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Article

Simultaneous Oxidation of Emerging Pollutants in Real Wastewater by the Advanced Fenton Oxidation Process

by
Alexis Rubén Bracamontes-Ruelas
1,
Yolanda Reyes-Vidal
2,
José Rafael Irigoyen-Campuzano
1 and
Liliana Reynoso-Cuevas
3,*
1
Departamento de Ingeniería Sustentable, Centro de Investigación en Materiales Avanzados, S.C., Calle CIMAV 110, Ejido Arroyo Seco, Durango 34147, Mexico
2
Centro de Investigación y Desarrollo Tecnológico en Electroquímica, S.C., Parque Tecnológico Querétaro s/n, Pedro Escobedo, Querétaro 76703, Mexico
3
CONACYT, Centro de Investigación en Materiales Avanzados, S.C., Calle CIMAV 110, Ejido Arroyo Seco, Durango 34147, Mexico
*
Author to whom correspondence should be addressed.
Catalysts 2023, 13(4), 748; https://doi.org/10.3390/catal13040748
Submission received: 28 February 2023 / Revised: 21 March 2023 / Accepted: 7 April 2023 / Published: 14 April 2023

Abstract

:
Since the conventional processes employed in most wastewater treatment plants (WWTPs) worldwide are not designed to entirely remove or oxidize emerging pollutants, which, due to their incidence and persistence, can cause damage to both the environment and human health, several options for their degradation and removal have emerged. Coupling the advanced Fenton oxidation process as a polishing or tertiary wastewater treatment alternative within conventional WWTP processes stands out among the treatment options. Therefore, the main objective of this research was to evaluate, at the laboratory level, the ability of the advanced Fenton oxidation process to oxidize triclosan, ibuprofen, DEET (N, N-diethyl-meta-toluamide), carbamazepine, caffeine, and acesulfame-K, which represent several groups of emerging pollutants in real wastewater from the second settling tank of a municipal WWTP. The compound used as a catalyst (Fe2+) supplier in the advanced Fenton oxidation process was ferrous sulfate heptahydrate (FeSO4•7H2O). The results obtained upon application showed that the advanced Fenton oxidation process could simultaneously oxidize and remove practically the total concentration of the above-mentioned emerging pollutants, except for DEET (85.21%), in conjunction with the chemical oxygen demand (COD), total suspended solids (TSS), and fecal coliforms (FC, pathogen group) in the effluent generated by the advanced Fenton oxidation process.

1. Introduction

The development of anthropogenic activities (agriculture, industry, and health, among others) has led to the production and use of chemicals called emerging pollutants or contaminants. Emerging pollutants are natural or synthetic organic chemicals, which are not commonly monitored in the environment but have the potential to cause harmful effects to both the environment and human health [1,2,3]. Emerging pollutants have been detected in surface water, groundwater, rivers, WWTPs, and drinking water [4]. Emerging pollutants can usually be classified into pharmaceuticals, personal care products, hygiene products, pesticides, hormones, food additives, flame-retardants, endocrine disruptors, lifestyle products, and others [4,5,6,7,8].
The emerging pollutants’ main entry route into the general environment is through effluents generated by WWTPs using conventional biological treatments [6]. The conventional process most used worldwide for wastewater treatment by WWTPs is the activated sludge process, as far as secondary treatment is concerned [9]. Nonetheless, WWTPs usually consist of a pretreatment, which is designed to remove grease and large solids, a primary sedimentation tank, a secondary treatment, which is a biological process of aerobic degradation (e.g., activated sludge) with a secondary settling tank, and a typical chlorination process, which is used to disinfect the effluent from the biological or secondary process [9]. However, the most used biological water treatment processes worldwide cannot remove emerging pollutants altogether [10,11], which leads to their release and constant input into the environment through treated wastewater effluents [4,6,12]. Moreover, Deblonde et al. [13], Gogoi et al. [14], and Tran et al. [15] have shown over the years that emerging pollutants are still present in the effluents of WWTPs using conventional biological processes.
Given such prospects, in recent years, there has been an increasing need to apply and add advanced tertiary treatments to conventional wastewater treatment plants (WWTP) for the emerging pollutants removal, since wastewater must be reintroduced into the environment in the most efficient way possible [6,16]. Researchers have reported that advanced oxidation processes (AOPs) are often a good option for use as tertiary or coupled processes in a conventional WWTP process for emerging pollutants removal because they generate hydroxyl radicals (HO) [17] that, in sufficient quantities, can oxidize or mineralize emerging pollutants to CO2, H2O, salts, and mineral acids [7,18]. It is essential to mention that the hydroxyl radicals generated by AOPs have high oxidative power, amounting to 2.8 eV [19,20].
Among the advanced oxidation processes, the advanced Fenton oxidation process stands out because it has been reported as an efficient method for removing organic matter [21], such as emerging pollutants, at low costs compared to other AOPs [9,22]. In addition, several studies have shown that the advanced Fenton oxidation process increases the biodegradability of the treated wastewater and the emerging pollutants oxidized by this process [7,23,24,25].
On the other hand, the advanced Fenton oxidation process has simple reaction mechanisms, in general, for generating hydroxyl radicals [26], as shown below (Equations (1)–(3)).
Fe2+ + H2O2→Fe3+ + HO + OH
Fe3+ + H2O2→Fe2+ + HO2 + H+
Organic matter (emerging pollutant) + HO→degradation or oxidation products
Furthermore, Equation (1) shows hydrogen peroxide participation as an oxidant and ferrous ion as a catalyst [27], generating hydroxyl radical (HO) as the main product [28], which then interacts with organic matter and emerging pollutants (Equation (3)) to degrade or oxidize such emerging pollutants (organic matter of interest). Consequently, the main objective of this study was to evaluate the capability of the advanced Fenton oxidation process, at the laboratory scale, when this process is applied as a tertiary treatment or polishing process to treated wastewater from a traditional WWTP to simultaneously oxidize different emerging and conventional pollutants to reach the maximum permissible limits within the Mexican regulations (NOM-001-SEMARNAT-2021 [29]).
For this study, the emerging pollutants selected for simultaneous oxidation by the advanced Fenton oxidation process in the sampled real wastewater were DEET, caffeine, carbamazepine, acesulfame-K, ibuprofen, and triclosan.
DEET is an active compound used in many insect repellents [30,31]. It was selected because it has been established that humans exposed to this chemical can develop neurological problems, such as encephalopathy [30] and skin reactions [31]. Caffeine was selected for this study because a simulation of a conventional WWTP chlorination process showed that caffeine interacts with the added chlorine and tends to form a compound called 8-chlorocaffeine, which can cause mutagenic effects, according to the Ames test [32]. Carbamazepine was selected because studies have reported that it can cause environmental damage, especially to organisms living in freshwater, and it has been consistently found in effluents from municipal WWTPs [33]. Acesulfame-K (a sweetener commonly used in beverages and food for human consumption) was selected because this compound contains a methyl group considered a toxic xenobiotic [11]. Ibuprofen was chosen because it is the third most prescribed drug worldwide and causes carcinogenic and endocrine-disrupting effects in microorganisms, algae, fish species, and humans [34]. Triclosan was also selected in this study, as it tends to cause problems such as dermatitis [35], endocrine disruption, and microbial resistance [5].
It should be noted that these emerging pollutants were also selected because they are representative of important groups of emerging pollutants such as pharmaceuticals (carbamazepine and ibuprofen), personal care and hygiene products (DEET and triclosan), and lifestyle compounds (caffeine and acesulfame-K). Additionally, to conclude this subsection, it should be emphasized that the selected emerging pollutants were determined in the real wastewater to be treated by the advanced Fenton oxidation process and were not added in spike form.

2. Results and Discussion

2.1. Physicochemical Characterization of the Influent (Real Wastewater) and Effluent Generated by the Advanced Fenton Oxidation Process

Table 1 shows the physicochemical characterization values of the influent subjected to the advanced Fenton oxidation process and the effluent generated by this process. The effluent generated by the advanced Fenton oxidation process decreased COD, TSS, and FC concentrations for the influent (real wastewater sampled from the secondary sedimentation tank of the WWTP).
The influent went from average concentrations of COD = 54 mg/L, TSS = 45 mg/L, and FC = 111,200 MNP/100 mL to average concentrations of 26.5 mg/L, 17.5 mg/L, and < 1 MNP/100 mL, respectively.
The 50.93% COD average removal (Table 1) indirectly indicates that there was also oxidation of the emerging pollutants of interest. López-Velázquez et al. [36] showed that, despite having an average COD removal of 37.33%, they could completely oxidize the emerging pollutants of interest for their research. Then, the reduction in COD also indicates the feasibility of the advanced Fenton oxidation process in removing this macro-pollutant from different types of wastewater, as several researchers have demonstrated in their studies over time [37,38,39,40,41].
In addition, the FC concentration reduction ( > 99.9%) in the effluent generated by the advanced Fenton oxidation process (Table 1) shows that the applied approach could act as a disinfection method, as indicated by Polo-López et al. [42].
Regarding the average removal of TSS (72%) (Table 1) generated by the advanced Fenton oxidation process, this is directly attributed to the precipitation of ferric ions since a large part of the suspended solids could adhere to such precipitates.
However, the average total iron concentration that remained in the effluent was 4.41 mg/L (Table 1). In terms of the total phosphate concentration, total nitrogen concentration, settleable solids concentration, and floating matter, there was no considerable change in these parameters after the advanced Fenton oxidation process.
Furthermore, according to the current regulations in Mexico (NOM-001-SEMARNAT-2021 [29]), the effluent provided by the advanced Fenton oxidation process at the laboratory level fulfills the quality required for wastewater discharges into receiving water bodies.
Additionally, as is displayed in Table 1, Equations (1), (5), and (6) were shown to be good choices for the hydrogen peroxide (H2O2, oxidant) and ferrous sulphate heptahydrate (FeSO4•7H2O, catalyst supplier) dosage, in terms of COD, total suspended solids (TSS), and fecal coliforms (FC) reduction in the real wastewater treated by the advanced Fenton oxidation process.

2.2. Simultaneous Oxidation of the Emerging Pollutants by the Advanced Fenton Oxidation Process

Figure 1 shows the concentrations of the emerging pollutants of interest in the real untreated wastewater and the water treated by the advanced Fenton oxidation process.
For the influent (real wastewater from the WWTP secondary settling tank), the initial concentrations determined for the emerging pollutants (Figure 1) of concern were as follows: triclosan (0.40 ± 0.56 ppb), ibuprofen (0.98 ± 1.39), DEET (2.32 ± 0.28 ppb), carbamazepine (0.33 ± 0.47 ppb), caffeine (1.96 ± 0.39 ppb), and acesulfame-K (23.03 ± 5.96 ppb) (Figure 1).
It should be noted that concentrations detected in the real wastewater from the second settling tank of the WWTP, subjected to the advanced Fenton oxidation process, are evidence that the conventional methods used in WWTPs cannot usually degrade all emerging pollutants [10,11,43].
However, it can be observed how the real wastewater treated by the advanced Fenton oxidation process brought most of the emerging pollutants of concern (Figure 1) to unquantifiable levels ( < LOQ) in 1 h. This indicates that the advanced Fenton oxidation process did oxidize the emerging pollutants of concern despite having an average COD removal of 50.93%, which is like those previously reported by Lopez-Velazquez et al. [36], who, despite having a COD removal of 37.33%, managed to oxidize the emerging pollutants of interest in their research. Consequently, based on the results obtained (Figure 1), it is feasible to use Equations (1), (5) and (6) in the advanced Fenton oxidation process to dose hydrogen peroxide (H2O2, oxidant) and ferrous sulfate heptahydrate (FeSO4•7H2O, catalyst supplier), using wastewater COD as the basis of calculation.
Additionally, it should be noted that the advanced Fenton oxidation process did not wholly oxidize DEET since 0.34 ± 0.69 ppb remained in the real treated wastewater (Figure 1).
On the other hand, the average oxidation percentage of most emerging pollutants of interest was almost 100%. For example, in the case of DEET, the average oxidation percentage was as high as 85.21% ± 20.92%. Therefore, the advanced Fenton oxidation process is an excellent option for simultaneously oxidizing and removing emerging pollutants of interest in real wastewater.
The simultaneous oxidation of emerging pollutants generated by the advanced Fenton oxidation process is attributed to the hydroxyl radicals (HO) generated because these radicals are non-selective [6] and attack any contaminant indiscriminately.
Concerning research that has employed the advanced Fenton oxidation process and its variants, specifically for triclosan removal or oxidation, it has been observed that the studies carried out over time have had good removal percentages that vary from 90% to 99.5% [44,45,46]. However, unlike the present study, the studies mentioned above used synthetic triclosan solutions and not real wastewater as an influent of the advanced Fenton oxidation process.
Various research works using the advanced Fenton oxidation process to eliminate ibuprofen had removal percentages ranging between 60 and 84.68% [47,48], which are lower than those obtained in the present study. However, this could be attributed to the fact that different hydraulic retention times have been used in the research, and dosage calculations of the oxidant and the catalyst added to the wastewater have been different compared to those used in the present study.
Regarding carbamazepine and acesulfame-K, the present study shows higher oxidation yields in comparison to other works on acesulfame-K (50%) [49] and carbamazepine (53.73%) [50]. Nevertheless, for caffeine, the removal percentages are quite similar to those found in other works [36,51].
It should be highlighted that no research was found in the case of DEET. However, these results show that it can be removed by the advanced Fenton oxidation process (oxidation yield = 85.21%).
Moreover, all the investigations referenced in this subsection regarding removing the emerging pollutants of interest used different experimental conditions. They treated different water matrices than those used in this study. Therefore, the results obtained at the laboratory level show that the advanced Fenton oxidation process is a good option for the tertiary treatment of real wastewater with different emerging pollutants.

3. Materials and Methods

3.1. Real Wastewater Sampling

Real wastewater samples came from a WWTP in Durango, Mexico (23°58′30″ N, 104°38′10″ W). Before disinfection, the sampling was conducted after the second settling tank (Figure 2). The WWTP has a conventional activated sludge process as a secondary treatment.
The samples were taken after the second settling tank because the AOPs are intended to be used as tertiary or polishing treatments to oxidize emerging pollutants. Then, the real wastewater sampled had already been subjected to the primary and secondary treatment (conventional biological activated sludge process).
Real wastewater sampling and preservation followed the standard Mexican NMX-AA-003-1980 [52].

3.2. Characterization of the Real Wastewater (Influent) and Effluent Generated by the Advanced Fenton Oxidation Process

The physicochemical characterization of the real wastewater sampled and treated by the advanced Fenton oxidation process was carried out based on the standards specified in Table 2. Due to the nature of the advanced Fenton oxidation process, the total iron was determined for the effluent generated.

3.3. Quantification of the Emerging Pollutants of Concern

The method and instrument used to quantify the emerging pollutants of interest were solid phase extraction and a liquid chromatography–mass spectrometer (Figure 2).

3.3.1. Solid Phase Extraction (SPE)

Waters Oasis HLB cartridges of 1 cubic centimeter were used for the solid phase extraction. The cartridges were initially activated with 1 mL of methanol and 0.3 mL of deionized water (the vacuum pump throughout the extraction process should have a vacuum of approximately 10 psi). All the reagents used were of chromatographic grade.
Then, 25 mL of real wastewater from the second settling tank of the WWTP untreated and treated by the advanced Fenton oxidation process was passed through the cartridges. Given the pore size of the HLB cartridge, all the samples subjected to the extraction process were previously filtered with a Whatman grade 1 filter; then, disodium EDTA was added at a concentration of 500 mg/L, and the pH was adjusted to 2 with concentrated (98.08% m/m) sulfuric acid (H2SO4) before passing it through the extraction cartridge.
Subsequently, 0.5 mL of deionized water at pH 2 was passed through, and the cartridges were allowed to dry for 10 min with the vacuum pump on. As a final part of the extraction process, the compound of interest was eluted by passing 6 mL of methanol and 3 mL of acetone. Next, the extract was dried using nitrogen gas gently. Afterward, the dried extract was dissolved in 1 mL of formic acid (0.1% v/v) diluted in methanol.

3.3.2. Quantification of Emerging Contaminants of Interest

The liquid chromatograph used to quantify the emerging pollutants of interest was an Acquity UPLC®, class I. The chromatographic system was coupled to a triple quadrupole mass spectrometer (XEVO-TQ-S micro (Waters)). The mobile phase composition is given in Table 3.
The concentration of each emerging pollutant of interest was calculated based on Equation (4). The volume of the concentrate considered in Equation (4) refers to the volume of the sample used in the solid phase extraction, which is 25 mL
R e a l   c o n c e n t r a t i o n = [ C o n c e n t r a t e   r e a d   b y   t h e   c h r o m a t o g r a p h ] S P E   c o n c e n t r a t e   v o l u m e

3.4. Experimental Setup (Advanced Fenton Oxidation Process)

The experimental setup is shown in Figure 2. The experiments were operated in batch mode. It should be noted that the experiments were carried out in duplicate, and the volume of real wastewater taken for each experiment was 0.5 L.
The pH was adjusted by adding concentrated sulfuric acid (H2SO4) at 98.08% m/m purity. On the other hand, the aqueous solution pH for the whole experiment was measured with a Thermo Electron Corporation ORION 3 STAR potentiometer. As a result, the initial pH in each trial was adjusted to 3, the pH value identified as the optimum level for carrying out the advanced Fenton oxidation process [61,62,63].
Now, ferrous sulfate heptahydrate (FeSO4•7H2O, catalyst supplier (Fe2+)) of analytical grade ( > 99%) was the reagent used to obtain the ferrous ions (Fe2+) since it is a reagent widely used in different investigations [64,65] where the homogeneous advanced Fenton oxidation process is applied. The hydrogen peroxide (H2O2, oxidant) concentration was 30% v/v.
The hydrogen peroxide (H2O2) and ferrous sulfate heptahydrate (FeSO4•7H2O) to be added to the real wastewater were calculated using Equation (1) [25,66,67], Equation (5) [6,68,69], and Equation (6), considering a V = 0.5 L as the sample base.
Equation (5) was used to determine the amount of hydrogen peroxide (H2O2) as a wastewater COD function. On the other hand, Equations (1) and (6) served as a reference to determine the ferrous ion (Fe2+) amount to be added using ferrous sulfate heptahydrate (FeSO4•7H2O) in relation to that calculated by Equation (5).
Since the advanced Fenton oxidation process is non-selective, wastewater COD is used as a basis of calculation to define the amounts of hydrogen peroxide (H2O2), ferrous ion (Fe2+), and ferrous sulfate heptahydrate (FeSO4•7H2O). On the contrary, if the amount of reagents is calculated based on the emerging pollutants of interest, they would be underestimated [6].
Equation (1) denotes the molar ratio necessary to initiate the Fenton reaction based on Equation (5).
In Equation (5), COD is the chemical oxygen demand concentration of the real wastewater to be treated in milligrams per liter. V is the volume of real wastewater to be treated in liters.
Quantity   ( mg )   H 2 O 2   = 17 8 C O D , m g L ( V L )
In Equation (6), nmol Fe2+ are the moles of the ferrous ion calculated by Equation (1) in relation to Equation (5), and 278,010 is the molecular weight, in milligrams, of ferrous sulfate heptahydrate (FeSO4•7H2O).
Quantity (mg) FeSO4•7H2O = (278,010) (nmol Fe2+)
As shown Figure 2, in step 5, the beaker is orange because when the Fenton reaction is initiated, in addition to hydroxyl radicals (HO), ferric ions (Fe3+) are also produced, which turn the color of the water orange.
The experiments were carried out through the jar test. The equipment used was Phipps & Bird (model PB-700), and all experiments were shaken at 110 rpm in the jar test (Figure 2). The hydraulic retention time used in the jar test was 1 h.
To raise the pH of the solution to 7, sodium hydroxide (NaOH) was added at 2 mol·L−1. This was carried out to remove the ferric ions (Fe3+) generated in the advanced Fenton oxidation process from the effluent in the form of ferric hydroxides [67]. In the final part, the precipitation time was 5 min, and the effluent was obtained using a peristaltic pump (Figure 2).

3.5. Oxidation Percentage

The oxidation yield of each emerging pollutant was calculated using Equation (7).
O x i d a t i o n % = C i C f C i * 100
C i is the initial wastewater concentration of each emerging pollutant, and C f is the final concentration of the emerging pollutant that resulted after subjecting the wastewater to the advanced Fenton oxidation process.
Note that the final concentrations of the emerging pollutants after the advanced Fenton oxidation process that were below the limit of quantification ( < LOQ) were considered as C f = 0 in Equation (7) for the percent oxidation calculations. Equation (7) was also used to calculate the removal yields of some physicochemical parameters obtained in the advanced Fenton oxidation process.

4. Conclusions

The increase and persistence of emerging pollutants in natural water bodies could be attributed to the treated wastewater discharge, where the conventional process was insufficient to remove these compounds before being returned to the environment. The results presented in this research show that the advanced Fenton oxidation process is a treatment alternative that can be coupled or integrated into the conventional treatment train, efficiently removing emerging pollutants, COD, TSS, and FC.
According to the results obtained at the laboratory level, the advanced Fenton oxidation process could oxidize different emerging pollutants simultaneously since the oxidation yields of the emerging pollutants present in samples of real wastewater were close to 100%, except for DEET, which had an average oxidation yield of 85.21%.
It should be highlighted that the advanced Fenton oxidation process could be used as a tertiary or polishing process coupled with a conventional WWTP since, as well as eliminating the emerging pollutants of interest, it also upgraded the quality of the treated water in terms of COD, TSS, and FC (pathogens).
Finally, based on the physicochemical characteristics established by the Mexican standard NOM-001-SEMARNAT-2021 [29], the advanced Fenton oxidation process provides an effluent with enough quality to be discharged into receiving water bodies owned by the nation or for use in garden irrigation systems, among other indirect benefits.

Author Contributions

Conceptualization, A.R.B.-R., Y.R.-V. and L.R.-C.; methodology, A.R.B.-R., J.R.I.-C. and L.R.-C.; software, A.R.B.-R. and L.R.-C.; validation, A.R.B.-R., J.R.I.-C. and L.R.-C.; formal analysis, A.R.B.-R., Y.R.-V., J.R.I.-C. and L.R.-C.; investigation, A.R.B.-R. and L.R.-C.; resources, L.R.-C.; data curation, A.R.B.-R., Y.R.-V., J.R.I.-C. and L.R.-C.; writing—original draft preparation, A.R.B.-R., Y.R.-V., J.R.I.-C. and L.R.-C.; writing—review and editing, A.R.B.-R., Y.R.-V., J.R.I.-C. and L.R.-C.; visualization, A.R.B.-R. and L.R.-C.; supervision, L.R.-C.; project administration, L.R.-C.; funding acquisition, L.R.-C. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Council of Science and Technology (CONACYT), with scholarship grant number 805457 and project number CF-2019/102967.

Data Availability Statement

Data are available only upon request to the authors.

Acknowledgments

M.S.A. acknowledges Luis A. Torres-Castañón from CIMAV-DGO for his valuable technical support and collaboration.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Vasilachi, I.C.; Asiminicesei, D.M.; Fertu, D.I.; Gavrilescu, M. Occurrence and Fate of Emerging Pollutants in Water Environment and Options for Their Removal. Water 2021, 13, 181. [Google Scholar] [CrossRef]
  2. Rodriguez-Narvaez, O.M.; Peralta-Hernandez, J.M.; Goonetilleke, A.; Bandala, E.R. Treatment technologies for emerging contaminants in water: A review. Chem. Eng. J. 2017, 323, 361–380. [Google Scholar] [CrossRef] [Green Version]
  3. Jari, Y.; Roche, N.; Necibi, M.C.; El Hajjaji, S.; Dhiba, D.; Chehbouni, A.G. Emerging Pollutants in Moroccan Wastewater: Occurrence, Impact, and Removal Technologies. J. Chem. 2022, 2022, 9727857. [Google Scholar] [CrossRef]
  4. Lama, G.; Meijide, J.; Sanromán, A.; Pazos, M. Heterogeneous Advanced Oxidation Processes: Current Approaches for Wastewater Treatment. Catalysts 2022, 12, 344. [Google Scholar] [CrossRef]
  5. Arman, N.Z.; Salmiati, S.; Aris, A.; Salim, M.R.; Nazifa, T.H.; Muhamad, M.S.; Marpongahtun, M. A Review on Emerging Pollutants in the Water Environment: Existences, Health Effects and Treatment Processes. Water 2021, 13, 3258. [Google Scholar] [CrossRef]
  6. Bracamontes-Ruelas, A.R.; Ordaz-Díaz, L.A.; Bailón-Salas, A.M.; Ríos-Saucedo, J.C.; Reyes-Vidal, Y.; Reynoso-Cuevas, L. Emerging Pollutants in Wastewater, Advanced Oxidation Processes as an Alternative Treatment and Perspectives. Processes 2022, 10, 1041. [Google Scholar] [CrossRef]
  7. Lima, J.P.P.; Tabelini, C.H.B.; Aguiar, A. A Review of Gallic Acid-Mediated Fenton Processes for Degrading Emerging Pollutants and Dyes. Molecules 2023, 28, 1166. [Google Scholar] [CrossRef]
  8. Roznere, I.; An, V.; Robinson, T.; Banda, J.A.; Watters, G.T. Contaminants of emerging concern in the Maumee River and their effects on freshwater mussel physiology. PLoS ONE 2023, 18, e0280382. [Google Scholar] [CrossRef] [PubMed]
  9. Zagklis, D.P.; Bampos, G. Tertiary Wastewater Treatment Technologies: A Review of Technical, Economic, and Life Cycle Aspects. Processes 2022, 10, 2304. [Google Scholar] [CrossRef]
  10. Tufail, A.; Price, W.E.; Mohseni, M.; Pramanik, B.K.; Hai, F.I. A critical review of advanced oxidation processes for emerging trace organic contaminant degradation: Mechanisms, factors, degradation products, and effluent toxicity. J. Water Process. Eng. 2021, 40, 101778. [Google Scholar] [CrossRef]
  11. Parida, V.K.; Saidulu, D.; Majumder, A.; Srivastava, A.; Gupta, B.; Gupta, A.K. Emerging contaminants in wastewater: A critical review on occurrence, existing legislations, risk assessment, and sustainable treatment alternatives. J. Environ. Chem. Eng. 2021, 9, 105966. [Google Scholar] [CrossRef]
  12. Necibi, M.C.; Dhiba, D.; El Hajjaji, S. Contaminants of Emerging Concern in African Wastewater Effluents: Occurrence, Impact and Removal Technologies. Sustainability 2021, 13, 1125. [Google Scholar] [CrossRef]
  13. Deblonde, T.; Cossu-Leguille, C.; Hartemann, P. Emerging pollutants in wastewater: A review of literature. Int. J. Hyg. Environ. Health 2011, 214, 442–448. [Google Scholar] [CrossRef] [PubMed]
  14. Gogoi, A.; Mazumder, P.; Tyagi, V.K.; Tushara Chaminda, G.G.; An, A.K.; Kumar, M. Occurrence and fate of emerging contaminants in water environment: A review. Groundw. Sustain. Dev. 2018, 6, 169–180. [Google Scholar] [CrossRef]
  15. Tran, N.H.; Reinhard, M.; Gin, K.Y.H. Occurrence and fate of emerging contaminants in municipal wastewater treatment plants from different geographical regions-a review. Water Res. 2018, 133, 182–207. [Google Scholar] [CrossRef]
  16. Bermúdez, L.A.; Pascual, J.M.; Martínez, M.d.M.M.; Poyatos Capilla, J.M. Effectiveness of Advanced Oxidation Processes in Wastewater Treatment: State of the Art. Water 2021, 13, 2094. [Google Scholar] [CrossRef]
  17. Yang, L.; Jiao, Y.; Xu, X.; Pan, Y.; Su, C.; Duan, X.; Sun, H.; Liu, S.; Wang, S.; Shao, Z. Superstructures with Atomic-Level Arranged Perovskite and Oxide Layers for Advanced Oxidation with an Enhanced Non-Free Radical Pathway. ACS Sustain. Chem. Eng. 2022, 10, 1899–1909. [Google Scholar] [CrossRef]
  18. Fast, S.A.; Gude, V.G.; Truax, D.D.; Martin, J.; Magbanua, B.S. A Critical Evaluation of Advanced Oxidation Processes for Emerging Contaminants Removal. Environ. Process. 2017, 4, 283–302. [Google Scholar] [CrossRef]
  19. Ma, D.; Yi, H.; Lai, C.; Liu, X.; Huo, X.; An, Z.; Li, L.; Fu, Y.; Li, B.; Zhang, M.; et al. Critical review of advanced oxidation processes in organic wastewater treatment. Chemosphere 2021, 275, 130104. [Google Scholar] [CrossRef]
  20. Solanki, V.S.; Pare, B.; Gupta, P.; Jonnalagadda, S.B.; Shrivastava, R. A Review on Advanced Oxidation Processes (AOPs) for Wastewater Remediation. Asian J. Chem. 2020, 32, 2677–2684. [Google Scholar] [CrossRef]
  21. Lima, L.B.; Pereira, L.O.; Moura, S.G.; Magalhães, F. Degradation of organic contaminants in effluents—Synthetic and from the textile industry—By Fenton, photocatalysis, and H2O2 photolysis. Environ. Sci. Pollut. Res. 2017, 24, 6299–6306. [Google Scholar] [CrossRef] [PubMed]
  22. Mousset, E.; Loh, W.H.; Lim, W.S.; Jarry, L.; Wang, Z.; Lefebvre, O. Cost comparison of advanced oxidation processes for wastewater treatment using accumulated oxygen-equivalent criteria. Water Res. 2021, 200, 117234. [Google Scholar] [CrossRef] [PubMed]
  23. Tekin, H.; Bilkay, O.; Ataberk, S.S.; Balta, T.H.; Ceribasi, I.H.; Sanin, F.D.; Dilek, F.B.; Yetis, U. Use of Fenton oxidation to improve the biodegradability of a pharmaceutical wastewater. J. Hazard. Mater. 2006, 136, 258–265. [Google Scholar] [CrossRef]
  24. Ishak, S.; Malakahmad, A. Optimization of Fenton process for refinery wastewater biodegradability augmentation. Korean J. Chem. Eng. 2013, 30, 1083–1090. [Google Scholar] [CrossRef]
  25. Ding, R.; Wang, Y.; Chen, X.; Gao, Y.; Yang, M. Extended Fenton’s process: Toward improving biodegradability of drilling wastewater. Water Sci. Technol. 2019, 79, 1790–1797. [Google Scholar] [CrossRef]
  26. Thomas, N.; Dionysiou, D.D.; Pillai, S.C. Heterogeneous Fenton catalysts: A review of recent advances. J. Hazard. Mater. 2021, 404, 124082. [Google Scholar] [CrossRef]
  27. Litter, M.I.; Slodowicz, M. An overview on heterogeneous Fenton and photoFenton reactions using zerovalent iron materials. J. Adv. Oxid. Technol. 2017, 20, 20160164. [Google Scholar] [CrossRef]
  28. Priyadarshini, M.; Das, I.; Ghangrekar, M.M.; Blaney, L. Advanced oxidation processes: Performance, advantages, and scale-up of emerging technologies. J. Environ. Manag. 2022, 316, 115295. [Google Scholar] [CrossRef]
  29. NOM-001-SEMARNAT-2021 (Which Establishes the Permissible Limits of Pollutants in Wastewater Discharges into Receiving Bodies Owned by the Nation). Available online: https://www.dof.gob.mx/nota_detalle.php?codigo=5645374&fecha=11/03/2022#gsc.tab=0 (accessed on 8 February 2023).
  30. Sudakin, D.L.; Trevathan, W.R. DEET: A review and update of safety and risk in the general population. J. Toxicol. Clin. Toxicol. 2003, 41, 831–839. [Google Scholar] [CrossRef]
  31. Swale, D.R.; Bloomquist, J.R. Is DEET a dangerous neurotoxicant? Pest Manag. Sci. 2019, 75, 2068–2070. [Google Scholar] [CrossRef]
  32. Zarrelli, A.; DellaGreca, M.; Iesce, M.R.; Lavorgna, M.; Temussi, F.; Schiavone, L.; Crisculo, E.; Parrella, A.; Previtera, L.; Isidori, M. Ecotoxicological evaluation of caffeine and its derivatives from a simulated chlorination step. Sci. Total Environ. 2014, 470, 453–458. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  33. Bahlmann, A.; Brack, W.; Schneider, R.J.; Krauss, M. Carbamazepine and its metabolites in wastewater: Analytical pitfalls and occurrence in Germany and Portugal. Water Res. 2014, 57, 104–114. [Google Scholar] [CrossRef] [PubMed]
  34. Sol, D.; Menéndez-Manjón, A.; Arias-García, P.; Laca, A.; Laca, A.; Rancaño, A.; Díaz, M. Occurrence of Selected Emerging Contaminants in Southern Europe WWTPs: Comparison of Simulations and Real Data. Processes 2022, 10, 2491. [Google Scholar] [CrossRef]
  35. Dhillon, G.S.; Kaur, S.; Pulicharla, R.; Brar, S.K.; Cledón, M.; Verma, M.; Surampalli, R.Y. Triclosan: Current Status, Occurrence, Environmental Risks and Bioaccumulation Potential. Int. J. Environ. Res. Public Health 2015, 12, 5657–5684. [Google Scholar] [CrossRef] [PubMed]
  36. López-Velázquez, K.; Villanueva-Rodríguez, M.; Mejía-González, G.; Herrera-López, D. Removal of 17α-ethinylestradiol and caffeine from wastewater by UASB-Fenton coupled system. Environ. Technol. 2021, 42, 3771–3782. [Google Scholar] [CrossRef]
  37. Lee, H.; Shoda, M. Removal of COD and color from livestock wastewater by the Fenton method. J. Hazard. Mater. 2008, 153, 1314–1319. [Google Scholar] [CrossRef]
  38. Lucas, M.S.; Peres, J.A. Removal of COD from olive mill wastewater by Fenton’s reagent: Kinetic study. J. Hazard. Mater. 2009, 168, 1253–1259. [Google Scholar] [CrossRef]
  39. Chen, Y.; Liu, C.; Nie, J.; Wu, S.; Wang, D. Removal of COD and decolorizing from landfill leachate by Fenton’s reagent advanced oxidation. Clean Technol. Environ. Policy 2014, 16, 189–193. [Google Scholar] [CrossRef]
  40. Abedinzadeh, N.; Shariat, M.; Monavari, S.M.; Pendashteh, A. Evaluation of color and COD removal by Fenton from biologically (SBR) pre-treated pulp and paper wastewater. Process Saf. Environ. Prot. 2018, 116, 82–91. [Google Scholar] [CrossRef]
  41. Hakika, D.C.; Sarto, S.; Mindaryani, A.; Hidayat, M. Decreasing COD in Sugarcane Vinasse Using the Fenton Reaction: The Effect of Processing Parameters. Catalysts 2019, 9, 881. [Google Scholar] [CrossRef] [Green Version]
  42. Polo-López, M.I.; Nahim-Granados, S.; Fernández-Ibáñez, P. Homogeneous Fenton and Photo-Fenton Disinfection of Surface and Groundwater. In Applications of Advanced Oxidation Processes (AOPs) in Drinking Water Treatment, 1st ed.; Gil, A., Galeano, L., Vicente, M., Eds.; Springer: Cham, Germany, 2018; Volume 67, pp. 155–177. [Google Scholar] [CrossRef]
  43. Martínez-Orgániz, A.; Becerril Bravo, J.E.; Llompart, M.; Dagnac, T.; Lamas, J.P.; Vázquez, L.; Sampedro-Rosas, L. Emerging pollutants and antibiotics removed by conventional activated sludge followed by ultraviolet radiation in a municipal wastewater treatment plant in Mexico. Water Qual. Res. J. Canada 2021, 56, 167–179. [Google Scholar] [CrossRef]
  44. Munoz, M.; de Pedro, Z.M.; Casas, J.A.; Rodriguez, J.J. Triclosan breakdown by Fenton-like oxidation. Chem. Eng. J. 2012, 198–199, 275–281. [Google Scholar] [CrossRef] [Green Version]
  45. Cokay, E.; Oztamer, M. Degradation of triclosan by photo-fenton oxidation. J. Sci. Eng. 2017, 19, 583–598. [Google Scholar] [CrossRef]
  46. Peng, J.; Zhang, Y.; Zhang, C.; Miao, D.; Li, J.; Liu, H.; Wang, L.; Gao, S. Removal of triclosan in a Fenton-like system mediated by graphene oxide: Reaction kinetics and ecotoxicity evaluation. Sci. Total Environ. 2019, 673, 726–733. [Google Scholar] [CrossRef]
  47. Klamerth, N.; Rizzo, L.; Malato, S.; Maldonado, M.I.; Aguera, A.; Fernández-Alba, A.R. Degradation of fifteen emerging contaminants at mg.L−1 initial concentrations by mild solar photo-Fenton in MWTP effluents. Water Res. 2010, 44, 545–554. [Google Scholar] [CrossRef]
  48. Lekikot, B.; Mammeri, L.; Talbi, K.; Benssassi, M.E.; Abdessemed, A.; Sehili, R. Homogeneous modified Fenton-like oxidation using FeIII-gallic acid complex for ibuprofen degradation at neutral pH. Desalination Water Treat. 2021, 234, 147–157. [Google Scholar] [CrossRef]
  49. Law, J.C.-F.; Leung, K.S.-Y. Redox mediators and irradiation improve fenton degradation of acesulfame. Chemosphere 2019, 217, 374–382. [Google Scholar] [CrossRef]
  50. Üstün Odabaşı, S.; Maryam, B.; Büyükgüngör, H. Fenton oxidation of carbamazepine in wastewater with fewer reagents. Sigma J. Eng. Nat. Sci. 2018, 36, 289–298. [Google Scholar]
  51. Oliveira, T.D.; Martini, W.S.; Santos, M.D.R.; Matos, M.A.C.; Rocha, L.L. Caffeine Oxidation in Water by Fenton and Fenton-Like Processes: Effects of Inorganic Anions and Ecotoxicological Evaluation on Aquatic Organisms. J. Braz. Chem. Soc. 2015, 26, 178–184. [Google Scholar] [CrossRef]
  52. NMX-AA-003-1980 (Mexican Standard for Wastewater Sampling). Available online: https://agua.org.mx/biblioteca/nmx-aa-003-1980-aguas-residuales-muestreo/ (accessed on 4 February 2023).
  53. NMX-AA-008-SCFI-2011 (Water Analysis—pH Determination). Available online: http://www.economia-nmx.gob.mx/normas/nmx/2010/nmx-aa-008-scfi11.pdf (accessed on 4 February 2023).
  54. NMX-AA-007-SCFI-2013 (Water Analysis-Temperature Measurement in Natural, Waste and Treated Wastewater). Available online: http://legismex.mty.itesm.mx/normas/aa/aa007-2014_01. (accessed on 4 February 2023).
  55. NMX-AA-006-SCFI-2010 (Water Analysis-Determination of Floating Matter in Wastewater and Sewage Water). Available online: https://www.gob.mx/cms/uploads/attachment/file/166765/NMX-AA-006-SCFI-2010.pdf (accessed on 4 February 2023).
  56. NMX-AA-004-SCFI-2013 (Water Analysis-Measurement of Settleable Solids in Natural, Waste and Wastewater). Available online: https://www.gob.mx/cms/uploads/attachment/file/166763/NMX-AA-004-SCFI-2013.pdf (accessed on 4 February 2023).
  57. HACH (HACH Methods Manual). Available online: https://www.hach.com/resources/water-analysis-handbook (accessed on 4 February 2023).
  58. NMX-AA-034-SCFI-2015 (Water Analysis-Measurement of Dissolved Solids and Salts in Natural, Waste and Treated Wastewater). Available online: https://www.gob.mx/cms/uploads/attachment/file/166146/nmx-aa-034-scfi-2015.pdf (accessed on 4 February 2023).
  59. NMX-AA-042-SCFI-2015 (Water Analysis-Enumeration of Total Coliform Organisms, Fecal Coliform Organisms (Thermotolerant) and Escherichia Coli-Most Probable Number Method in Multiple Tubes). Available online: https://www.gob.mx/cms/uploads/attachment/file/166147/nmx-aa-042-scfi-2015.pdf (accessed on 4 February 2023).
  60. NMX-AA-051-SCFI-2016 (Water Analysis—Measurement of Metals by Atomic Absorption in Natural Waters Atomic Absorption in Natural Waters, Drinking Water, Wastewater and Treated Wastewater). Available online: http://www.economia-nmx.gob.mx/normas/nmx/2010/nmx-aa-051-scfi-2016.pdf (accessed on 4 February 2023).
  61. Babuponnusami, A.; Muthukumar, K. A review on Fenton and improvements to the Fenton process for wastewater treatment. J. Environ. Chem. Eng. 2014, 2, 557–572. [Google Scholar] [CrossRef]
  62. Wang, S.; Wang, J. Comparative study on sulfamethoxazole degradation by Fenton and Fe(II)-activated persulfate process. RSC Adv. 2017, 7, 48670–48677. [Google Scholar] [CrossRef] [Green Version]
  63. Modi, H.J. Fenton Treatment: A Review on Treatment of Waste Water. Int. Res. J. Eng. Technol. 2018, 7, 41–44. [Google Scholar] [CrossRef]
  64. Karale, R.S.; Manu, B.; Shrihari, S. Fenton and Photo-Fenton Oxidation Processes for Degradation of 3-Aminopyridine from Water. APCBEE Procedia 2014, 9, 25–29. [Google Scholar] [CrossRef] [Green Version]
  65. Valderrama, M.; Javier, C.; del Águila, M.; Miche, E.; Pio, C.; Erika, L. Fenton process optimization in the treatment of landfill leachates lixiviated. Rev. Soc. Quim. Perú. 2016, 82, 454–466. [Google Scholar]
  66. Pignatello, J.J.; Oliveros, E.; MacKay, A. Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry. Crit. Rev. Environ. Sci. Technol. 2006, 36, 1–84. [Google Scholar] [CrossRef]
  67. Kastanek, F.; Spacilova, M.; Krystynik, P.; Dlaskova, M.; Solcova, O. Fenton Reaction–Unique but Still Mysterious. Processes 2023, 11, 432. [Google Scholar] [CrossRef]
  68. Carmona, P.B. Tratamiento de Aguas Residuales de la Industria Cosmética Mediante el Proceso Fenton y con el Sistema Fe/𝛾-Al2O3/H2O2. Ph.D. Thesis, Universidad Autónoma de Madrid, Madrid, Spain, 2008. [Google Scholar]
  69. Taco Ugsha, M.; Mayorga Llerena, E. Aplicación del proceso Fenton en la disminución de materia orgánica en aguas residuales de la industria termoeléctrica. Quím. Cent. 2013, 3, 25–30. [Google Scholar] [CrossRef]
Figure 1. Emerging pollutants’ concentration in untreated and treated real wastewater.
Figure 1. Emerging pollutants’ concentration in untreated and treated real wastewater.
Catalysts 13 00748 g001
Figure 2. Experimental setup.
Figure 2. Experimental setup.
Catalysts 13 00748 g002
Table 1. Results of the physicochemical characterization of the influent and effluent generated by the advanced Fenton oxidation process.
Table 1. Results of the physicochemical characterization of the influent and effluent generated by the advanced Fenton oxidation process.
DeterminationInfluent (Sampled Real Wastewater)Effluent Generated by the Advanced Fenton Oxidation ProcessPercentage Removal (%)
pH8.017.12 ± 0.07ND
Temperature (°C)2525.35 ± 0.35ND
Floating matterAbsenceAbsenceND
Settleable solids (mL/L)AbsenceAbsenceND
COD (mg/L)54 ± 1.4126.50 ± 7.7850.93 ± 14.40
TSS (mg/L)45 ± 21.2117.50 ± 5.0072 ± 7.54
Total phosphates (mg/L)0.71.55 ± 1.63ND
Total nitrogen (mg/L)2.52.8ND
FC (*MPN/100 mL)111,200 < 1 > 99.9%
Iron total (mg/L)*ND4.41 ± 0.38ND
*ND: Not determined; *MPN: Most probable number.
Table 2. Methods and techniques used for the physicochemical characterization of real wastewater sampled and treated by the advanced Fenton oxidation process.
Table 2. Methods and techniques used for the physicochemical characterization of real wastewater sampled and treated by the advanced Fenton oxidation process.
DeterminationMethod or TechniqueReference
pHNMX-AA-008-SCFI-2011[53]
TemperatureNMX-AA-007-SCFI-2013[54]
Floating matterNMX-AA-006-SCFI-2010[55]
Settleable solidsNMX-AA-004-SCFI-2013[56]
Chemical oxygen demand (COD)HACH®[57]
Total suspended solids (TSS)NMX-AA-034-SCFI-2015[58]
Total phosphatesHACH®[57]
Total nitrogenHACH®[57]
Fecal coliforms (FC)NMX-AA-042-SCFI-2015[59]
Total ironNMX-AA-051-SCFI-2016[60]
Table 3. Technical details of the operation of the liquid chromatograph–mass spectrometer.
Table 3. Technical details of the operation of the liquid chromatograph–mass spectrometer.
Chromatograph
ColumnACQUITY Premier CSH C18 1.7 µm, 2.1 × 150 mm
Flow (mL/min)0.4
Sample temperature (°C)7
Column temperature (°C)40
Mobile phase A compositionwater (Milli-Q) with 10 mM ammonium formate (chromatographic grade) plus 0.1% formic acid (chromatographic grade).
Mobile phase B compositionMethanol–Acetonitrile (50% v/v–50% v/v)
Injection volume ( μ L)10
Elution (min)A (%)B (%)
0298
0.5298
149010
16955
16.5298
19298
Mass spectrometer
Ionization sourceElectrospray (ESI)
PolarityES+ and ES−
Source temperature (°C)150
Capillary voltage (kV)3
Cone gas flow (L/h)50
Desolventizing temperature (°C)500
Desolvation gas flow (L/h)100
Coalition gas (argon)0.15 mL/min
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Bracamontes-Ruelas, A.R.; Reyes-Vidal, Y.; Irigoyen-Campuzano, J.R.; Reynoso-Cuevas, L. Simultaneous Oxidation of Emerging Pollutants in Real Wastewater by the Advanced Fenton Oxidation Process. Catalysts 2023, 13, 748. https://doi.org/10.3390/catal13040748

AMA Style

Bracamontes-Ruelas AR, Reyes-Vidal Y, Irigoyen-Campuzano JR, Reynoso-Cuevas L. Simultaneous Oxidation of Emerging Pollutants in Real Wastewater by the Advanced Fenton Oxidation Process. Catalysts. 2023; 13(4):748. https://doi.org/10.3390/catal13040748

Chicago/Turabian Style

Bracamontes-Ruelas, Alexis Rubén, Yolanda Reyes-Vidal, José Rafael Irigoyen-Campuzano, and Liliana Reynoso-Cuevas. 2023. "Simultaneous Oxidation of Emerging Pollutants in Real Wastewater by the Advanced Fenton Oxidation Process" Catalysts 13, no. 4: 748. https://doi.org/10.3390/catal13040748

APA Style

Bracamontes-Ruelas, A. R., Reyes-Vidal, Y., Irigoyen-Campuzano, J. R., & Reynoso-Cuevas, L. (2023). Simultaneous Oxidation of Emerging Pollutants in Real Wastewater by the Advanced Fenton Oxidation Process. Catalysts, 13(4), 748. https://doi.org/10.3390/catal13040748

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