A review of approaches to atrazine treatment employing advanced oxidation processes technologies

Uma revisão das abordagens de tratamento da atrazina empregando tecnologias de processos oxidativos avançados

ABSTRACT

Atrazine is a synthetic pesticide widely used in many crops. It is considered a contaminant to soil and water, and due to its leaching and recalcitrant capacities, new treatment technologies have been developed for its removal, with an emphasis on advanced oxidation processes (AOPs), since conventional wastewater treatments show reduced capacity to remove persistent organic pollutants. This article provides a literature review of the main AOP approaches, such as photolysis, ozonation, photoperoxidation, fenton and photo-fenton, photocatalysis, and electrochemical processes, for the atrazine treatment and the fundamentals behind each process. In addition, the innovations and applications of hybrid AOP systems were documented. It is worth mentioning that despite the high efficiency obtained by AOPs in the degradation of ATZ, it is important to evaluate the resulting toxicity and by-products formed, as well as the costs associated with the application of these processes.

Keywords:
oxidative process; degradation pathways; removal efficiency; contaminated environment; atrazine by-products

RESUMO

A atrazina é um agrotóxico sintético amplamente utilizado em diversas culturas. É considerado um contaminante do solo e da água, e, devido à sua capacidade lixiviante e recalcitrante, novas tecnologias de tratamento têm sido desenvolvidas para sua remoção, com destaque para os processos oxidativos avançados (POAs), uma vez que os tratamentos convencionais de efluentes apresentam capacidade reduzida de remover poluentes orgânicos persistentes. Este artigo fornece uma revisão da literatura sobre as principais abordagens de POAs, como fotólise, ozonização, fotoperoxidação, fenton e fotofenton, fotocatálise e processos eletroquímicos, para tratamento da atrazina e os fundamentos reacionais por trás de cada processo. Em adição, as inovações e as aplicações de sistemas POAs híbridos foram documentadas. Vale ressaltar que apesar da alta eficiência obtida pelos POAs na degradação da ATZ, é importante avaliar a toxicidade resultante e os subprodutos formados, além dos custos associados à aplicação desses processos.

Palavras-chave:
processo oxidativo; vias de degradação; eficiência de remoção; ambiente contaminado; subprodutos da atrazina

INTRODUCTION

Among many organochlorine pesticides, atrazine (ATZ), as a s-triazine pesticide, has been used primarily to control broadleaf weeds and grasses in agriculture crops (Xu et al., 2019). The extensive use and persistence of ATZ cause contamination of soil and water (Hanson et al., 2019). Its presence in the environment is alarming, due to its potential toxicity in animals as a reproductive corruptor and immunomodulator (Albuquerque et al., 2020; Jiang, C. et al., 2020) and in humans as a potential endocrine deregulator and probably carcinogenic (Komtchou et al., 2020; Zhu et al., 2021).

From around 20 different classes of existing pesticides, the class of triazine substances is among the most consumed throughout the world, and the focus of this study is on ATZ, which remains among the most frequently monitored and studied compounds in groundwater, surface water, and soil (Lee, 2003; Hong et al., 2019; Jiang, C. et al., 2020; Esquerdo et al., 2021). Due to its inevitable aquatic contamination, ATZ was banned in the European Union (EU) in 2003 (Yue et al., 2017). Yet most countries, including the USA, India, China, and Brazil, still have large-scale consumption (Chandra; Usha, 2021). And even in territories where it has already been forbidden, ATZ is still found in aquatic environments. While the hydrological cycle is the main cause of contamination due to leaching, the water-contaminated influx by runoff is continuous (Pascal-Lorber; Laurent, 2010). The study by Vizioli et al. (2023) reports the detection of ATZ and three of its by-products, at concentrations ranging from 2.0 to 2.7 ng L⁻¹, in the surface waters of the Capivari and Atibaia rivers, as well as detection in treated water (Campinas, Brazil). In addition, ATZ has also been detected in the Yangtze and Huangpu rivers in China, from 8 to 180 μg L⁻¹ (Sun et al., 2018), and in surface and groundwater in the United States, from 1 to 25 μg L⁻¹ (Tillitt et al., 2010; Wang et al., 2022).

The physical–chemical properties of ATZ (Table 1) match its characteristics of high hydrophobicity (high log K_ow value), moderate polar nature, which is linked to its moderate solubility in water, high dipole moment, and complex molecular structure (Oliveira Jr; Koskinen; A Ferreira, 2001). Due to its half-life between 41 and 231 days (Karlsson et al., 2016), low adsorption in soils, and moderate aqueous solubility, it has the potential to contaminate not only agricultural fields but also groundwater, mainly in a well-structured soil profile with macropores (Dias et al., 2019).

Table 1
Physicochemical properties of atrazine.

Atrazine (ATZ)
Molecular structurea
Formulaa	C8H14N5Cl
IUPAC nameb	2-Chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine
Molecular weightc	215.685 g mol−1
Melting pointa	171–174 °C
Solubilitya in water at 20–25 °C	33 mg L−1
pKaa	1.68
Log Kowc	2.61
Dipole momentc	4.6 D
Polluted biotopesd	Fields, Water networks
Geo-localizationd	Watersheds
Persistenced	15–100 days
Plant uptaked	High
Phytotoxicityd	High

• Source: Adapted from ^aLee (2003), ^bet al, ^cChandra and Usha (2020), and ^dPascal-Lober and Laurent (2010).

It is known that the presence of ATZ in the aquatic environment directly interferes with the food chain of aquatic animals, as the pesticide can significantly inhibit algae growth and photosynthesis (Zhu et al., 2016). Singh et al. (2018) reviewed studies in which ATZ manifested acute toxicity to some species of amphibians and fish, interfering mainly in biotransformation, generating a significant increase in genotoxic damage and oxidative stress, inducing changes in enzymatic activities, and damaging the endocrine and liver systems of these animals. Albuquerque et al. (2020) also reviewed studies that analyzed the toxic effect on mollusks, crustaceans, and insects, disrupting biomarkers, hormones, morphology, the reproductive system, and genetics, and also on reptiles, damaging the immune system and their development. In mammals, the main action of ATZ is to disrupt the endocrine system (La Casa-Resino et al., 2012; Jin et al., 2014; Cook et al., 2020; Galbiati et al., 2021), followed by oxidative stress (Jestadi et al., 2014; Saalfeld et al., 2018; Semren; Žunec; Pizent, 2018; He et al., 2022), sexual hormone imbalance (Bohn et al., 2011; Govers et al., 2020; Abarikwu et al., 2021), DNA damage (Yang et al., 2010; Sánchez et al., 2020; Xie et al., 2021), which can even affect cardiovascular functioning (Lin et al., 2016; Li et al., 2017; Li et al., 2018), as well as liver damage (Campos-Pereira et al., 2012; Foulds et al., 2017; Harper; Finger; Green, 2020). Proven evidence of ATZ’s toxicity culminated in its classification as an endocrine-disrupting pesticide by the United States Environmental Protection Agency (USEPA, 2007) and also its entry into the International Agency for Research on Cancer’s list of carcinogenic pesticides (IARC, 1999).

ATZ may be removed by conventional techniques such as coagulation–flocculation by the addition of ferrous iron coagulants or low-cost biosorbents (Cheng et al., 2017; Liu et al., 2020), adsorption on humic substances, clays, oxyhydroxides, and activated carbon (Hong et al., 2019; Sun et al., 2021), nanofiltration and microfiltration membranes (Ahmad; Tan; Shukor, 2008; Chandra; Usha, 2021), or reverse osmosis (Naidu et al., 2017). However, these technologies only transfer the contaminant from one state to another (Romero et al., 2020). Other traditional wastewater treatment methods, such as biodegradation (Derakhshan et al., 2018; Singh et al., 2018), may not efficiently and completely remove ATZ in a short period, making the degradation of ATZ even more challenging. To mitigate this, a great deal of research effort has been invested to remove ATZ and its by-products with different approaches, mainly methods based on chemical reactions, which can eliminate the contaminants through complete mineralization (Komtchou et al., 2020).

The advanced oxidation processes (AOPs), which involve the formation of radicals with excellent reactivity, have emerged as an effective solution to eliminating persistent organic pollutants (Hong et al., 2019). Since the 21st century, publications on ATZ degradation by AOPs have increased exponentially over traditional methods, including Fenton and photo-Fenton reactions (Cheng et al., 2017), photolysis (Moreira et al., 2017), ozonation (Yang et al., 2016), peroxidation (Kida; Ziembowicz; Koszelnik, 2018), heterogeneous catalysis (Santacruz-Chávez et al., 2015), and even applications of combined AOPs (Ahmed et al., 2017). These processes stand out for their increased efficiency in removing ATZ and its byproducts in a shorter time (Dhangar; Kumar, 2020). Furthermore, currently, advanced oxidation processes based on sulfate radicals have drawn considerable attention due to their high efficiency over a wide pH range and multiple operation advantages (Wang et al., 2019). This review article makes a unique contribution to the literature on the application of AOPs in the degradation of atrazine, aiming to critically evaluate the feasibility of AOPs in physical, chemical, and hybrid treatments as a means of removing ATZ from water. Specifically, this article provides a summary of the effectiveness of different AOPs in water treatment for ATZ removal combined with their degradation pathways and the formation of by-products. It is discussed beyond conventional AOPs and hybrid processes for the removal of ATZ, including the challenges and current knowledge gaps that limit the effectiveness of AOPs.

BIOLOGICAL AND PHYSICAL TREATMENT TECHNOLOGIES

Biological treatment technology is one of the leading techniques applied for atrazine degradation (He et al., 2019). Biological nitrification or denitrification is considered an alternative. Phan et al. (2014) observed this process in an anoxic–aerobic membrane bioreactor applied to a set of 30 compounds, including atrazine, but only 8% was removed. Kamaz et al. (2020) also applied a membrane bioreactor to remove ATZ detected at 0.02 ppm in a real effluent, resulting in approximately 20% removal, consequently; it could estimate the probability of ATZ biodegradation in that wastewater treatment plant. Microorganisms (such as bacteria, fungi, and microalgae) with great adaptability and mutability in a polluted environment were also studied for the biodegradation capacity of atrazine alone and/or in vitro, including Pseudomonas sp. (Zhao et al., 2017; Fernandes et al., 2018; Sharma et al., 2019), Achromobacter sp. (Fernandes et al., 2018; Cao et al., 2020; Jiang, Z. et al., 2020), Aspergillus niger (Herrera-Gallardo et al., 2021), Aspergillus oryzae (Lu et al., 2021), and microalgae of the Phylum Chlorophyta (Matamoros et al., 2015).

Regarding physical methods, sedimentation and flocculation processes are not effective for removing pesticides such as ATZ, as they remain partitioned in the aqueous phase (Ahmed et al., 2017). However, membrane filtration and adsorption technologies stand out. The membrane filtration process has been used in wastewater treatment plants, with the type of membrane varying according to the type of pollutant to be treated (Jatoi et al., 2021). The study carried out by Ahmad, Tan, and Shukor (2008) evaluated the adsorption capacity of ATZ on four nanofiltration membranes: NF90, NF200, NF270, and DK, with the best result being obtained for NF90, with 95% retention of ATZ at 2 mg L⁻¹. According to Bodzek and Konieczny (2018), the type of membrane material and the molecular weight cut-off (MWCO) are the main parameters that influence ATZ removal in ultrafiltration processes, obtaining approximately 60% removal when using a membrane with an MWCO of 1–2 kDa. The adsorption process is characterized by the use of adsorbents such as activated carbon, biochar, zeolite, and bentonite, among others (He et al., 2019). The efficiency of the adsorption process in the treatment of ATZ varies according to the surface area, the number of active sites available, and the type of interaction that occurs between the adsorbent and the adsorbate (Jatoi et al., 2021).

The biological processes mentioned here have limitations, such as ambient temperature, salinity, pH, nutrient content, toxic substances, and other factors that will affect the efficiency of microorganism degradation. Among the advantages are the non-generation of toxic by-products, as occurs in some chemical treatments, low energy consumption, and low operating costs (Ahmed et al., 2017). Therefore, there is still a search for microorganisms with better performance and environmental tolerance when applied to real conditions (He et al., 2019). Physical processes such as membrane filtration and adsorption generally have a high efficiency in removing recalcitrant organic contaminants such as ATZ. In the case of nanomaterials, despite having excellent adsorption properties, they have a high preparation cost (He et al., 2019), and the adsorption process involves the challenge of regenerating the adsorbent. The main disadvantage of physical processes is that most of them involve transferring the contaminant from the aqueous phase to a solid phase, leading to the problem of discarding or reusing this solid material.

ADVANCED OXIDATION PROCESSES (AOPs)

With the increasing detection frequency of contaminants in the water, new treatment technologies had to be developed. Currently, AOPs are recognized as one of the most effective alternatives for the degradation of compounds of environmental relevance (Lelario et al., 2016). AOPs are based on the formation of reactive radicals, which have a high oxidizing power and can result in the degradation of different pollutant compounds in relatively short periods (Jiang, C. et al., 2020). These radicals can be formed by several processes that can be classified into homogeneous or heterogeneous systems, depending on the absence or presence of catalysts in the solid state, in addition to whether it may be under irradiation (Oliveira et al., 2020). The main AOPs can be identified as the processes of photolysis, ozonation, photoperoxidation, photo-Fenton, photo-catalysis, electro-Fenton, ultrasound, or gamma ray irradiation (Saleh et al., 2021), and their reactions are shown in Table 2, besides combined approaches. These processes can be applied to ATZ removal from wastewater with high efficiency (Salimi et al., 2017), as presented in Figure 1.

Table 2
The generalized reactions of advanced oxidative processes.

AOP	Reactions	Light energy required
Photolysis	$${\text{H}}_2\text{O}+hv\to \text{HO}*+\text{H}*$$
Ozonation Photo-ozonation	$${\text{O}}_3+\text{OM}\to {\text{O}}_2+\text{oxidized}\text{OM}$$ $${\text{O}}_3+hv\to {\text{O}}_2+\text{O}{(}^1\text{D})$$ $$\text{O}{(}^1\text{D})+{\text{H}}_2\text{O}\to 2\text{HO}*$$	λ < 310 nm
Photoperoxidation	$${\text{H}}_2{\text{O}}_2+hv\to 2\text{HO}*$$	λ < 280 nm
Fenton Photo-Fenton	$${\text{Fe}}^{2+}+{\text{H}}_2{\text{O}}_2\to {\text{Fe}}^{3+}+{\text{HO}}^{-}+\text{HO}*$$ $${\text{Fe}}^{3+}+{\text{H}}_2{\text{O}}_2\leftrightarrow {\text{H}}^{+}+{\text{FeOOH}}^{2+}$$ $${\text{FeOOH}}^{2+}\to {\text{Fe}}^{2+}+{{\displaystyle \text{HO}}}_2^{*}$$ $${\text{Fe}}^{2+}+{\text{H}}_2{\text{O}}_2\to {\text{Fe}}^{3+}+{\text{HO}}^{-}+\text{HO}*$$ $$\text{Fe}{(\text{OH})}^{2+}+hv\to {\text{Fe}}^{2+}+\text{HO}*$$	λ < 580 nm
Photocatalysis	$${\text{TiO}}_2+hv\to {\text{TiO}}_2({\text{e}}_{\text{CB}}{}^{-})+{\text{TiO}}_2({{\displaystyle \text{h}}}_{\text{VB}}^{+})$$ $${\text{TiO}}_2({\text{e}}_{\text{CB}}{}^{-})+{\text{OH}}^{-}\to {\text{TiO}}_2+\text{HO}*$$	λ < 280 nm
Electro-Fenton	$$\text{OM}+{\text{H}}_2\text{O}\to \text{OM}(\text{HO}*)+{\text{H}}^{+}+{\text{e}}^{-}$$ $$\text{MO}(\text{HO}*)+\text{R}\to \text{MO}+{\text{CO}}_2+{\text{H}}_2\text{O}+{\text{H}}^{+}+{\text{e}}^{-}$$ $$2{\text{H}}_2\text{O}+2{\text{e}}^{-}\to {\text{H}}_2+2{\text{OH}}^{-}$$

• OM: organic matter; R: pollutant.
Source: author (2023).

Figure 1
Comparison of removal efficiencies of ATZ by oxidation processes.

Photolysis

The initial studies involving atrazine photolysis were published in the 1990s, with emphasis on the study made by Bourgine et al. (1995), which achieved 30% degradation of ATZ when applied energy of 200 Wh m⁻³ and 70% with 700 Wh m⁻³, promoting the statement that the degradation rate of atrazine is directly proportional to the photolytic energy supplied to the system. Chen et al. (2009) used a cylindrical reactor equipped with an immersible low-pressure mercury lamp (8 W), providing the system with an ultraviolet intensity of 0.96 mW cm⁻². The atrazine was mineralized at 90% after 50 min of reaction. In their work, it was observed that the pH of the reaction medium suffered a slight decrease, explained by the formation of acidic by-products such as cyanuric acid, ammelide, and ammeline. Hence, the possible reaction pathways for the photodecomposition of atrazine have been identified and quantified by liquid chromatography-mass spectrometry and the intermediates were determined: chloro-dealkylation, dechlorination-hydroxylation, alkylic-oxidation, dechlorination-hydrogenation, dechloro-dealkylation, deamination-hydroxylation, and olefination. And due to the formation of these byproducts that do not absorb the lower wavelengths of the spectrum of light, complete mineralization has been difficult to achieve. This same occurred with studies such as the one by Kong et al. (2016); they checked the direct photolysis of atrazine using a low-pressure UV lamp with λmax=254 nm and UV irradiance of 0.15 mW cm⁻² after calibration. For [ATZ]=1.0 μM and pH=7.0, the process reached approximately 40% of the mineralization of ATZ. Similarly, Moreira et al. (2017) studied the atrazine degradation process (3 mg L⁻¹) and the formation of metabolites using the same kind of UV lamp, recording a 34% atrazine reduction after 300 s. These authors observed a substantial increase in the presence of atrazine-2-hydroxy (HAT), resulting from the hydroxylation of the halogenated carbon.

Ozonation

The ozonation process has been widely applied in water and wastewater treatment, as well as for disinfection and the degradation of toxic organic pollutants. Nevertheless, ATZ can be considered resistant to degradation by ozonation due to its low reactivity with ozone (Acero; Stemmler; von Gunten, 2000). In water, the ATZ and other ozone-refractory compounds were eliminated with lower efficiency; this was caused by the production phenomenon of OH• during aqueous ozonation. Yang et al. (2016) observed that only 20% of ATZ at an initial concentration of 2 μM was degraded by ozonation at a neutral pH. In an alkaline medium, Yixin et al. (2014) witnessed that the ATZ degradation rate significantly increased with ozone applications. The removal of ATZ with an initial concentration of 10 μM ATZ reached 98% when the solution was pH 10, five times greater than at pH 2. That was because the OH– ion is one of the main initiators of the decomposition of aqueous ozone into hydroxyl radicals. However, in addition to the high energy consumption and high cost, according to Wang and Chen (2020), some toxic disinfection by-products can be formed during the ATZ ozonation process, especially trihalomethanes and haloacetic acids, which have had a negative effect on human health. To mitigate this environmental impact, the catalytic ozonation process has earned increasing attention in recent years, as recent studies report a potentiate of the efficiency of ozone in the degradation of ATZ in the presence of other oxidants such as hydrogen peroxide, nitrite, and hydroxylamine, among others, as well as combined processes with microwaves, UV, and membranes (Kolosov; Yargeau, 2019; Rajah et al., 2019).

Photoperoxidation

Beltrán, Ovejero, and Acedo (1993) carried out one of the first studies involving the degradation of the pesticide atrazine in water as a function of the photoperoxidation process. In this study, the addition of different concentrations of H₂O₂ was analyzed with the aid of a mercury lamp (15 W), emitting radiation at 254 nm. For an H₂O₂ concentration of 0.01 M, approximately 99% of the ATZ oxidation rate was obtained just after 7 min of the process. When subjected to higher concentrations of H₂O₂, there was an abrupt decrease in efficiency, which was explained by the excess reagent added to the reaction. It is known that with excess peroxide and high concentrations of HO^•, competitive reactions occur that slow the degradation rate (Ferreira; Maniero; Guimarães, 2015), but the conversion of H₂O₂ to hydroxyl radicals did not show results greater than 10% in any of the cases studied. These results were due to the amount of H₂O₂ added. However, it should be noted that there was a higher generation of hydrogen peroxide molecules because of the parallel reactions of the generation of the hydroperoxyl radical.

De Laat et al. (1999) performed a comparative kinetic study of processes using H₂O₂ in a cylindrical photochemical reactor with a low-pressure mercury-vapor lamp. The initial study conditions were [ATZ]=100 μg L⁻¹, and the pH was adjusted to 3.0 using solutions of perchloric acid and sodium perchlorate. At a dosage of 0.5–5 mM H₂O₂, a degradation of 90% of ATZ was achieved. Chen et al. (2011) investigated the oxidative decomposition of atrazine in water using a photochemical reactor and determined the ideal conditions for its decomposition. For [ATZ]=20.8 mg L⁻¹, total degradation was achieved with a dose of 300 mg L⁻¹ of hydrogen peroxide. In this study, the experiments were restricted to a nearly neutral pH value, between 5.0 and 7.0. The oxidation rate of the atrazine molecule depended on three distinct contributions in this case: UV incidence, H₂O₂ addition, and HO^• radicals generated. Thus, the action of hydrogen peroxide alone without combined photolysis did not result in a considerable oxidation potential for the degradation of this contaminant. In this case, two decomposition pathways of ATZ were highlighted: direct photolysis and HO^• radical oxidation. The applied treatment was not able to reach complete mineralization of the molecule, but it had a great contribution in inducing the dealkylation of aromatic ring lateral chains, including its byproducts having less toxicity than the original compound.

Fenton and photo-Fenton

The study conducted by Gallard and de Laat (2000) was one of the pioneers in the kinetic evaluation of atrazine decomposition in the Fe^III:H₂O₂ process. The concentrations used were 0.2 mM<H₂O₂ <1 mM and 1<H₂O₂:Fe^III <5.103 at pH 3.0, and the degradation rate reached approximately 100% in less than 30 min. Chan and Chu (2003) also studied ATZ removal by the Fenton reaction in multiple concentration ratios of ferrous ions (3<Fe^II:H₂O₂ <0.33) and hydrogen peroxide (0.01 mM<H₂O₂ <0.2 mM), obtaining a sharp removal curve in the first minutes and then gradually slower during the reaction. The concentrations of ferrous ion and hydrogen peroxide are significant in the oxidation rate of ATZ. When a high dose of iron was employed, the number of ferrous ions consumed by the process was not considerable, and the oxidation capacity was not affected. Conversely, when the Fe²⁺ dosage was low, the action of H₂O₂ was notable in the oxidation by the Fenton process.

The research conducted by Barreiro et al. (2007) evaluated the oxidative decomposition of ATZ at different pHs in an abiotic process using ferrihydrite and H₂O₂ to investigate the influence of parameters such as pH, ferrihydrite, and H₂O₂ concentrations. The applied process was the Fenton-like reaction, which is characterized by the use of native or synthesized iron oxide (FeO, Fe₂O₃, and Fe₃O₄) instead of free iron ions (Cheng et al., 2016). The contribution of pH was confirmed by detecting oxidation rates 10 times faster at pH 3.0, stimulated by the formation of Fe^III species. Therefore, when conducting experiments in a high pH range (6.5–8), the oxidation rate decreases, which can be explained by the reduction in the concentration of solubilized iron compounds in the system since ferrihydrite is better solubilized at acid pH.

Fenton-like reactions have an unconventional character for not using free iron ions, which means that they are replaced by iron-based industrial by-products or native iron compounds, thus making the Fenton-like reaction a sustainable alternative. However, this process is three times slower than conventional Fenton, as the regeneration of Fe^II is mainly responsible for the total reaction time. In this system, there is also the production of HO₂^•, which is a radical with a lower oxidation potential compared to HO^• (Romero et al., 2020). Therefore, there is a growing interest in designing working conditions more favorable to the Fenton-like reaction, expanding the time and pH range required (Zhang; Zhou, 2019). Rocha et al. (2024) used the extraction residue, basalt powder, as a natural photo-Fenton catalyst for ATZ degradation under UV-C (96%) and visible (56%) light under circumneutral pH. The authors evaluated the reusability of the catalyst, the degradation of by-products desethyl-atrazine (DEA), desisopropyl-atrazine (DIA), and hydroxyatrazine (HA), and toxicity tests. The research carried out by Gonçalves et al. (2020) evaluated a photo-Fenton process using organic iron ligands, biodegradable ethylenediamine-N and N′-disuccinic acid, to allow application in a wide pH range (3–9). This system achieved a 98% degradation of ATZ in only 15 min at pH 6.0, achieving greater mineralization than classic photo-Fenton at pH 2.7.

Photocatalysis

In the 1960s, photocatalysis emerged as an alternative to remove pesticides such as ATZ from contaminated water (Ameta et al., 2018; Long et al., 2020). The homogeneous catalytic degradation processes include transition metal ions (Mn²⁺, Fe³⁺, Co²⁺, Cu²⁺, and Zn²⁺) as catalysts and result in the efficient degradation of organic pollutants (Xu et al., 2019; Wang; Chen, 2020). Wang et al. (2019) studied the degradation of ATZ at an initial concentration of 23 μM in the presence of activated peroxymonosulfate (PMS) by Cu-doped LaFeO₃ perovskite. In both heterogeneous and homogenous activation of PMS, ATZ was removed almost in its entirety; however, the homogeneous reaction process contributed limitedly to PMS activation. Cobalt-mediated activation of PMS was investigated by Chan and Chu (2009) with 95% ATZ removal by homogeneous process at an initial concentration of 0.1 mM, but four times slower than by heterogeneous process, in which PMS was activated by Co-TiO₂ particles in the presence of UV-Vis. Although homogeneous catalysis is an efficient process for removing organic pollutants because of the high solubility of transition metals, it is not technologically feasible to recover them, thus leading to secondary pollution caused by residual metal ions (Wang et al., 2019; Xu et al., 2019).

Therefore, research has focused on heterogeneous catalysis and photocatalysis by insoluble metal oxides. Santacruz-Chávez et al. (2015) used TiO₂ in metallic nanoparticles, including Au, Ni, and Cu, by deposition–precipitation for the degradation and mineralization of the pesticide atrazine in solutions with an initial concentration of 25 ppm. The Au/TiO₂ catalyst was the most successful in approximately 80% of the degradation of ATZ, followed by Cu/TiO₂ and Ni/TiO₂. Aragay, Pino, and Merkoçi (2012) reported that photocatalysis of ATZ by ceramic modified with TiO₂ resulted in excellent catalyst performance concerning the degradation of ATZ with a removal efficiency of 96% of total organic carbon (TOC).

Moreover, recent studies on heterogeneous catalysis have been published that aim to remove ATZ, mainly regarding persulfate-based advanced oxidation processes (Li et al., 2019). Shen et al. (2020) applied bismuth molybdate nanosheets (Bi₂MoO₆) to activate PMS, resulting in a 99% ATZ removal efficiency at an initial concentration of 2.5 mg L⁻¹ under visible light irradiation after 60 min of reaction. Xu et al. (2019) fabricated a new Fe₃O₄-sepiolite magnetic composite that was used as a catalyst to activate persulfate and resulted in the degradation of 71.6% of ATZ and 20.9% of solution TOC after 60 min with an initial concentration of 10 mM of ATZ. In short, heterogeneous catalysis, more specifically semiconductor-supported solar photocatalysis, has attracted attention in environmental remediation for removing atrazine owing to its unique characteristics of low cost and higher thermal and mechanical stability without residue formation. Although excellent pollutant removal efficiency exists, the catalyst properties, such as synthesis methods, energy-bandgap structure, crystallinity, surface features, and reusability, must be investigated.

Electrochemical processes

Malpass et al. (2006) published a study of the electrochemical oxidation of the pesticide ATZ at a Ti/Ru_0.3Ti_0.7O₂ dimensionally stable anode under the effect of using different supporting electrolytes, such as NaCl, NaOH, NaNO₃, NaClO₄, H₂SO₄, and Na₂SO₄. It was observed that the removal of ATZ was achieved only at considerable rates when NaCl was used as the supporting electrolyte because of the oxidizing species formed in this electrolyte. Therefore, the efficiency of these electrochemical processes would be directly related to the performance of fluid dynamics in the cells used. Barbosa et al. (2018) indicated factors that must be considered when designing an electrochemical reactor, such as size and geometry, fluid flow and electrode reaction kinetics, current intensity, potential difference and concentration distribution, heat transfer, costs, and operational simplicity.

Studies have supported the improvement of Electro-Fenton for the degradation of ATZ. Cao et al. (2020) improved the electro-Fenton process by designing a bifunctional catalyst with FeOx nanoparticles embedded into nitrogen-doped hierarchically porous carbon. The activity and selectivity for the catalytic production of H₂O₂ were improved. The catalyst exhibited excellent electro-Fenton performance for the degradation of sulfamethoxazole, atrazine, rhodamine B, and 2,4-dichlorophenol (all at 50 ppm) in a neutral reaction solution with 95%, 96%, 99%, and 99% in 90 min, respectively. In Electro-Fenton processes, there can be in situ generation of Fenton’s reagents, and the formation of sludge is too low. But the problem is that energy is required for their installation and operational costs. However, the advantage of this process is that it can degrade pesticides such as atrazine in higher concentrations more successfully than by some conventional processes.

Emerging hybrid systems

Due to the poor performance of conventional treatment processes for the removal of several emerging contaminants, a variety of hybrid treatment systems have been reported in the literature, and significant improvements have been achieved in their application in wastewater treatment in the last few years (Dhangar; Kumar, 2020; Ahmed et al., 2017). The different aspects of AOPs have been used to improve the effectiveness of various physical and biological treatment systems through the exploration of hybrid systems. Hybrid systems using AOPs are summarized in Table 3.

Table 3
Removal efficiencies of ATZ by hybrid systems.

Treatment technology	Source	Catalyst/Adsorbent	Influent (μg L−1)	Removal (%)	References
UV-Solar+Cl	Simulated drinking W	-	0.5	75	Cheng et al. (2019)
UV-Solar+HomoCat	River W modified	Fe3+-Montmorillonite	1077.5	100	Hong et al. (2019)
UV-Solar+HeteCat	Synthetic WW	TiO2/SiO2-Graphene	10,000	93.3	Li et al. (2013)
UV-Vis+HeteCat	Synthetic WW	TiO2/N/P	2500	94	Sacco et al. (2015)
UV-Vis+HeteCat	Synthetic WW	ZnO-Chitosan	2,50,000	80.29	Atarodi and Faghihian (2019)
UV-Vis+HeteCat	Synthetic WW	TiO2/B	60,000	94	Yola, Eren, and Atar (2014)
UV+HeteCat	Synthetic WW	TiO2/Au	25,000	60	Santacruz-Chávez et al. (2015)
UV+HeteCat	Synthetic WW	TiO2-Polyimide	2156.8	30	Ramasundaram et al. (2017)
CF+NF+UV+HeteCat	Synthetic/Real Agro WW	TiO2/N/W	100	99	Komtchou et al. (2020)
MW+UV+HeteCat	Synthetic WW	TiO2	20,000	98.5	Zhanqi et al. (2007)
MW+UV+H2O2	Synthetic WW	-	20,800	100	Chen et al. (2011)
O3+HeteCat	Synthetic WW	Polonite®	100	99	Kolosov and Yargeau (2019)
O3+HeteCat	Synthetic WW	Rutile TiO2	2156.8	100	Yixin et al. (2014)
O3+AD	Synthetic WW	AC	2800	90	Rozas et al. (2017)
O3+AD	Ultrapure/Natural W	AC	1	75	Restivo et al. (2013)
UV+O3	Synthetic WW	-	21,568	65	Bianchi et al. (2006)
NF+O3+AD	Real WW	BAC	0.001	70	Ahmed et al. (2017)
NF+O3+H2O2	River W	-	720	98	Saquib, Vinckier, and van der Bruggen (2010)

• AC: activated carbon; AD: adsorption; AgroWW: Agriculture Wastewater; BAC: biological activated carbon; CF: coagulation/flocculation; Cl: chlorination; H₂O₂: peroxidation; HeteCat: heterogeneous catalysis; HomoCat: homogeneous catalysis; NF: nanofiltration; MW: microwave; O₃: ozonation; UV: photolysis by ultraviolet radiation; UV-Solar: photolysis by solar radiation; UV-Vis: photolysis by visible light radiation; W: water; WW: wastewater.
Source: author (2023).

Li et al. (2013), Sacco et al. (2015), Yola, Eren, and Atar (2014), Atarodi and Faghihian (2019), and Santacruz-Chávez et al. (2015) evaluated the heterogeneous photocatalysis process with modified TiO₂ and ZnO catalysts through the deposition–precipitation procedure on sol-gel, agitation, ultrasonic bath, and calcination, providing high efficiency of ATZ removal (80%–94%) under UV-Solar and UV-Vis exposure. The use of these catalysts is conventionally carried out under UV irradiation, considering the energy required for the activation of the photocatalysts. However, after co-doping by graphene-SiO₂, nitrogen and phosphorous (N/P), chitosan, and boron (B), respectively, showed high efficiency in the visible spectrum. Komtchou et al. (2020), in addition to modifying the catalyst by introducing N₂ reactive gas into TiO₂ and WO₃ targets and through the magnetron sputtering process on photoanodes for higher photoelectrocatalytic efficiency, performed a coagulation/flocculation process followed by nanofiltration combined with heterogeneous photocatalysis, resulting in a 99% removal of ATZ.

It should be noted that the simultaneous application of microwave (MW) and UV irradiation leads to better results in photochemical processes because of its potential to accelerate the chemical reaction, therefore providing higher yields and selectivity in photochemical processes (Církva; Hájek, 1999). In this perspective, the study conducted by Chen et al. (2011) focused on combined AOP photoperoxidation with MW, resulting in the complete mineralization of ATZ. Zhanqi et al. (2007) proposed the addition of MW-assisted photocatalysis on conventional TiO₂ with 98.5% removal of ATZ. Ramasundaram et al. (2017), Rozas et al. (2017), Restivo et al. (2013), and Ahmed et al. (2017) reported that the ozonation process combined with activated carbon (AC) and biological activated carbon (BAC) promoted an efficiency of 70%–90% in ATZ degradation. When combined, ozonation promotes the generation of hydroxyl radicals that oxidize the contaminant adsorbed by activated carbon (Reungoat et al., 2012).

Furthermore, there is the development of technologies to remove organic pollutants using the physicochemical properties of AOPs and the mineralization promoted by microorganisms (He et al., 2019). Mahlalela et al. (2021) proposed a biological treatment based on an activated sludge system coupled with a photoreactor using a heterojunction of BiVO₄–Bi₂O₃ as the photocatalyst to remove ATZ at 0.0185 mM. The biological process was ineffective in the degradation of ATZ due to the possible toxicity of the compounds to the microorganisms present in the activated sludge, as the acclimatization time suggested by the authors (27–40 days) was not sufficient to increase the resistance of microorganisms to the pesticide, which generated a reduction in the efficiency of the treatment. However, with the application of the photocatalytic treatment, 70% degradation of ATZ was obtained. Hu et al. (2021) evaluated the removal and bioaccumulation capacity of ATZ by Chlorella sp. microalgae under UV-A irradiation (365 nm), and the photocatalytic degradation results showed that 31.4% of atrazine degradation occurred after 60 min, with detection of three degradation products, DIA, DEA, and desethyl-desisopropyl-atrazine (DEIA), and 83.0% removal of ATZ at 40 μg L⁻¹ after 8 days. Similarly, Shin, Kim, and Park (2019) used microorganisms immobilized on catalytic materials to form a biomaterial with physicochemical and biological efficiency simultaneously. Yu et al. (2018) synthesized a magnetic bionanomaterial of Penicillium sp. yz11-22N2 doped with nano Fe₃O₄ entrapped in gel beads polyvinyl alcohol-sodium alginate (PVA-SA) (PFEPS) and promoted the degradation of 91.2% ATZ at 8 mg L⁻¹. According to the authors, nano Fe₃O₄ may promote atrazine degradation by reductive dichlorination. Moreover, nano Fe₃O₄ provided nutrients for the growth of the microorganism, which enabled atrazine degradation through its metabolism because it was the sole source of either carbon or nitrogen.

TOXICITY ASSESSMENT

Several studies have focused on both identifying such substances and assessing their toxicity in comparison to ATZ, as the main goal in ATZ removal and degradation processes is to obtain by-products (described in detail in Supplementary Information) that are less toxic than the former pollutant to justify the application of the chosen treatment. In this regard, toxicity analysis has been implemented to enable a better evaluation of the effluent. Some of the main toxicity tests conducted in studies about the treatment of recalcitrant pollutants are bioassays with Vibrio fischeri luminescent bacteria, Daphnia magna crustacean, Hyalella azteca and Diporeia spp. amphipods, Pseudokirchneriella subcapitata unicellular algae, Drosophila melanogaster fly, and Lactuca sativa lettuce seeds (Choi; Kim; Lee, 2013; Gonçalves et al., 2020; Tavares et al., 2020).

ATZ is potentially toxic at different trophic levels, causing photosystem inhibition, changes in growth and enzymatic processes in microalgae, mutagenicity, genotoxicity, and endocrine disruption in aquatic organisms, oxidative stress and DNA damage in worms, enzyme inhibition, and changes in hepatic metabolism in fish, as well as affecting soil microbiota. ATZ contamination in humans can also cause carcinogenic effects as well as negative effects on the endocrine system, such as reduced testosterone production and sperm abnormalities (Rostami et al., 2021). Regarding the ATZ toxicity by-products, Xu et al. (2019) stated that the dealkylation by-products (DEA and DIA) are less toxic than themselves, and the hydroxylated products do not show toxicity in aquatic organisms. According to the study conducted by Choi, Kim, and Lee (2013) about the by-products of the UV and UV/H₂O₂ processes in the degradation of ATZ, the toxicity analysis of the intermediates follows the order: HA>ATZ>DEA~DIA>DEIA. The hydroxydeethylatrazine and ammeline (DEHA and DEIHA) are two compounds that show no toxicity through the Daphnia magna toxicological method.

FUTURE PERSPECTIVES

Despite the high efficiency in the degradation of ATZ and its intermediates, the AOPs hardly reach the total mineralization of this compound. One of the main challenges in the field of treatment of emerging pollutants is to promote a treatment in which these analytics are decomposed into inorganic compounds characteristic of the end of their degradation pathways. Accordingly, there is an incentive for research involving the study of hybrid treatments, whether between AOPs, with modification of heterogeneous catalysts, or even the addition of physical processes (see Table 3).

Whereas, when compared with other treatment technologies, the operating cost of AOP methods can be relatively high, the preparation of photocatalysts with excellent solar properties, reusability capacity, and low environmental impact is also the focus of future research. However, the view of the unique physicochemical properties of atrazine, it is difficult to achieve ideal removal efficiency without the generation of hazardous intermediates during the treatment in real matrices. In this sense, there is a lack of studies that emphasize the design of water treatment plants with economical approaches to remove several types of pesticides simultaneously. Furthermore, the identification of toxicity should be part of journal publishing requirements, as should a cost evaluation of the process with the finality of providing additional information to improve communication and transparency for the application of these AOPs.

CONCLUSIONS

A variety of different physical, chemical, and biological technologies have been used to remove or degrade atrazine from water in recent decades. Difficulty in biodegradation using physical and biological treatments has been reported. Chemical oxidation treatment technologies such as photolysis, ozonation, photoperoxidation, Fenton and photo-Fenton, photocatalysis, and electrochemical processes are considered the most efficient. The advantages and challenges of the different AOPs are summarized in Table 4. In conclusion, hybrid systems have recently been applied to improve the removal of this pollutant in real matrices.

Table 4
Advantages and challenges of different technologies in the removal of ATZ.

Treatment technology	Advantages	Challenges	References
Photolysis	High efficiency with UV-C light	Alone is frequently not adequate to degrade pollutants, so it is used in combination with other technologies	Jatoi et al. (2021)
Ozonation	High efficiency in the presence of H2O2; Disinfection and sterilization	High energy consumption; Formation of toxic by-products; Interference of radical scavengers	Ahmed et al. (2017); Jatoi et al. (2021)
Photoperoxidation	High efficiency with UV-C light	Excess peroxide causes a decrease in the rate of degradation; Formation of toxic by-products	Ferreira, Maniero, and Guimarães (2015)
Fenton and photo-Fenton	Degradation and mineralization; Degrades within short duration; Sunlight can be used by avoiding UV light	Decrease of OH• forming chloro and sulfato-Fe(III) complexes or due to scavenge of OH• forming Cl2 • and SO4 •− in the presence of chloride and sulfate ions; pH values are low in application; Massive sludge is generated during the reaction	Ahmed et al. (2017); Jatoi et al. (2021); Dhangar and Kumar (2020); He et al. (2019)
Heterogeneous photocatalysis	Sunlight can be used by avoiding UV light; High reaction rates upon using catalysts with low price, chemical stability, and easier recovery	Difficult to treat large volume of wastewater; Cost associated with artificial UV lamps and electricity; Separation and reuse of photocatalytic particles from slurry suspension; Some materials only possess photocatalytic properties under specific illumination	Ahmed et al. (2017); Ahmed et al. (2021); He et al. (2019)
Eletro-Fenton	Situ generation of the Fenton’s reagents; Degradation and mineralization; Degrades within short duration	High energy consumption	Cao et al. (2020)

Source: author (2024).

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• Funding:

  Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), and Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG).

Publication Dates

• Publication in this collection
  23 Sept 2024
• Date of issue
  2024

History

• Received
  08 Feb 2024
• Accepted
  17 June 2024