 2015). Moreover hormone residues can reach the aquatic
paper is to review the applications and suitability of different types of environment through manure agricultural application (Zhang et al.,
CWs and their hybrid systems to remove EDCs from the contaminated 2015) and the discharge of raw and treated municipal and industrial
environment, specifically water and waste water. This review paper also wastewater (Pessoa et al., 2014). Other EDCs such as antibiotics are
highlights EDCs removal mechanisms of CWs, factors affecting EDCs commonly present in wastewater effluents, sludge, sediment, natural
removal efficiency of CWs, and recommendations for future research waters, drinking water, and groundwater (Jiang et al., 2013). The
direction. presence of these compounds in Environment promotes the develop­
ment of antibiotic-resistant genes in soil bacteria (Serwecińska, 2020).
2. Occurrence, sources, and public health concerns of EDCs Pharmaceuticals and Personal Care Products (PPCPs) such as non­
ylphenol (NP) and octylphenol (OP) are more toxic than the parent
The occurrence and fate of EDCs in the environment and the possible compound and are known to disrupt endocrine function in wildlife and
adverse effects imposed on living organisms have attracted the attention humans. Study results revealed that both NP and OP can induce vitel­
of the scientific community worldwide, and they are labeled as first- logenin (VTG) synthesis and feminization in male fish at the ppb con­
priority or emerging pollutants. Research findings revealed that EDCs centration level, and the estrogenic activity of OP is 20 times that of NP
could enter water resources and the environment through point and according to previous research (Servos et al., 2005). Some of the EDCs
non-point sources (Cai et al., 2012; Luo et al., 2014; Pessoa et al., 2014). with their Public Health and Environment effects are illustrated in
Studies reported that Alkylphenols which are metabolites of their Table 1.
ethoxylate precursors and EDCs have been used in many industrial,
agricultural, commercial and household functions (Luo et al., 2014). 3. Constructed wetland system, operating conditions and EDCs
These types of EDCs are added to emulsifiers, adhesives, and pesticides removal mechanisms
and tend to be adsorbed by sediment (Sangeetha et al., 2021). Alkyl­
phenols have been found in ambient waters (Ronderos-Lara et al., 2022) 3.1. Constructed wetland systems
and landfill leachates as well as effluent from industrial and municipal
wastewater treatment facilities (Ateş and Argun, 2021; Montenegro Constructed wetland systems can be defined as engineered systems
et al., 2021). The presence of estrogen hormones in surface water and in planned, designed and constructed to imitate natural wetland systems
effluents from municipal wastewater treatment plants (WWTP) at con­ utilizing natural wetland processes including wetland plants, soil, and
centrations capable of causing changes in the reproductive system of fish associated microorganisms to remove contaminants from wastewater in
have been stated by previous studies (Sousa et al., 2022; Jenila et al., a controlled environment (Hassan et al., 2021). This remedial technol­
2023). The existence of those EDCs in wastewater mainly arises from ogy is a low cost and environmentally friendly sanitation alternative to
direct women excretion, in particular from pregnant females and women conventional methods and recommended for on-site wastewater treat­
using oral contraception or hormone replacement therapies (Luo et al., ment in small communities to meet required effluent discharge stan­
2014; Liu et al., 2020). Regarding pharmaceuticals and personal care dards (Waly et al., 2022). It is also used widely for the removal of
product (PPCP) industries are one of the possible sources of these pol­ emerging micro-pollutants such as EDCs due to several advantages
lutants. Moreover hospital effluents and municipal wastewaters can also associated with CWs as compared to other waste water treatment
be significant pathways of the above mentioned emerging pollutants technologies, which include simple, robust, eco-friendly, cost-effective
(Ajala et al., 2022). Agriculture is another important source of micro processes with low operational cost and have relatively good wastewater
pollutants, mainly due to the pesticides used to improve the productivity purification efficiencies for nutrient mass load (Vymazal et al., 2017;
(e.g., controlling the pests and vectors), which can be found in Sánchez et al., 2022). According to studies conducted by Kathe Seidel in

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S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

Table 1 Table 1 (continued )


Environmental and public health effects of different categories of EDCs. EDCs category Selected Adverse effects Reference
EDCs category Selected Adverse effects Reference compounds
compounds
proliferation,
Natural estrogens Estrone (E1) Provoke Meijide et al. 2016; decreased uterine
feminization in Borrull et al., receptivity,
male fish, sexual 2020. increased tubule
differentiation of atrophy, decreased
fish. sertoli cell number
Estrodiol (E2) Sexual ; Borrull et al., function, cause
differentiation of 2020; Martyniuk breast cancer,
fish, changes in the et al., 2020 cause miscarriage
production of for pregnant
vitellogenin (egg women, premature
yolk precursor deliveries of baby,
protein expressed Type-2 diabetes,
in the females of cardiovascular
oviparous species disease,
such as fish, hypertension and
amphibians, increased
reptiles, birds and cholesterol levels,
most dysfunction in the
invertebrates) kidneys, disruption
Estriol (E3) Intersex behaviors Ortiz-Zarragoitia of the thyroid
and the induction et al., 2014; hormone
of plasma Wojnarowski concentration
vitellogenin in fish et al., 2021 Carbamazepine Affect the health of Zhu et al., 2023
exposed to the (CBZ the flora and fauna
environment next of aquatic
to the outfalls as a ecosystems,
result of estriol causing damage to
being present in organs such as the
water kidney, liver, and
Testosterone The feminization Belfroid et al., gills, in addition to
(TES) of male fish and the 1999, Gharaei alterations in the
induction of et al., 2020 growth of fish,
vitellogenin in algae, and small
male trout are two crustaceans
consequences of Ibuprofen(IB) Affect the health of Ogunwole et al.,
testosterone. the flora and fauna 2021; Jan-Roblero
Progesterone Research revealed Kuster et al., 2010; of aquatic & Cruz-Maya,
(PRO) that progesterone xu et al., 2009; ecosystems, cause 2023
at pollution levels Chang et al., 2007 kidney and liver
can negatively damage, bleeding
affect fish output, in the stomach and
induce population bowels and risks of
decrease, and skew heart attack.
sex ratios. It can Diclofenac Oncorhynchus Smiljanić et al.,
also cause sperm mykiss: alterations 2020
motility in male to the renal system
fish, as well as in and gills
frogs and mussels. Naproxen (NPX) Fish and human Stancová et al.,
Synthetic Ethinyl estradiol Feminization of Leet et al., 2015; intestines are 2015; Ríos et al.,
estrogens (EE3) male fish and adversely affected 2022
altered oogenesis by NPX and its
in females derivatives.
Progestin Causes androgenic Leet et al., 2015; Acetaminophen Acetaminophen Baron et al., 2014;
levonorgestrel effect, which leads Runnalls et al., can enter the body Fisher and Curry,
(LNG) to masculinization 2015, Svensson of a person through 2019.
in fish, inhibited et al., 2014; the drinking of
spermatogenesis, Overturf and tainted water,
reduced egg Huggett, 2015 resulting in
production, negative health
decreased fish effects that over
reproduction, time may lead to
increased the chronic illnesses,
weight and lengths cancer, and
of female fish, and resistance.
led females to Penicillin, It results in Serwecińska, 2020
acquire male sulfonamides, bacterial pathogen
characteristics tetracyclines resistance, which
Pharmaceuticals Bisphenol A Causes polycystic Caserta et al. 2013; (antibiotics) affects the higher
and Personal (BPA) ovary syndrome, Ghosh et al., 2022; food chain and
Care Products fertility problems Tang et al., 2022 alters the structure
(PPCPs) and endometriosis, of microbial
impaired uterine communities in
endometrial nature

397
S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

the 1960s and Reinhold Kickuth in the 1970s, CWs are thought to have combination of wetlands with other pond systems such as lagoons and
originated in Germany (Kadlec and Wallace 2009). CWs have been facultative ponds in parallel or in series. Such hybrid systems are nor­
widely employed since its first full-scale application in the late 1960s. mally laid out in two or three stages in order to realize the improvement
Constructed wetlands (CWs) have attracted considerable attention and of treatment efficiencies. The combination of different types of CWs may
extensively applied to treat domestic sewage, agricultural wastewater, build hybrid CW systems that have higher removal efficiencies than
industrial effluent, mine drainage, landfill leachate, urban runoff, and individual CWs.
polluted river water in the last several decades due to their low-cost,
easy-operation/maintenance (Vymazal, 2010; Wu et al., 2014).
The constructed wetlands used for the removal of contaminants from 3.2. Components of constructed wetlands
wastewater can be classified into three categories (Fig. 1), based on their
configurations and operation modes, which includes loose water sub­ In artificial wetlands, the substrate not only supports the develop­
surface (FWS) CWs, subsurface flow (SSF) CWs, and hybrid CWs. In ment of plants and microbes, but also directly interacts with toxins
details, SSF CWs are sub-categorized into vertical subsurface flow through sorption processes. Physical, chemical and biological processes
(VSSF) and horizontal subsurface flow (HSSF) relying on flow patterns such as volatilization, sorption and sedimentation, photo-degradation,
(Vymazal, 2010). The SF-CWs are composed of shallow channels or plant uptake and microbial degradation, may occur simultaneously,
basins planted with vegetation (which encompass rooted and floating contributing to eliminate several types of compounds including micro-
plants) in which unfastened wastewater flows at rather shallow intensity pollutants (Zhang et al., 2014; Carvalho et al., 2014; Li et al., 2014).
over the impermeable backside liner or the packed substrate layer .In the Substrate (also known as support matrix) is an important component in
HSSF-CW systems, wastewater is fed into the wetland at the inlet vi­ constructed wetlands, especially in subsurface flow constructed wet­
cinity and flows horizontally through the substrate under the ground of lands. In artificial wetlands, the substrate not only supports the devel­
wetland bed this is planted with vegetation. After the remedy of opment of plants and microbes but also directly interacts with pollutants
wetland, the wastewater effluent is accrued at the opening zone. For the through sorption processes. Sorption of pollutants onto the surface of
VSSF-CW systems, wastewater is dosed onto the ground of wetland bed substrate involves different mechanisms such as hydrophobic parti­
and then flows vertically from the planted layer down through the tioning, van der Waals interaction, electrostatic interaction, ion ex­
substrate until it reaches the outlet zone (Vymazal, 2007, 2011). The change, and surface complexation (Dordio and Carvalho, 2013a; Pei
hybrid CW systems are the combination of two or more wetlands or the et al., 2016). The most frequently used substrate for emerging contam­
inant removal in constructed wetlands is gravel which was found

Fig. 1. Different configurations of constructed wetlands: (A) Horizontal flow CW, (B) Vertical flow CW), and (C) Free water surface CW, (D) Hybrid constructed
wetland (Parde et al., 2021).

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S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

efficient for sorption removal of the micro-pollutants including EDCs Additionally; Avila et al. (2015) reported that biodegradation and
which are refractory to biodegradation but with relatively high hydro­ sorption were the main removal mechanisms for BPA from waste water
phobicity, for example, carbamazepine (Li et al., 2014). Another com­ by SSVFCW and it was confirmed that vertical flow units appear to be
mon substrate used in constructed wetlands is soil. Study was done by more efficient in the removal of BPA, due to their increased oxygen
Hussain et al. (2012) to investigate the removal efficiencies of three transfer to the media. Other study also supports this by stating aerobic
antibiotics (monensin, salinomycin, and narasin) in two SF-CWs with degradation processes enhances the removal of organic micro-pollutants
different soil substrates and the study finding showed that higher such as EDCs from various types of waste water (Verlicchi and Zambello,
removal efficiency was observed for the sandy soil when compared with 2014). Moreover, Matamoros et al. (2007) evaluated the ibuprofen and
the sandy loam soil. Additionally, some biosorbents such as rice husk, caffeine removal efficiency of sub surface vertical flow CWs and re­
pine bark, and granulated cork have been considered as interesting al­ ported that the biodegradation and sorption in systems’ substrate are the
ternatives to the common substrate materials in constructed wetlands main mechanisms of these emerging contaminants removal.
due to their low cost, economical value of reuse, and easy disposal by In SSHFCWs, wastewater is kept below the media’s surface and
incineration (Li et al., 2014). Plants are other component in constructed travels through the bed horizontally until it reaches the outlet (Kadlec
wetlands system and play a significant role in direct uptake of many and Wallace, 2009). In this type of CW, anaerobic biodegradation is an
organic pollutants in wastewater. In the cell membranes of plant roots, important removal mechanism of micro pollutants. Study conducted in
there are no specific transporters for the xenobiotic organic compounds Greece by Papaevangelou et al. (2016) to assess Endocrine Disrupting
like pharmaceuticals to move into the plants tissues, but the uptake and Chemicals removal efficiency of SSHF constructed wetlands (pilot-scale)
translocation of these compounds within plants can be simply driven showed that anaerobic degradation and sorption were the main removal
through diffusion (Dordio and Carvalho, 2013b). Several plant species mechanisms for these emerging micro pollutants. The results of a
have been reported for use in pharmaceutical wastewater treatment continuous injection experiment conducted in a pilot-scale horizontal
wetlands among which the most popular plants are Phragmites australis, subsurface flow constructed wetland system to assess the behavior of
Typha spp. Typha angustifolia and Typha latifolia (Li et al., 2014). four pharmaceuticals and personal care products (ibuprofen, naproxen,
Moreover, Microbes in constructed wetlands usually play the main diclofenac, and tonalide) and a phenolic estrogenic compound
role in the processes of transformation and mineralization of nutrients (bisphenol A) showed that overall removal efficiencies for the chosen
and organic pollutants (Liang et al., 2017; Malyan et al., 2021). compounds ranged from 97 % to 99, with anaerobic degradation and
Biodegradation of organic compounds by microbes in constructed wet­ sorption as a likely removal mechanism (Avila et al., 2010).
lands can occur under both the aerobic and the anaerobic conditions Furthermore, the investigation done by Wagner et al. (2020) illus­
involving the activities of various microorganisms such as heterotrophic trated that the main removal mechanisms of benzotriazole in CWs are
bacteria, autotrophic bacteria, fungi (basidiomycetes and yeasts), and adsorption, biodegradation and plant uptake, followed by
specific protozoa (Kadlec and Wallace, 2009). photo-degradation with a minor role. Another study aimed to assess
removal efficiency of horizontal subsurface Flow and Vertical Flow
3.3. EDCs removal mechanisms in constructive wetland pilot-Scale constructed wetlands for emerging pollutants stated that
biodegradation under aerobic and/or anaerobic conditions and
The general removal mechanisms of pollutants in CWs are adsorp­ adsorption on the substrate are the main removal mechanisms (Gikas
tion, biodegradation, plant uptake, and volatilization (Vymazal, 2014; et al., 2021). Furthermore, other studies also found that 95–100 %
Sharma and Malaviya, 2022). The initial removal mechanism of pol­ removal efficiency of Acetaminophen (ACE) was achieved in SSHFCWs
lutants in CWs is adsorption to treatment media such as gravel, soil, and and concluded that biodegradation was the main removal mechanism,
plant roots (Chen et al., 2016a; Ji et al., 2022). Consequently, microbes although sorption could also contribute to its degradation (Chen et al.,
in the plant rhizosphere degrade organic pollutants adsorbed onto the 2016a; Phong Vo et al., 2019). On the other hand, research work con­
media (Chen et al., 2016a; Kurzbaum et al., 2010). Plant–microbe in­ ducted to evaluate the removal efficiency of Emerging pollutant from
teractions in the rhizosphere have attracted attention for degrading waste water (Ofloxacin) showed that 90 % of the contaminant removed
toxic compounds (Toyama et al., 2011, 2013). Plants can preserve big in lab scale SSHFCWs and biodegradation could the probable removal
microbial populations with inside the rhizosphere. According to Chen mechanism (Yan et al., 2016). In SFCWs/FWS wetland the removal ef­
et al. (2016a) and Rocha et al. (2015), root exudates containing oxygen, ficiency of BPA was fairly high if compared to the SSHFCWs unit and it
aromatics, aliphatics, carbohydrates, and amino acids stimulate their was noted that biodegradation, sorption and photo-degradation were
metabolic activity. The plant is shielded from dangerous pollutants by the main mechanisms for their removal (Avila et al., 2013; Matamoros
rhizosphere microbes through a process called biodegradation. There­ et al., 2012; Witthayaphirom et al., 2020). In addition to this, several
fore, the plant–microbe systems in CWs are expected to contribute to authors confirmed that photo-degradation is a principal removal
removal of EDCs -emerging compounds from waste water. Several re­ mechanism involved in Diclofenac (DCF) attenuation in water bodies by
searchers noted that EDCs removal mechanism of constructed wetlands FWS constructed wetland system (Matamoros and Salvadó, 2013; Avila
varies depending on their type/configuration and related previous study et al., 2014b; Kumar et al., 2023).
findings are reviewed as follows. The combination of several wetland types has demonstrated to
In SSVFCW, the beds are pulse-loaded with a large amount of water optimize a number of significant treatment processes, achieving an
to temporarily flood the surface of the bed (Kadlec and Wallace 2009). outstanding overall reduction in EDCs as well as removal of conven­
According to a prior study, aerobic biodegradation—rather than sorp­ tional water quality parameters (Avila et al., 2014a). Earlier research
tion on sand—was the primary mechanism responsible for the removal work done by Avila et al. (2015) obtained EE2 removal efficiencies be­
of oestrone, 17 beta-oestradiol, and 17 alpha-ethynylestradiol in vertical tween 60 and 80 % in hybrid CW composed of three unities: a vertical
flow CWs treating the effluent of a traditional wastewater treatment subsurface flow, a horizontal subsurface flow and a free-water surface or
system, achieving satisfactory removal rates (from 67.8 to 84.0 %) (Song surface flow constructed wetland treating municipal wastewater. They
et al., 2009). In addition to this, studies approaching sewage treatment concluded that photo-degradation was the main mechanism for EE2
focusing on the removal of micro-pollutants have shown that SSVFCW removal in the free-water surface system due to the direct incidence of
have potential to minimize emerging contaminants disposal (Li et al., radiation. The study done in China stated that an integrated constructed
2016; Zhang et al., 2017; Lima et al., 2018; Zhang et al., 2018b), and wetland (ICW) system effectively removed the steroid hormones (97.4 ±
sorption is one of the mechanisms that contribute to the removal of some 0.09 %) and biocides (92.4 ± 0.54 %) from domestic waste water and
of these emerging micro pollutants (Dordio and Carvalho, 2013a; Huang these results indicate that adsorption onto the media was an important
et al., 2015). aqueous-phase removal mechanism (Chen et al., 2019). Additionally,

399
S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

previous study aimed to evaluate antibiotics and antibiotic resistance et al., 2007). A recent study done to compare micro pollutant removal
genes (ARGs) removing efficiency of integrated constructed wetlands efficiencies different CW designs showed that The removal efficiency of
(ICWs) from rural domestic wastewaters confirmed that ICW system methylparaben was higher in FWSCW (90 ± 1 %). A recent study
could significantly reduce most of the detected antibiotics and ARGs comparing the micro pollutant removal efficiencies of several CW de­
with their aqueous removal rates of 78 to 100 % and >99 %, respectively signs revealed that FWSCW had a better methylparaben removal effi­
(Chen et al., 2014). ciency (90 ± 1 %) (llyas and van Hullebusch 2020)

4. Application of constructed wetlands for EDCs removal from 4.2. Performances of sub-surface flow constructed wetland (SSFCW)
wastewater system

Recently, CWs have been proven effective to remove a variety of In CWs with subsurface flow, the water passes through the support
micropollutants from agricultural and municipal wastewater (Carvalho matrix, which is frequently made of sand or gravel. In comparison to
et al., 2013; Sossalla et al., 2021). According to earlier research works, SFCWs, where the water flows on top of the support matrix, the support
the effectiveness of CWs to remove pharmaceuticals has been shown to matrix of subsurface flow CWs encourages more adsorption and inter­
be at least as good as that of conventional wastewater treatment action between wastewater, support matrix, plants, and microorgan­
methods using natural processes involving plants, microorganisms, and isms, which increases the potential to remove biodegradable micro
solid support matrices (Liu et al., 2014; Sossalla et al., 2021). These pollutants (Gorito et al., 2017). In order to establish subsurface flow
published investigations, however, primarily concentrated on EDCs, constructed wetlands (SSFCWs), one of two hydrologic mechanisms can
pharmaceuticals and personal care products (PPCPs), antibiotics, and be used. Subsurface flow constructed wetlands (SSFCWs) can be built
ARGs in urban, residential, and animal wastewater. The removal effi­ using either the vertical or horizontal hydrologic modes. Water flows
ciency of various types of CWs are shown Table 2 and reviewed as either horizontally or vertically through the wetland bed medium in
follows. both, maintaining water below the surface (Kadlec and Wallace, 2009).
Typically, pea gravel, coarse gravel, and sandy loams are used to build
4.1. Performances of surface flow constructed wetland (SFCW) these wetlands. The presence or lack of oxygen is the main distinction
between the two hydrologic schemes (Kadlec and Wallace, 2009).
Free water surface built wetlands, also known as FWS CWs, are made Wetlands created with subsurface vertical flow (SSVF) are distinguished
up of basins or channels that include soil or another suitable medium to by a surplus of oxygen. Water periodically seeps into and drains through
support any rooted vegetation that may be present. Water that is moving soil pores, resulting in an aerobic environment that supports some
through the unit is at a relatively shallow depth. According to Vymazal, biochemical processes like nitrification and solids breakdown (Kadlec
2011, plug-flow conditions are ensured in long, narrow channels and Wallace, 2009). Strongly anaerobic, or anoxic, conditions inside the
because of the shallow water depth, low flow velocity, and presence of marsh bed medium are a characteristic of subsurface horizontal flow
plant stalks and litter. A biological treatment technology that uses a lot (SSHF) constructed wetlands. In these conditions, oxygen transmission
of land is free-surface built wetlands with emergent macrophytes. is reduced at the soil-air interface, which favors anaerobic biochemical
Because of air diffusion, FWS treatment wetlands often contain aerated reactions including the denitrification of nitrate to elemental nitrogen
zones near the water’s surface as well as anoxic and anaerobic zones in and the reduction of sulfate to hydrogen sulfide (Kadlec and Wallace,
the sediments and nearby. In densely populated FWS wetlands, the 2009).
anoxic zone can shift quite near to the water surface. Biomass decay
provides a carbon source for denitrification, but the same decay com­ 4.2.1. Performance of subsurface horizontal flow (SSHF) constructed
petes with nitrification for oxygen supply. It was also noted that Low wetland system
winter temperatures inhibit microbial activity while increasing oxygen The term "reed bed system" is another name for "horizontal flow
solubility in water (Kadlec and Wallace, 2009). The study aimed to constructed wetland," and in this form of CW system, wastewater
provide information on the efficiency of a SFCW in treating estrogens effectively flows horizontally over the support media (50–100 cm active
and androgens in dairy wastewaters in north east Ireland showed that an zone) at a depth of 5 to 15 cm (Tee et al., 2012; DBT, 2019). During this
average hormone removal efficiency of 95.2 % for estrogens and 92.1 % passage the wastewater containing pollutant will come into contact with
for androgens was achieved. However, the study noted that additional a network of aerobic, anoxic and anaerobic zones. The wastewater un­
design improvements may be required to further enhance removal ef­ dergoes aerobic and anaerobic condition.
ficiency of peak hormone concentrations (Cai et al., 2012). The E2 In HFCW, anaerobic conditions lead to the degradation of organic
removal efficiency of SFCW planted with Typha latifolia, Typha domi­ materials while aerobic conditions occur in the root zone (DBT, 2019).
ngensis, Scirpus acutus, Scirpus validus and Scirpus californicus in Califor­ HSSFCWs are the simplest and most affordable types of CWs that are
nia was investigated and found 36 % removal efficiency with sorption as now available when compared to other CW types. According to Kadlec
a removal mechanism (Gray and Sedlak, 2005). Another study done in and Wallace (2009), VF systems are effective at removing nutrients more
Ireland to assess the performances of SFCW treating dairy wastewaters effectively than HSSFCWs. However, VF systems frequently needed
showed that74.6 % of E2 was removed (Cai et al., 2012). In contrast, specialized technical equipment, such as expensive and infrequently
earlier research done in North Carolina, USA revealed that no removal of accessible effluent collectors and pumps. As a result, VF systems are now
E2 was observed in a SFCW treating swine wastewaters (Shappell et al., less widely used than HSSFCWs. In comparison to other CW variations
2007). Study carried out in Spain to investigate the emerging organic like FWS, HSSFCWs also has benefits. Although photo-degradation in
contaminant removal in a full-scale hybrid constructed wetland system FWS provides additional water purification, HSSFCWs have the major
for wastewater treatment and reuse showed that SFCW performed well advantage of limiting mosquito breeding since tainted water seeps
in removing BPA as compared to the SSHFCW unit. This could be below the surface of the CW. This is especially advantageous in areas
explained through enhanced biodegradation of this substance under where mosquito-borne illnesses can pose a severe threat to public health
higher redox and dissolved oxygen conditions within the water column (Kengne et al., 2003). Several studies have been carried out to assess the
of the SFCWs (Avila et al., 2014b). Previous research done in North­ performance of SSHFCWs to remove emerging compound from various
eastern Spain to investigate Organic micro-pollutant removal efficiency types of wastewater and findings are reviewed as follows and also see
in a full-scale surface flow constructed wetland fed with secondary Table 2. The study aimed to evaluate the removal efficiency of the
effluent showed that more than 90 % of them were removed, with the endocrine disruptors; ethinyl estradiol (EE2), the progestin levonor­
exception of carbamazepine and clofibric acid (30–47 %) (Matamoros gestrel (LNG), and bisphenol A (BPA) using laboratory scale constructed

400
S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

Table 2
Endocrine-disrupting chemicals removal efficiency of various types of Constructed wetland systems.
EDCS Sub class Types of WW Types and Wetland type Operating Influent conc. Removal References
design of CWs conditions efficiency (
%)

Natural estrogens Estrone (E1) Raw domestic DVF (80 cm × Thalia Inflow rate = 58.9 ± 8.3 mg/L, 74–90 % Dai et al., 2016
Sewage 60 cm × 80 dealbata, 5, 10, 20 L/h COD =258 ± 90 COD = 43 –
cm)+ gravel Arundo donax HLRs = 0.125, mg/L 73 %
(10–20 mm, var, versicolor 0.25, 0.5 m/d
porosity = 50
%)
Domestic Surface-flow – HRT= 27.5, 10.5 ng/L 0.0 %, 46.2 Chen et al., 2014
sewage and wetlands(135 45.9 and (median) %, and 84.3
livestock mx 5 m x 1 m) 137.5 h %
wastewater respectively
Raw Sub surface flow Phragmites, - 17.26 57.09 % Guedes-Alonso
wastewater CWs (depth of Cyperus, (12.46–19.99) et al., 2020
the CW is 0.8 Pontederia, ng/L
m). Canna and
Typha
Waste water FWS(340 cm (L) Native cattail, HRT= 53hrs 189.0 + 274.1 95.2 % Hsieh et al., 2015
from livestock x 140 cm (W) x Cyperus, ng/L
operations and 150 cm (H)) Phragmites,
aquaculture and Vetiveria.
farms
Estrodiol (E2) Raw domestic DVF (80 cm × Thalia Inflow rate = 23.4 ± 5.2 ng/L 70–81 % Dai et al., 2016
Sewage 60 cm × 80 dealbata, 5, 10, 20 L/h COD =258 ± 90 COD=43 –
cm)+ gravel Arundo donax HLRs = 0.125, mg/L 73 %
(10–20 mm, var, versicolor 0.25, 0.5 m/d
porosity = 50
%)
Domestic Surface-flow – HRT= 27.5, 3.0 ng/L 0.0 %, 44.6 Chen et al., 2014
sewage and wetlands(135 45.9 and (median) %, 59.2 %
livestock mx 5 m x 1 m) 137.5 h respectively
wastewater
Raw Sub surface flow Phragmites, - <LOQ 100 % Guedes-Alonso
wastewater CWs (depth of Cyperus, et al., 2020
the CW is 0.8 Pontederia,
m). Canna and
Typha
Waste water FWS(340 cm (L) Native cattail, HRT= 53hrs 156.2 + 139.6 76.6 % Hsieh et al., 2015
from livestock x 140 cm (W) x Cyperus, ng/L
operations and 150 cm (H)) Phragmites,
aquaculture and Vetiveria.
farms
Estriol (E3) Domestic Surface-flow - HRT= 27.5, 2.8 ng/L 0.0 %, 0.0 Chen et al., 2014
sewage and wetlands(135 45.9 and (median) %, 40 %
livestock mx 5 m x 1 m) 137.5 h respectively
wastewater
Raw Sub surface flow Phragmites, - <LOQ 100 % Guedes-Alonso
wastewater CWs (depth of Cyperus, et al., 2020
the CW is 0.8 Pontederia,
m). Canna and
Typha
Waste water FWS(340 cm (L) Native cattail, HRT= 53hrs 24.8 + 38.5 31.8 Hsieh et al., 2015
from livestock x 140 cm (W) x Cyperus,
operations and 150 cm (H)) Phragmites,
aquaculture and Vetiveria.
farms
Testosterone (TES) Raw Sub surface flow Phragmites, - 183.23 82.1 % Guedes-Alonso
wastewater CWs (depth of Cyperus, (37.12–382.54) et al., 202,020
the CW is 0.8 Pontederia, ngL−
m). Canna and
Typha
Progesterone (PRO) Raw Sub surface flow Phragmites, - 53.05 70.4 % Guedes-Alonso
wastewater CWs (depth of Cyperus, (2.91–163.17)) et al., 2020
the CW is 0.8 Pontederia, ngL− 1
m). Canna and
Typha
Boldenone (BOL) Raw Sub surface flow Phragmites, - 53.97 90.6 % Guedes-Alonso
wastewater CWs (depth of Cyperus, (2.73–105.38) et al., 2020
the CW is 0.8 Pontederia, ngL− 1
m). Canna and
Typha
Synthetic Ethinyl estradiol (EE3) Synthetic Subsurface flow Cyperus HRT =2 and 4 15.6 ± 3.8 μg L − 9.0- 95.6 % Campos et al.,
1
estrogens waste water type –CW(0.60 isocladus, days; Flow with 2-day HRT 2019
× 0.40 × 0.32 to 17.6 ± 2.5 μg
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401
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Table 2 (continued )
EDCS Sub class Types of WW Types and Wetland type Operating Influent conc. Removal References
design of CWs conditions efficiency (
%)

m)+gravel Eichhornia rate = L − 1 with 4-day


(9.5–19.0 mm) crassipes 1–2mLmin− 1 HRT
Low-strength vertical Water lettuce HRT = 72hrs 201.01 μg L − 1 64–76 % Marcelino et al.,
synthetic subsuperficial (Pistia 2020
wastewater CWs(0.5 mx 0.4 stratiotes L.)
mx 0.3 m)
Municipal Hybrid CWs – HRT = 0.17 >10 μg 100 % Masi et al., 2004
wastewater system(Surface min for HF
Area HF (m2) and 0.15 min
=160; Surface for VF
area VF (m2)
=180; HF depth
(m) = 0.7)
Progestin Synthetic Subsurface flow Cyperus HRT =2 and 4 57.2 ± 23.3 μg L 39.1 - 100.0 Campos et al.,
− 1
levonorgestrel (LNG) waste water type –CW(0.60 isocladus, days; Flow in 4-day HRT % 2019
× 0.40 × 0.32 Eichhornia rate = to 74.7 ± 17.0 μg
− 1
m)+gravel crassipes 1–2mLmin− L in 2-day
(9.5–19.0 mm) HRT
Pharmaceuticals Oxytetracycline Waste water FWS(340 cm (L) Native cattail, HRT= 53hrs 12.2–552 ng/L Exceeded 87 Hsieh et al., 2015
and Personal (OTC), from livestock x 140 cm (W) x Cyperus, %.
Care Products operations and 150 cm (H)) Phragmites,
(PPCPs) aquaculture and Vetiveria.
farms
Piggery CW (4492 m2 P. australis HRT= 48.4hrs 12.33 to 48.83 μg <10 % Choi et al., 2016
wastewater surface area (PA) and L− 1
and4006 m3of a Miscanthus
total storage sacchariflorus
volume) (MS)
Ciprofloxacin (CIP), Waste water FWS(340 cm (L) Native cattail, HRT= 53hrs 12.2–552 ng/L > 72.1 % Hsieh et al., 2015
from livestock x 140 cm (W) x Cyperus,
operations and 150 cm (H)) Phragmites,
aquaculture and Vetiveria.
farms
Sulfamethazine Piggery CW (4492 m2 P. australis HRT= 48.4hrs 1055 to 85.00 % Choi et al., 2016
(SMA) wastewater surface area (PA) and 30,033.33 μg L −

and4006 m3of a Miscanthus 1

total storage sacchariflorus


volume) (MS)
Chloramphenicol Waste water FWS(340 cm (L) Native cattail, HRT= 53hrs 12.2–552 ng/L above 87 % Hsieh et al., 2015
(CAP), from livestock x 140 cm (W) x Cyperus,
operations and 150 cm (H)) Phragmites,
aquaculture and Vetiveria.
farms
Tetracycline (TC), Piggery CW (4492 m2 P. australis HRT= 48.4hrs 8.41 to 69.5 μg L <10 % Choi et al., 2016
wastewater surface area (PA) and − 1
and4006 m3of a Miscanthus
total storage sacchariflorus
volume) (MS)
Sulfamonomethoxine Waste water FWS(340 cm (L) Native cattail, HRT= 53hrs 12.2–552 ng/L > 87 %. Hsieh et al., 2015
(SMM) from livestock x 140 cm (W) x Cyperus,
operations and 150 cm (H)) Phragmites,
aquaculture and Vetiveria.
farms
Sulfadimethoxine Waste water FWS(340 cm (L) Native cattail, HRT= 53hrs 12.2–552 ng/L Exceeded 87 Hsieh et al., 2015
(SDM) from livestock x 140 cm (W) x Cyperus, %.
operations and 150 cm (H)) Phragmites,
aquaculture and Vetiveria.
farms
Ibuprofen(IB) Effluents from Hybrid CW Phragmites HRT=7.4day 18.66±3.89 µg/L >99 % Avila et al.,
wastewater system at full- australis and 2014a
treatment scale (317m2 mixtures of
plants VF, 229 m2 HF plants for FWS
and 240m2
FWS)
Low-strength vertical Water lettuce HRT = 72hrs 5.92 µg/L 77–92 % Marcelino et al.,
synthetic subsuperficial (Pistia 2020
wastewater CWs(0.5 mx 0.4 stratiotes L.)
mx 0.3 m)
Synthetic HSSF CW (120 Typha HRTs = 2 and – 71.0 % for 2- Zhang et al.,
wastewater × 60 × 60 + angustifolia 4 days. day HRT and 2011
gravel layer 79.7 % for 4-
(diameter of day HRT
4–10 mm
(continued on next page)

402
S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

Table 2 (continued )
EDCS Sub class Types of WW Types and Wetland type Operating Influent conc. Removal References
design of CWs conditions efficiency (
%)

Diclofenac (DCF) Effluents


Synthetic from Hybrid
HSSF CW CW(120 Typha
Phragmites HRTs = 2 and
HRT=7.4day 0.77±0.52 µg/L
– 47.5
89 %for 2- Zhangetetal.,
Avila al.,
wastewater system
× 60 × at60full-
+ australis and
angustifolia 4 days. day HRT and 2014a
2011
treatment scale layer 2
gravel(317m mixtures of 55.4 for 4-
2
plants VF, 229 mofHF
(diameter plants for FWS day HRT
mm 2
and 240m
4–10
FWS)
Carbamazepine Synthetic HSSF CW (120 Typha HRTs = 2 and – 28.4 % for 2- Zhang et al.,
wastewater × 60 × 60 + angustifolia 4 days. day HRT and 2011
gravel layer 26.7 % for 4-
(diameter of day HRT
4–10 mm
Acetaminophen(ACE) Effluents from Hybrid CW Phragmites HRT=7.4day 3.50±3.42 µg/L 99 % Avila et al.,
wastewater system at full- australis and 2014a
treatment scale (317m2 mixtures of
plants VF, 229 m2 HF plants for FWS
and 240m2
FWS)
Low-strength vertical sub- Water lettuce HRT = 72hrs 2.61 µg/L 71–96 % Marcelino et al.,
synthetic superficial CWs (Pistia 2020
wastewater (0.5 mx 0.4 mx stratiotes L.)
0.3 m)
Naproxen Synthetic HSSF CW (120 Typha HRTs = 2 and – 2.8 % for 2- Zhang et al.,
wastewater × 60 × 60 + angustifolia 4 days. day HRT and 2011
gravel layer 91.3 % for 4-
(diameter of day HRT
4–10 mm
Bisphenol A (BPA), Municipal HSF CWs (3 mx Phragmites HRT=14 and 0.508+0.101 µg/ 49.6 % (in Papaevangelou
wastewater 0.75 × 1 m)+ australis(HSF- 20 days; HLR L HSF-R), 50.0 et al., 2016
gravel(range R), Typha = ranged from % (in HSF-C)
4–25 mm at a latifolia(HSF- 15.8 to 28.6 and 55.4 %
thickness of 45 C), unplanted, L/day. (in HSF-Z)
cm (HSF-Z).
VF CWs (0.82 m Phragmites HRT= 4 and 6 0.508+0.101 µg/ 45.6 %(in
x 1.5 m) +gravel australis(VF- days; HLR= VF-R), 60.0
(at a thickness R), Typha 0.209 m/ % (in VF-C),
of 50 cm) latifolia(VF-C), d and 0.283 and 59.0 %
unplanted, (VF- m/d (in VF-Z)
Z).
Synthetic Hydroponic D.sanderiana – 20µM 82.7 %, 73.9 Saiyood et al.,
solution system (ribbon plant) % 2010
and D.fragrans respectively
Effluents from Horizontal Phragmites Design flow 8.80+6.40 µg/L 73.3(±19 Toro-Vélez et al.,
wastewater subsurface flow australis; rate = 3.5 %); 70.2 ± 2016
treatment constructed Heliconia m3day− 1; 27 %)
plants wetlands (HSSF- psitacorum HRT= 1.8 respectively
CW) (0.6 mx 9 day; Surface
mx3 m)+ Gravel loading rate=
(diameter 20 0.13 m day− 1
mm Porosity 40
%)
Synthetic Subsurface flow Cyperus HRT =2 and 4 22.5 ± 5.5 μg L − 29.5 to 91.2 Campos et al.,
1
waste water type –CW(0.60 isocladus, days; Flow with 2-day % 2019
× 0.40 × 0.32 Eichhornia rate = HRT, and 24.1 ±
m)+gravel crassipes 1–2mLmin− 1 1.5 μg L − 1 with
(9.5–19.0 mm) 4-day HRT
Effluents from Hybrid CW Phragmites HRT=7.4day 4.06±1.19 μg L − >99 % Avila et al.,
1
wastewater system at full- australis and 2014a
treatment scale (317m2 mixtures of
plants VF, 229 m2 HF plants for FWS
and 240m2
FWS)
Synthetic vertical flow Phragmites HRT= 0.5–8 50 mg/L 9–99 % Dan et al., 2017
leachate CWs (18 × 63 australis days, Flow
cm) with a 50- rate = 4.7
cm layer of mL/ min
gravel
EDCs vertical-flow Phragmites Flow rate = 5 mg/L 35–93 % Wirasnita et al.,
contaminated CWs(150 × 650) australis 149 3.6 L/day 2018
synthetic + pumice rock (HRT = 1 day)
wastewater (grain size, 3–8
mm)
Bisphenol F (BPF), EDCs vertical-flow Phragmites Flow rate = 5 mg/L 45–95 % Wirasnita et al.,
contaminated CWs(150 × 650) australis 149 3.6 L/day 2018
+ pumice rock (HRT = 1 day)
(continued on next page)

403
S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

Table 2 (continued )
EDCS Sub class Types of WW Types and Wetland type Operating Influent conc. Removal References
design of CWs conditions efficiency (
%)

synthetic (grain size, 3–8


wastewater mm)
Bisphenol S (BPS) EDCs vertical-flow Phragmites Flow rate = 5 mg/L 0–78 % Wirasnita et al.,
contaminated CWs(150 × 650) australis 149 3.6 L/day 2018
synthetic + pumice rock (HRT = 1 day)
wastewater (grain size, 3–8
mm)
4‑tert-butylphenol EDCs vertical-flow Phragmites Flow rate = 5 mg/L 25–93 % Wirasnita et al.,
(4‑tert-BP). contaminated CWs(150 × 650) australis 149 3.6 L/day 2018
synthetic + pumice rock (HRT = 1 day)
wastewater (grain size, 3–8
mm)
Nonylphenol Municipal HSF CWs (3 mx Phragmites HRT=14 and 0.423+0.095 µg/ 51.4 %(in Papaevangelou
monoethoxylate wastewater 0.75 × 1 m)+ australis(HSF- 20 days; HLR L HSF-R), 99.0 et al., 2016
(NP1EO), gravel(range R), Typha = ranged from %(in HSF-
4–25 mm at a latifolia(HSF- 15.8 to 28.6 C), 98.9 %
thickness of 45 C), unplanted, L/day. (in HSF-Z)
cm (HSF-Z)
VF CWs (0.82 m Phragmites HRT= 4 and 6 L0.423+0.095 41.5 %(in
x 1.5 m) +gravel australis(VF- days; µg/L VF-R), 99.0
(at a thickness R), Typha HLR=0.209 %(in VF-C)
of 50 cm) latifolia(VF-C), m/d and and98.7 %
unplanted, (VF- 0.283 m/d (in VF-Z)
Z).
Nonylphenol Municipal HSF CWs (3 mx Phragmites HRT=14 and 0.586+0.073 µg/ 48.4 %(in Papaevangelou
diethoxylate (NP2EO) wastewater 0.75 × 1 m)+ australis(HSF- 20 days; HLR L HSF-R), 66.0 et al., 2016
gravel(range R), Typha = ranged from %(in HSF-C)
4–25 mm at a latifolia(HSF- 15.8 to 28.6 and 80.3 %
thickness of 45 C), unplanted, L/day. (in HSF-Z)
cm (HSF-Z).
VF CWs (0.82 m Phragmites HRT= 4 and 6 0.586+0.073 µg/ 72.2 % (in
x 1.5 m) +gravel australis(VF- days; HLR= L VF-R), 59.0
(at a thickness R), Typha 0.209 m/ % in VF-C)
of 50 cm) latifolia(VF-C), d and 0.283 and 99.8 %
unplanted, (VF- m/d (in VF-Z)
Z).
Nonylphenols (NP) Effluents from Horizontal Phragmites Design flow 1671+838 µg/L 62.8(±20.1 Toro-Vélez et al.,
wastewater subsurface flow australis; rate = 3.5 %), 52.1 2016
treatment constructed Heliconia m3day− 1; (±37.1 %)
plants wetlands (HSSF- psitacorum HRT= 1.8 respectively
CW) (0.6 mx 9 day; Surface
mx3 m)+ Gravel loading rate=
(diameter 20 0.13 m day− 1
mm Porosity 40
%)
Tonalide (AHTN) Effluents from Hybrid CW Phragmites HRT=7.4day 0.54±0.22 µg/L 90 % Avila et al.,
wastewater system at full- australis and 2014a
treatment scale (317m2 mixtures of
plants VF, 229 m2 HF plants for FWS
and 240m2
FWS)
Triclosan (TCS) Effluents from Hybrid CW Phragmites HRT=7.4day 0.15±0.03 µg/L 79 % Avila et al.,
wastewater system at full- australis and 2014a
treatment scale (317m2 mixtures of
plants VF, 229 m2 HF plants for FWS
and 240m2
FWS)
Phthalates (PAHs) Municipal Hybrid CWs – HRT = 0.17 100- 300 mg/l 60–70 % Masi et al., 2004
wastewater system(Surface min for HF
Area HF (m2) and 0.15 min
=160; Surface for VF
area VF (m2)
=180; HF depth
(m) = 0.7)
Diethyl phthalate Landfill HSSF CW unit Typha sp. HLR = 0.04 87–182 μg/L for 74.7 % % Witthayaphirom
(DEP) leachate (1.0 m X 2.0 m X m3/m2/d; et al., 2020
1.0 m) with HRT = 5.8
sand media of − 6.9 days
0.02–2 mm size
Dibutyl phthalate Landfill HSSF CW unit Typha sp. HLR = 0.04 257–786 μg/L 72.5 % Witthayaphirom
(DBP) leachate (1.0 m X 2.0 m X m3/m2/d; et al., 2020
1.0 m) with HRT = 5.8
sand media of − 6.9 days
0.02–2 mm size
(continued on next page)

404
S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

Table 2 (continued )
EDCS Sub class Types of WW Types and Wetland type Operating Influent conc. Removal References
design of CWs conditions efficiency (
%)

Bis (2- ethylhexyl) Landfill HSSF CW unit Typha sp. HLR = 0.04 748–3769 μg/L 57.9 % Witthayaphirom
phthalate (DEHP) leachate (1.0 m X 2.0 m X m3/m2/d; et al., 2020
1.0 m) with HRT = 5.8
sand media of − 6.9 days
0.02–2 mm size

Note: DVF, Downward vertical subsurface-flow; LOQ, Limits of quantification.

wetlands (CW) (cultivatedwith Cyperus isocladus (WL1), Eichhornia 4.2.2. Performance of vertical sub-surface flow (VSSF) constructed wetland
crassipes (WL3), without macrophyte (WL2)) indicates an average re­ system
movals efficiency ranged from 9.0 to 95.6 % for EE2, from 29.5 to 91.2 Vertical flow constructed wetland is one where wastewater is
% for BPA and from 39.1 to 100.0 % for LNG (Campos et al., 2019). drained out of the bottom and submerged from the top of the wetland. A
A research work done in a pilot-scale horizontal subsurface flow level bed of graded gravel covered in sand and planted with macro­
constructed wetland system to evaluate the behavior of four pharma­ phytes is the basic structure of vertical flow (VF) built wetlands.
ceuticals and personal care products (i.e. ibuprofen, naproxen, diclofe­ In vertical subsurface flow (VSF) CWs, the wastewater is normally
nac and tonalide) and a phenolic estrogenic compound (i.e. bisphenol A) distributed along the entire surface and then travels vertically into the
revealed that overall removal efficiencies for the selected compounds media (with a 50–100 cm active zone) (Engida et al., 2021; Turcios
ranged from 97 % to 99 with anaerobic degradation and sorption as a et al., 2021). Vertical flow constructed wetland offers aerobic condition,
probable removal mechanism (Avila et al., 2010). The investigation therefore, achieved high nitrification, BOD, COD and other pollutant
done by Wagner et al., al.(2020) illustrated that the main removal removals (DBT, 2019). The reason for growing interest in using vertical
mechanisms of benzotriazole in CWs are adsorption, biodegradation and flow systems are greater oxygen transfer capacity resulting in good
plant uptake, followed by photo-degradation with a minor role . Another nitrification; smaller land requirement (1–3 m2 /PE) as compared with
study aimed to assess removal efficiency of horizontal subsurface Flow SSHF constructed wetland and can efficiently remove BOD5, COD and
and Vertical Flow pilot-Scale constructed wetlands for emerging pol­ pathogens (Zhao et al., 2011; Witthayaphirom et al., 2020). Further­
lutants stated that biodegradation under aerobic and/or anaerobic more, the environmental impact of SSVF constructed wetland is smaller
conditions and adsorption on the substrate are the main removal than that of SSHF constructed wetland because of their lower con­
mechanisms (Gikas et al., 2021). Cai et al. (2012) reported that removal struction requirements and the fact that VFs emit less greenhouse gases
efficiencies of 95 % and 92 %for oestrogens and androgens respectively during wastewater treatment (Fuchs et al., 2011). Recently, they were
was achieved in surface flow CW system treating dairy wastewaters. proved to effectively remove a variety of micro-pollutants such as EDCs,
Vymazal et al. (2015) also found that three SSHF-CW treating municipal pharmaceuticals and personal care products from municipal and agri­
sewage in the Czech Republic were particularly effective in the removal cultural wastewater (Papaevangelou et al., 2016; Huang et al., 2015).
of oestrogens, progesterone and testosterone. The study done by Del­ Investigations on the antibiotic removal treatment efficacies of CWs
gado et al., al.(2020) to evaluate the efficiency of subsurface horizontal have been conducted under a variety of system configurations, substrate
flow constructed wetlands (planted in polyculture and unplanted), in types, hydraulic loads, and flow directions (Dan et al., 2013; Huang
removing two pharmaceuticals: carbamazepine (Cbz) and sildenafil et al., 2015). In comparison to their horizontal subsurface flow and free
(Sil); and a personal care product: methylparaben (Mp), present in do­ water surface flow counterparts, the vertical subsurface flow built
mestic wastewater revealed that 97 % were achieved for Sil,and greater wetlands had better antibiotic removal efficiency (Liu et al., 2014).
than 97 % were achieved for Mp. However, less than 10 % removal ef­ Study done in Sendai city of Japan to evaluate the effectiveness of
ficiency was achieved for Cbz . the study finding also noted that con­ vertical-flow wetland as polishing step of conventional wastewater
structed wetlands can efficiently remove simple molecular structure treatment in the removal of estrogens revealed that highest removal
compounds such as Mp, and complex structures such as Sil. But Cbz efficiency of 67.8 ± 28.0 %, 84.0 ± 15.4 % and 75.3 ± 17.6 % for E1, E2
persisted as a recalcitrant contaminant. Furthermore, other studies also and EE2, respectively, was achieved through the shallowest wetland
found that 95–100 % removal efficiency of Acetaminophen (ACE) was among three constructed wetlands with different filter layer depth (i.e.
achieved in SSHFCWs and concluded that biodegradation was the main 7.5, 30 and 60 cm). This finding also noted that the highest efficiency
removal mechanism, although sorption could also contribute to its was achieved in extremely shallow wetland and this might be due to the
degradation (Chen et al., 2016a; Phong Vo et al., 2019). On the other highest root density and the superior condition for penetration of oxygen
hand, research work conducted to evaluate the removal efficiency of (Song et al., 2009). In earlier study, the performance of vertical up-flow
emerging pollutant from waste water (Ofloxacin) showed that 90 % of constructed wetlands (VUF-CWs) on swine wastewater containing
the contaminant removed in lab scale SSHFCWs and biodegradation tetracycline compounds (TCs) and tet genes was evaluated and high
could the probable removal mechanism (Yan et al., 2016). Study done to removal efficiencies (69.0–99.9 %) were achieved for oxytetracycline
evaluate EDCs removal performance of pilot-scale SSHFCW reported (OTC), tetracycline (TC) and chlortetracycline (CTC) (Huang et al.,
that 49.6 % BPA was removed n those cultivated with Phragmites aus­ 2015). Another study conducted in china to assess the performance of
tralis, 50.0 % in CW cultivated with Typha latifolia, and 55.4 % in CW vertical-flow constructed wetland on removal of antibiotics and anti­
without plants (Papaevangelou et al., 2016). biotic resistance genes (ARGs from swine wastewater showed that more
Another research work aimed to investigate the emerging pollutant than 84 % of oxytetracycline and difloxacin and 33.2 to 99.1 % of ARGs
removal efficiency of pilot-scale horizontal subsurface flow CW was removed (Huang et al., 2017).
confirmed that 73.3 ± 19 % of BPA was removed from waste water in Furthermore, previous study done in Brazil reported 97 and 89 %
wetland cultivated with Heliconia psittacorum, 70.2 ± 27 % in the unit removal efficiency for EDCs (caffeine and ibuprofen, respectively) was
cultivated with Phragmites australis whereas 62.2 ± 33 % of it removed achieved in the vertical flow CW systems (sand as filter media), using
in the one without plant (Toro-Vélez et al., 2016). In addition to this, Heliconia rostrata, with and without earthworms operated under
Carranza-Diaz et al. (2014) investigated BPA removal by SSHFCW different organic loadings rates (de Oliveira et al., 2019). In Brazil, also
treating municipal waste water and appreciable removal efficiency was carried out research treating sewage from a university campus with a
reported in both planted and unplanted CWs. vertical flow constructed wetland, where the effluent came from a septic

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S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

tank and 86 and 83 % removal efficiency was achieved for caffeine and was achieved. It was noted that the high temperatures as well as the
ibuprofen, respectively. Recent study investigated the efficiency of - differing existing physico-chemical conditions occurring at different CW
pilot-scale vertical flow constructed wetlands built in Jinan University in configurations, which would allow for the combination and synergy of
South China on the removal of Estrone (E1) and Estradiol (E2) from raw various abiotic/biotic removal mechanisms to occur (e.g. biodegrada­
domestic sewage and the finding showed that 61–90 % and 48–81 % of tion, sorption, volatilization, hydrolysis, photo-degradation) were the
E1 and E2 removal efficiency respectively. High removal efficiencies mentioned reasons for high rate removal of EOCs (Avila et al., 2015).
(26.42–84.05 %) were achieved for sulfadiazine (SDZ), sulfamethoxa­ Previous study findings also confirmed that higher EOC removal effi­
zole (SMX) and sulfamethazine (SMZ) when mesocosm-scale vertical ciency was achieved in meso‑scale hybrid constructed wetland system
flow constructed wetlands were applied to abate nutrients and antibi­ which combined different CW configurations (VF, HF and FWS) as
otics in swine wastewater containing sulfonamides. In this study, sorp­ compared with other types constructed wetland types (Avila et al., 2013;
tion and microbial degradation was found to be the most important Avila et al., 2014a; Hijosa-Valsero et al., 2010). Similarly Matamoros
removal mechanism for sulfonamides in VF-CWs (Chen et al., 2020). et al. (2012) observed very high removal efficiencies (around 90 %) for
Additionally, four adjacent pilot-scale vertical flow (VF) constructed most studied EDCs-emerging compounds at a full-scale reclamation
wetlands of various designs were assessed for the removal of eight pond-FWS wetland system in Girona, Spain, treating secondary effluent
commonly utilized emergent organic pollutants from municipal waste­ from a conventional waste water treatment plant (WWTP). Another
water (i.e. ibuprofen, acetaminophen, diclofenac, tonalide, oxybenzone, one-year study conducted in Mexico to evaluate the removal of carba­
triclosan, ethinylestradiol, bisphenol A) and the result revealed that high mazepine (CBZ) in three pilot-scale two-stage hybrid constructed wet­
removal efficiency of these emerging organic contaminants were ach­ lands as well as to evaluate the performance of three emergent species
ieved in the system (Avila et al., 2014b). Additionally, Song et al. (2009) (Thypha latifolia, Iris sibirica and Zantedeschia aethiopica) planted as a
reported E2 removal in a vertical flow constructed wetland of 84 % in a poly-culture revealed that 62.5 % removal efficiency was achieved . In
7.5 cm shallow system while deeper systems provided lower treatment addition to this, findings of several studies conducted to evaluate the
efficiency. Other recent studies also reports the higher removal effi­ EDCs -emerging micro-pollutants removal efficiency of hybrid system
ciency VFCWs for EDCs (Montenegro et al., 2021; de Carvalho Silva are summarized in Table 2.
et al., 2024)
4.4. Integrating CWs with other techniques for enhanced EDCs removal
4.3. Removal performance of hybrid constructed wetlands
Previous findings noted that CWs have some intrinsic drawbacks that
According to Parde et al. (2021), a hybrid constructed wetland is a can limit their application and long-term stability such as substrate
system with a multistage treatment that combines HFCW and VFCW. clogging (Ruiz et al., 2010), low nitrogen removal efficiencies due to low
The design consists of two stages: a number of parallel VF beds (also oxygen transfer or denitrification limited due to low amounts of avail­
known as "filtration beds") followed by a number of consecutive HF beds able organics (Wu et al., 2014). Furthermore, some recalcitrant micro
(also known as "elimination beds"). Phragmites australis was typically pollutants such as EDCs and heavy metals in industrial wastewater also
planted in the VF stages, whereas other emergent macrophytes, such as present challenges to the performance of CWs (Ruiz et al., 2010; Shi
Iris, Schoenoplectus (Scirpus), Sparganium, Carex, Typha, and Acorus, were et al., 2023). It was also stated that many existing or novel technologies
present in the HF stages (Vyzamal, 2014). A hybrid constructed wetland can, and have been, integrated and coupled with CWs to compensate for
has higher removal efficiency than other types of constructed wetlands. their individual shortcomings and improve their performance and
According to the aerobic or anaerobic circumstances and the prop­ long-term stability (Liu et al., 2015; Handayani et al., 2020; Ji et al.,
erties of the wastewater, the different forms of constructed wetland have 2022). As the result, integrating CWs with other existent or emerging
varying pollutant removal efficiencies (Saeed et al., 2012; Yazdani and technologies, such as membrane bio-reactor (MBR) (Mutamim et al.,
Golestani, 2019). The VSSF–HSSF combinations are probably the most 2012), electrochemical oxidation (Saha et al., 2020; Anglada et al.,
frequently used hybrid systems among the many types of combinations 2010), microbial fuel cells (MFCs) (Wen et al., 2021) etc. have emerged
and are gaining more attention in many countries due it efficiency in in recent years with the aim of maximizing the individual advantages of
removing emerging micro-pollutants from different types waste water constructed wetland systems in terms of emerging micro pollutant and
(Vymazal, 2007). Study done in Spain to investigate the BPA removal other pollutant removal from wastewater. All these technologies have
efficiency of hybrid system of CW cultivated with Phragmites australis been proven to be robust in the treatment of specific emerging
revealed that removal rates were between 11 % and 90 % (Avila et al., micro-pollutants such as EDCs and findings from several studies are
2014a). The reason for higher removal efficiency was due to d the reviewed as follows and are summarized in Table 3.
simultaneous occurrence of biodegradation, sorption, hydrolysis and Study done to investigate the effects of activated carbon(AC), used as
photo-degradation processes in the hybrid CW system as compared with constructed wetlands (CWs) medium on its ability to remove four
separate wetland types. Furthermore, Masi et al. (2004) investigated the emerging endocrine-disrupting chemicals (EDCs): bisphenol A (BPA),
effectiveness of a hybrid system made up of a VF and HF CWs and bisphenol F (BPF), bisphenol S (BPS) and 4‑tert-butylphenol (4‑tert-BP)
discovered that it could eliminate estrogens up to 90 %. revealed that all four EDCs were completely and sustainably removed
According to Reyes-Contreras et al. (2012), the removal of several (98–100 %). it was also noted that in AC–CW, final elimination step of
emerging organic contaminants (EOCs) was improved using a hybrid EDCs might be biodegradation. Additionally, bacterial populations on
system made up of a series of HF wetlands, FWS, and an upflow the AC component of AC–CW were one to two orders larger than those
anaerobic sludge blanket reactor (UASB). A full-scale hybrid constructed on the pumice rock of regular CW. Therefore, in AC–CW, EDCs were
wetland (CW) system based on three stages of different wetlands con­ initially adsorbed onto AC, where they could be effectively degraded by
figurations showed to be effective in removing emerging contaminants, high bacterial population (Wirasnita et al., 2018). Another research
which included various pharmaceuticals, personal care products and work conducted showed that biochar and activated carbon modified
endocrine disruptors (above 80 % for all compounds removed) (Avila with Fe3+ and Mn4+ were used as effective sorbents in the removal of
et al., 2015). Recently, Dan et al. (2021) also showed better antibiotic benzofluoranthene (BbFA), a typical polycyclic aromatic hydrocarbons
removal efficiency of the full-scale hybrid constructed wetland systems. (PAH), in CW microcosms (Guo et al., 2020). Authors confirmed that the
Additionally, study done to assess the emerging organic contaminant addition of metallic ions embedded carbon increased NO3–N accumu­
removal performance of full-scale hybrid constructed wetland (CW) lation by the reduction of Fe3+ and Mn4+, which led to improved BbFA
system based on three stages of different wetlands configurations degradation and proposed removal pathways of BbFA in the integrated
showed very high (above 80 % for all compounds) removal efficiency CWs were plant absorption and microbial degradation. Moreover, Chen

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Table 3
Performance of different integrated system in removing EDCs and other emerging micropollutants.
EDCS Sub class Types of Types and design of Wetland type Operating Influent Removal References
WW integrated CWs conditions conc. efficiency ( %)

Natural estrogens Estrone (E1) Secondary SCW coupled Cannaglauca, HLR= 2.34±0.51 48±7 % (1.25 Dai et al., 2017
effluent assembled bio-filter Thalia dealbata, 0.5–2.0 m/ ±0.42), 44±4
(ABF) Canna indica, day HRT % (1.29±0.22)
and Typha =24, 12, 8
angustifolia etc and6 hrs
Raw Pond-CW system are Phragmites, HRT = 2days 17.26 ng/l 76.7 % Guedes-Alonso
wastewater (15 × 20 m) Cyperus, et al., 2020
Pontederia,
Canna and Typha
Estriol (E3) Raw Pond-CW system are Phragmites, HRT = 2days <10 ng/l 100 % Guedes-Alonso
wastewater (15 × 20 m) Cyperus, et al., 2020
Pontederia,
Canna and Typha
Testosterone (TES) Domestic ICW -contains Myriophyllum HRT =36 hrs, 30.5 ± 1.25 100 % Chen et al., 2019
and regulating pool a verticillatum, OLR =6.5 μg /L - 105
livestock FWSCW, SSCW, two Pontederia m3/day ± 5.14 μg/L
wastewater SFCW and a cordata)
stabilization lagoon
Raw Pond-CW system are Phragmites, HRT = 2days 183.23 ng/l 98.9 % Guedes-Alonso
wastewater (15 × 20 m) Cyperus, et al., 2020
Pontederia,
Canna and Typha
Progesterone Domestic ICW -contains Myriophyllum HRT =36 hrs, 30.5 ± 1.25 94.3 %− 100 % Chen et al., 2019
(PRO) and regulating pool a verticillatum, OLR =6.5 μg /L - 105
livestock FWSCW, SSCW, two Pontederia m3/day ± 5.14 μg/L
wastewater SFCW and a cordata)
stabilization lagoon
Raw Pond-CW system are Phragmites, HRT = 2days 53.05 ng/l 82 % Guedes-Alonso
wastewater (15 × 20 m) Cyperus, et al., 2020
Pontederia,
Canna and Typha
4-androstene- Domestic ICW -contains Myriophyllum HRT =36 hrs, 30.5 ± 1.25 94.3 % Chen et al., 2019
3,17‑dione (AED) and regulating pool a verticillatum, OLR =6.5 μg /L - 105
livestock FWSCW, SSCW, two Pontederia m3/day ± 5.14 μg/L
wastewater SFCW and a cordata)
stabilization lagoon
Syntheticestrogens Androsta-1,4- Domestic ICW -contains Myriophyllum HRT =36 hrs, 30.5 ± 1.25 94.3 %− 100 % Chen et al., 2019
diene-3,17‑dione and regulating pool a verticillatum, OLR =6.5 μg /L - 105
(ADD) livestock FWSCW, SSCW, two Pontederia m3/day ± 5.14 μg/L
wastewater SFCW and a cordata)
stabilization lagoon
19-NTD 19- Domestic ICW -contains Myriophyllum HRT =36 hrs, 30.5 ± 1.25 94.3 %− 100 % Chen et al., 2019
norethindrone(19- and regulating pool a verticillatum, OLR =6.5 μg /L - 105
NTD) livestock FWSCW, SSCW, two Pontederia m3/day ± 5.14 μg/L
wastewater SFCW and a cordata)
stabilization lagoon
Ciprofloxacin Domestic integrated Various plant HRT= 36hrs - 61.88–84.07 % Shan et al., 2020
(CIP), waste water constructed wetland species used
(ICW) with six
subsystems
Sulfamethazine Synthetic Electrolysis- Cyperus HRT =24hrs 100–1000 42.81 %− Liu et al., 2020
1
(SMA) waste water integrated tidal flow alternifolius μg L − 68.47 %.
constructed wetland
system (E-TFCW)
(10 cm x60cm) filled
with zeolite and
gravel
Tetracycline (TC), Synthetic microbial fuel cells Canna indica HRT = 3 days 200 μg L-1 80.3–88.0 % Wen et al., 2018
wastewater with constructed
wetlands
(MFC–CWs)(19 cm
x 49 cm)
Sulfadimethoxine Domestic integrated Various plant HRT= 36hrs - 43.15 %− Shan et al., 2020
(SDM) waste water constructed wetland species used 86.69 %
(ICW) with six
subsystems
Sulfamethoxazole Synthetic Microbial fuel cell- Oenanthe HRT 2000 and >99.29 % Zhang et al., 2018b
1
(SMX) wastewater constructed wetland javanica =2.5days 400 μg L −
coupled biofilm
electrode reactor
system (MFC–CW-
BER).
(continued on next page)

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S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

Table 3 (continued )
EDCS Sub class Types of Types and design of Wetland type Operating Influent Removal References
WW integrated CWs conditions conc. efficiency ( %)

Domestic
Synthetic integratedfuel cells
microbial Variousindica
Canna plant HRT=
HRT = 36hrs
3 days -
100 μg L-1 96.9–98.2 % %
54.22–67.78 Wen et
Shan et al.,
al., 2018
2020
waste water
wastewater constructed
with wetland
constructed species used
(ICW) with six
wetlands
subsystems
(MFC –CWs)(19 cm
x 49 cm)
Ibuprofen(IB) Synthetic Electrolysis- Cyperus HRT =24hrs 100–1000 42.81 %− Liu et al., 2020
1
waste water integrated tidal flow alternifolius μg L − 68.47 %.
constructed wetland
system (E-TFCW)
(10 cm x60cm) filled
with zeolite and
gravel (10 cm x 60
cm) filled with
zeolite and gravel
WWTP Coupled system Cyperus ligularis HRT = 2.5 15 μg.L− 97.2 % Lancheros et al.,
influent between HSSFCWs days 2019
and an Ozonation
Synthetic Electrolysis- 1000 µg L −
28.83 % Liu et al., 2020
1
wastewater integrated tidal flow
constructed wetland
system (E-TFCW)
Diclofenac (DCF) Synthetic Electrolysis- Cyperus HRT =24hrs 100–1000 42.81 %− Liu et al., 2020
1
waste water integrated tidal flow alternifolius μg L − 68.47 %.
constructed wetland
system (E-TFCW)
(10 cm x60cm) filled
with zeolite and
gravel (10 cm x 60
cm) filled with
zeolite and gravel
− 1
Domestic Horizontal Cyperus ligularis OLR= 7.2 g 15 μg L , 92 % Casierra-Martinez
wastewater Subsurface Flow DBO5.m − 2 et al., 2020
Constructed d − 1 flow rate
Wetland (CW HSSF) = 18 L d − 1
and Solar Photo- and HRT=
Fenton 2.5 days
Carbamazepine Synthetic Electrolysis- Cyperus HRT =24hrs 100–1000 42.81 %− Liu et al., 2020
1
(CMP) waste water integrated tidal flow alternifolius μg L − 68.47 %.
constructed wetland
system (E-TFCW)
(10 cm x60cm) filled
with zeolite and
gravel (10 cm x 60
cm) filled with
zeolite and gravel
− 1
Domestic Horizontal Cyperus ligularis OLR= 7.2 g 15 μg L , 86 % Casierra-Martinez
wastewater Subsurface Flow DBO5.m − 2 et al., 2020
Constructed d − 1 flow rate
Wetland (CW HSSF) = 18 L d − 1
and Solar Photo- and HRT=
Fenton 2.5 days
Naproxen WWTP Coupled system Cyperus ligularis HRT = 2.5 15 μg.L− ≥97.3 % Lancheros et al.,
influent between HSSFCWs days 2019
and an Ozonation
Bisphenol A (BPA), Synthetic Up-flow microbial Ipomoea aquatica – 10 mg/l >60 % Li et al., 2019
waste water fuel cell-coupled Forsk
constructed
wetland, UCW-MFC
(10 cm x32 cm)
Secondary SCW coupled Cannaglauca, HLR= 563±160 45±15 % (295 Dai et al., 2017
effluent assembled bio-filter Thalia dealbata, 0.5–2.0 m/ ±103) and 32
(ABF) Canna indica, day HRT ± 13 % (385
and Typha =24, 12, 8 ±158)
angustifolia etc and6 hrs
Synthetic Activated carbon Phragmites Flow rate = 5 mg/L 98–100 %) Wirasnita et al.,
wastewater (AC) –CWs system australis 149 3.6 L/ 2018
(vertical, 150 × 650 day; HRT=1
mm) day
Bisphenol F (BPF), Synthetic Activated carbon Phragmites Flow rate = 5 mg/L 98–100 %) Wirasnita et al.,
wastewater (AC) –CWs system australis 149 3.6 L/ 2018
(vertical, 150 × 650 day; HRT=1
mm) day
Bisphenol S (BPS) Synthetic Activated carbon Phragmites Flow rate = 5 mg/L 98–100 %) Wirasnita et al.,
wastewater (AC) –CWs system australis 149 3.6 L/ 2018
(continued on next page)

408
S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

Table 3 (continued )
EDCS Sub class Types of Types and design of Wetland type Operating Influent Removal References
WW integrated CWs conditions conc. efficiency ( %)

(vertical, 150 × 650 day; HRT=1


mm) day
4‑tert-butylphenol Synthetic Activated carbon Phragmites Flow rate = 5 mg/L 98–100 %) Wirasnita et al.,
(4‑tert-BP). wastewater (AC) –CWs system australis 149 3.6 L/ 2018
(vertical, 150 × 650 day; HRT=1
mm) day

et al. (2019) investigated the removal of steroid hormones and biocides concentrations in the outflow than the intake. This fact could be
from rural wastewater by building an integrated constructed wetland explained through the synthesis of the parent compounds as a result of
(ICW) in the town of Kaihui, Hunan Province, South China. The result the biodegradation of their precursors, nonylphenol ethoxylates, under
demonstrated that examined ICW effectively reduced the levels of anaerobic circumstances. Previous study also noted that wetland
detected steroid hormones and biocides by 97.4 ± 0.09 % and 92.4 ± configuration also affected Di-(2-Ethylhexyl) phthalate (DEHP)
0.54 %, respectively and they conclude that microorganisms, substrates, removal, which varied between 19 and 49 %, being the highest removal
and plants were the major contributors for their removal. Liu et al., al. also observed in VSSF-C (Xiaoyan et al., 2015). Furthermore, earlier
(2020) indicated a novel electrolysis-integrated tidal flow constructed studies showed that the various CW designs also affected the removals of
wetland system (E-TFCW) can achieve highest removal efficiency for the erythromycin and clarithromycin. Erythromycin was only completely
four investigated PPCPs in which their removal efficiency increases from eliminated in a planted HSSF-CW system (64 %), while clarithromycin
4.41 % to 11.71 % to 28.83 %− 68.32 % . was only partially eliminated in a free water SF-CW (50 %) (Hijosa-­
Recent study conducted in China to evaluate performance and Valsero et al., 2011). A further study by Guo et al. (2020) demonstrated
mechanism of sulfamethoxazole (SMX) removal in different bio-electro the utilization of biochar and activated carbon modified with Fe3+ and
chemical technology-integrated constructed wetlands showed the SMX Mn4+ as efficient sorbents in the removal of benzofluoranthene (BbFA),
removal efficiency can reach 96.0 ± 2.4 % in the (MFC) and direct a typical polycyclic aromatic hydrocarbons (PAH), in CW microcosms.
current (EC)-CW and 97.2 ± 2.2 % in the microbial fuel cell (MFC)-CW The reduction of Fe3+ and Mn4+ caused by the addition of metallic ions
(Liu et al., 2021). Additionally, constructed wetlands integrated with to embedded carbon boosted NO3–N accumulation, which promoted
microbial fuel cells (MFC–CWs) have been recently developed and BbFA degradation. The authors advised that plant absorption and mi­
tested for removing antibiotics such as sulfamethoxazole (SMX) and crobial degradation be used to remove BbFA from the integrated CWs.
tetracycline (TC) removal and highest removal percentages of SMX Additionally, Lei et al. (2022) showed that the CWs with bark-biochar as
(99.4 %) and TC (97.8 %) were obtained (Wen et al., 2021). Another support matrix significantly enhanced the removal of irbesartan and
recent research work done to evaluate the ARG removal performance of carbamazepine (>40 %), compared to the CW filled with the conven­
bio electro-chemistry-enhanced constructed wetlands system designed tional support matrix sand.
in a vertical flow style and constructed in a greenhouse at 28 ± 3◦ C at
the Chinese Research Academy of Environmental Sciences showed that 5.1.2. Water depth
high sulfonamide resistance genes (sul ARGs) reduction in effluent was Water depth is a design component that can impact the hydraulic
observed (Liu et al., 2022). In a previous work, Li et al. (2019) used an performance and vegetation abundance of CWs, which in turn can affect
upflow CW (UCW) -MFC system to treat synthetic wastewater that had a treatment performances. In order to maximize the effectiveness of the
high concentration of pharmaceutical and personal care products (on CWs system’s pollutant removal, water depth is another crucial design
the order of 10 mg/L), such as ibuprofen (IBP) and bisphenol A (BPA), factor that must be taken into consideration (Guo et al., 2017). Due to
and found that the removal rates of IBP and BPA in the closed-circuit their saturated media or shallow water depths, CWs have a slow flow of
mode were increased by 9.3 % and 18 % respectively, compared to water. Then, as water moves through the wetland system, the low water
those in the open circuit mode. Moreover, the potential of CW-MFC for depth and slow water flow provide a favorable environment for sedi­
the degradation of recalcitrant micro pollutants has been explored by ments to settle. Additionally, in these circumstances, sufficient contact
several researchers (Wang et al., 2019; Di et al., 2020; Srivastava et al., time between the water, substrate, and wetland surfaces can be attained.
2020). Due to the abundance of accessible organic and inorganic elements, the
microbial population can therefore break down a wide range of chem­
5. Factors affecting the EDCs removal performance of CW system icals in wastewater (Azni et al., 2010). Furthermore, Wu et al.’s research
indicated that deeper water will allow for longer hydraulic residence
The configuration of the wetland, the soil/substrate matrix, the times, which will give more time for contaminant removal (Wu et al.,
depth of the substrate, the type of plants, the operating mode (batch or 2015). The study, which examined how water depth affected the effi­
continuous), and the hydraulic residence time (HRT) are all design and ciency of photodegradation of micropollutants in a free-water surface
operational aspects of CWs that can have an impact on the removal of constructed wetland receiving treated wastewater, revealed that all
pollutants (Zhang et al., 2014). According to Zhang et al. (2014), CWs micropollutants showed a significant decrease in photodegradation ki­
configuration has a significant impact on the physical-chemical condi­ netics between 10 and 30 cm, which corresponded to the significant
tions of the system, such as redox potential and insolation. attenuation of UV rays in the first 10 cm of the water column (Mathon
et al., 2019).
5.1. Role of design and operational factors of CWs in the removal of EDCs
5.1.3. Hydraulic retention time (HRT)
5.1.1. CWs configuration The duration of interaction between pollutants and bacteria is
Wetland configuration, among other factors, can significantly impact influenced by hydraulic retention time (HRT), which is a crucial factor.
the removal of pollutants. For instance, depending on how the CWs are Hydraulic retention time is the term used to describe how long the
configured, nonylphenol removal rates could range from 0 % to 88 % wastewater must remain in the wetland system before the treatment
(Papaevangelou et al., 2016). In VSSF-CWs, where aerobic conditions process is complete. It is important to consider when determining how
are common, the maximum removal was seen. Both planted and well a CW system will operate (Yan and Xu, 2014). It was also noted that
unplanted HSSF-CW systems often had greater nonylphenol the retention duration has a significant impact on the physical,

409
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chemical, and biological procedures that are used to remove contami­ ketoprofen, salicylic acid, sulfadiazine, and caffeine). According to
nants from wastewater (Minakshi et al., 2021). The removal efficiency of Kumar et al. (2022), high temperatures also favor biodegradation pro­
two endocrine-disrupting chemicals (EDCs), namely diclofenac (DCF) cedures and the endothermic hydrolysis reaction. According to Białk-­
and bisphenol A (BPA), was assessed using HFCWs and the results Bielińska et al. (2012), the majority of micropollutants, including EDCs,
showed that their removal efficiency increased as HRT was increased are hydrolytically stable and have a long half-life in typical environ­
from 6 h to 48 hr (Bessadok et al., 2023). Previous research also revealed mental settings. As a result, the most likely pathway for their removal in
a substantial link between HRT and the efficacy of removing six phar­ CWs is through microbial degradation, which is accelerated at warm
maceuticals (diclofenac, ketoprofen, clarithromycin, ofloxacin, sulfa­ temperatures (15–25 ◦ C) (Hijosa-Valsero et al., 2010). Another study
methazine, and gemfibrozil), indicating that a longer contact time found that warm weather increases root activity and plant growth
promotes the elimination of pharmaceuticals (Herrera-Cárdenas et al., (Matamoros et al., 2016). As a result, emerging pollutants like EDCs are
2016; Auvinen et al., 2017). Additionally, in a study involving the two removed by plant uptake more effectively (Hijosa-Valsero et al., 2010,
natural estrogens E2 and E1, there was no degradation at HRT 1/4 27.5 Hijosa-Valsero et al., 2016; Macci et al., 2015; Yan et al., 2016; Petrie
h, whereas the removals significantly increased (up to 59 % and 85 %, et al., 2018). These findings are in line with a study by llyas and van
respectively) with a HRT of 137.5 h. This difference is likely attributable Hullebusch (2020), which found that caffeine, salicylic acid, ketoprofen,
to a longer period of time in which the pollutant was in contact with the diclofenac, and naproxen were removed more quickly at hot tempera­
CW substrate (Chen et al., al.2014). Contrarily, study done by Balles­ tures (summer) than at low temperatures (winter).
teros et al. (2016) shown that raising the HRT past 8 days no longer
significantly increased efficiency and would require large-sized CWs. 5.3. Seasonality effects
Another study conducted by Vymazal (2010) also demonstrated the
negative consequences of long retention times. Several studies reported the variation in removal of emerging micro
pollutants such as EDCs in summer and winter is due to the difference in
5.2. Role of physicochemical parameters of CWs in the removal of EDCs external temperature, which directly affects water temperature and
oxygen solubility which have major role the removal processes of these
5.2.1. pH emerging compounds in CWs such as biodegradation, plant uptake, and
The influent wastewater’s pH might be regarded as a crucial adsorption/sorption processes (Kahl et al., 2017; Nivala et al., 2019).
parameter since it regulates a number of biotic processes. For the growth Previous researches have shown that microbial degradation, which is
of plants, nitrification, and heterotrophic microbial activities in CWs, accelerated at warm temperatures in the summer (15–250C), is the most
the ideal pH values are said to be close to neutral (Dordio et al., 2013b). likely pathway for the elimination of EDCs-emerging compounds in CWs
The degree of ionization of the ionizable substances determines the (Avila et al., 2013; Chen et al., 2016a; Zhang et al., 2011; Zhang et al.,
extent of their removal, which is governed by the pH of the system and 2018; Matamoros and Hijosa-Valsero, 2018). Other research findings
the presence of plants affects the performance of CWs by controlling the also reported that in summer, a more active vegetative stage of plants
pH (7.5) (Dordio et al., 2013b; Carvalho et al., 2013). llyas and van also contributes to variability in EDCs removing performances of CWs
Hullebusch (2019) found a significant positive correlation between pH (Matamoros and Hijosa-Valsero, 2018; Reyes-Contreras et al., 2012).
value and the removal efficiency of five of the studied pharmaceutical Additionally, it was established that the photodegradation rate of
compounds (ketoprofen, erythromycin, lincomycin, ofloxacin, and micropollutants like EDCs is accelerated by the greater sun irradiation
sulfamethazine). during the summer (Nuel et al., 2018; Zhang et al., 2018a). On the other
hand, researchers also reported that abiotic processes like adsorption are
5.2.2. Dissolved oxygen (DO) also temperature-dependent and, favored by low temperature (in
Dissolved oxygen (DO) is one of the most significant factors that can winter) (Reyes-Contreras et al., 2012). In previous study, a significant
affect the constructed wetland removal performance of pharmaceuticals influence of the season in the removal of nonylphenol was observed.
including EDCs. Discontinuous feeding, which replenishes the oxygen in Results show that the identical subsurface CW system performs consid­
the substrate pores as tested in horizontal sub-surface CWs, has been erably differently in winter and summer, with removals of 25 and 80 %,
shown to improve the removal efficiency of drugs including diclofenac respectively. Wintertime temperatures are thought to have less removal
(DCF), ibuprofen, and ketoprofen (Avila et al., 2013Zhang et al., 2012). because they can impede microbial activity (Qiang et al., 2013). In
In an earlier research work, Avila et al. (2014b) examined the impact of another study, the removal efficiency of clarithromycin varied in a
active aeration on the removal of pharmaceuticals in vertical VSSF-CW system, depending on the season (17 % in the summer and 89
sub-surface flow (VSSF) CWs and found that the actively aerated satu­ % in the winter), whereas the elimination of erythromycin was higher
rated CW performed similarly to the conventional unsaturated CW. A than 86 % in all sampling campaigns (Ruhmland et al., 2015). However,
study carried out by llyas and van Hullebusch (2019) confirmed that authors did not provide an explanation for these different behaviors.
effluent DO is among the most significant parameters, as indicated by its Hijosa-Valsero et al. (2010) reported that waste water treatment per­
significant correlation with the removal efficiency of eight phar­ formance of constructed wetland was better in the warm season than the
amacuetical compounds by constructed wetland systems. This was also cold season in seven systems (mesocosm) of various designs and for nine
supported by other previous studies (Avila et al., 2014b; Chen et al., EOCs. Another previous study done by Zhang et al. (2017) also stated
2016b). that removal of IBU in saturated mesocosm treatment wetlands fed with
artificial influent was positively influenced by water and air tempera­
5.2.3. Temperature ture, resulting in higher treatment performance in summer compared to
Emerging compounds like EDCs are removed from CWs primarily winter months. The higher performance in warm season was attributed
through plant absorption and microbial degradation. According to Van to increased biological activity.
De Moortel et al. (2010), a decrease in water temperature has a
considerable impact on both plant development and rhizosphere mi­ 5.4. Planted and unplanted CWs
crobial activity. Additionally, microbial activity in the bulk sediment
and rhizosphere is drastically decreased when soil and air temperatures In addition to direct uptake, plants’ indirect benefits include enzy­
are likewise low (Ji et al., 2022), leading to low emergent pollutant matic exudate degradation, oxygen release, and the release of root ex­
removal capability. llyas and van Hullebusch (2020) study found a udates (such as carbohydrates and amino acids) into the rhizosphere,
strong positive link between temperature and the efficacy of removing which can support microorganisms in producing organic carbon and a
six of the pharmaceuticals under study (naproxen, diclofenac, source of nutrients, thereby increasing the bioavailability of emerging

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S.B. Gebru and A.A. Werkneh South African Journal of Chemical Engineering 48 (2024) 395–416

pollutants like EDCs (He et al., 2018; Salcedo et al., 2018). This might be examination related to their performance.
the reason why planted CWs are more easily removed the pollutant than
unplanted CWs. According to a study by Li et al. (2017), acetaminophen Declaration of competing interest
was removed with an effectiveness of 98 % in systems planted with
Spirodela polyrhiza and 84 % in systems without plants. The removal of The authors declare that they have no known competing financial
erythromycin (63 %) was only achieved in the planted system (Phrag­ interests or personal relationships that could have appeared to influence
mites australis), demonstrating that the presence of plants favors its the work reported in this paper.
removal (Hijosa-Valsero et al., 2011). Previous research work aimed to
assess the emerging pollutant removal performance of HFCW systems Data Availability
revealed this. In an FWSCW, it was also discovered that planted systems
had greater sulfamethoxazole removal effectiveness (92 %) than No data was used for the research described in the article.
unplanted systems (73 %) (Xian et al., 2010). Furthermore, Phragmites
australis-planted systems had a greater removal efficiency of oxytetra­ References
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