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Article

Removal of Diclofenac in Wastewater Using Biosorption and Advanced Oxidation Techniques: Comparative Results

by
José M. Angosto
,
María J. Roca
and
José A. Fernández-López
*
Department of Chemical and Environmental Engineering, Technical University of Cartagena, Paseo Alfonso XIII, 52, 30203 Cartagena, Murcia, Spain
*
Author to whom correspondence should be addressed.
Water 2020, 12(12), 3567; https://doi.org/10.3390/w12123567
Submission received: 25 November 2020 / Revised: 16 December 2020 / Accepted: 17 December 2020 / Published: 19 December 2020
(This article belongs to the Special Issue Adsorbents for Water and Wastewater Treatment and Resource Recovery)
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Abstract

:
Wastewater treatment is a topic of primary interest with regard to the environment. Diclofenac is a common analgesic drug often detected in wastewater and surface water. In this paper, three commonly available agrifood waste types (artichoke agrowaste, olive-mill residues, and citrus waste) were reused as sorbents of diclofenac present in aqueous effluents. Citrus-waste biomass for a dose of 2 g·L−1 allowed for removing 99.7% of diclofenac present in the initial sample, with a sorption capacity of 9 mg of adsorbed diclofenac for each gram of used biomass. The respective values obtained for olive-mill residues and artichoke agrowaste were around 4.15 mg·g−1. Advanced oxidation processes with UV/H2O2 and UV/HOCl were shown to be effective treatments for the elimination of diclofenac. A significant reduction in chemical oxygen demand (COD; 40–48%) was also achieved with these oxidation treatments. Despite the lesser effectiveness of the sorption process, it should be considered that the reuse and valorization of these lignocellulosic agrifood residues would facilitate the fostering of a circular economy.

1. Introduction

Water is a renewable but limited natural resource, which forces us to manage it, especially in arid and semiarid areas where water resources are limited. The presence of some pollutants can jeopardize water recovery, and the reuse of urban and industrial effluents [1]. In addition to pollution from municipal discharges, water bodies are also contaminated by industry, mining, and pollution from agrochemicals used on irrigated land, which in many cases are discharged directly into lakes and rivers without prior treatment [2].
The reuse of urban and industrial wastewater with some pollutants can contribute to soil contamination, as well as its passage into the tissue of cultivated plants. This can produce adverse effects on the ecosystem [3,4,5,6].
While the international scientific community continues to make considerable efforts to minimize or alleviate the problem of what we may call traditional pollutants (heavy metals, organic matter, inorganic nutrients, etc.), other environmental pollutants, called emerging pollutants (ECs), are of growing concern [7] and are leading us to adapt our strategies to respond to their threats [8,9].
Aqueous effluents that arrive at urban wastewater-treatment plants show a complex composition associated with current human and industrial development. Therefore, the presence of certain pollutants can, in many cases, interfere with the proper functioning of biological wastewater-treatment systems. Emerging contaminants are considered among these pollutants [9]. Emerging contaminants are compounds of different origin and chemical nature of which the presence in the environment has gone largely unnoticed [10].
The lack of international monitoring programs for ECs makes it impossible to fully know their effects, problems, and behavior from an ecotoxicological point of view [2]. They can be a danger to the environment and human health [11,12]. Another particularity of this type of pollutant is that, due to its high production and consumption, and the constant and continuous introduction of these pollutants into the environment, they do not need to be persistent to cause negative effects.
Emerging contaminants can be classified as pharmaceutical and personal-care products, plasticizers, food additives, wood preservatives, contrast media, detergents, surfactants, fire retardants, biocides, hormones, and some disinfection byproducts. Advances in analytical technologies have helped to identify this group of contaminants [13,14].
These compounds have high transformation/disposal rates that can compensate for their continued introduction into the environment. For this reason, it is necessary to raise awareness of their origin and transformation, and the effects that this new generation of pollutants can have in order to propose modifications or improvements in water-treatment mechanisms. Some authors suggested the use of toxicity tests with chemical analysis to evaluate the efficiency of treatment methods [15,16,17,18].
The ongoing processing of aqueous effluents in conventional wastewater-treatment systems does not provide an adequate approach for the removal of emerging contaminants. These can arrive in their original form and/or be metabolized, making it difficult to operate biological wastewater treatment, sludge treatment, and the subsequent reuse of wastewater; there is also a lack of knowledge about the possible impact of these pollutants on the environment [19]. In many cases, products resulting from the transformation of the original emerging contaminants produce compounds that turn out to be more toxic than the original ones are [20].
Diclofenac (2-(2,6-dichloroanilino) phenylacetic acid) is one of the best-selling nonsteroidal anti-inflammatory drugs [21]. The high consumption level of this compound means that it is one of the most detected pharmaceuticals in aqueous effluents, and according to reported data, the measured values of diclofenac in municipal wastewater can be up 7.1 µg·L−1 [22,23]. A distinctive feature of diclofenac is that it undergoes low biodegradability and high persistence in wastewater-treatment plants, leading to its bioaccumulation in surface waters, sediments, and sludges [24,25]. Therefore, it is necessary to implement specific treatments to reduce or eliminate its presence in effluents.
Different sorption studies of diclofenac are reported in the literature. The highest bioremoval efficacies were obtained with carbon nanotubes [26], clays [27], and biochars [28] as sorbents. Raw lignocellulosic biomass was also used as a low-cost biosorbent, but the achieved efficiency was not as high as that with previous sorbents [29,30]. Despite this, biosorption has lately been presented as a very interesting technology, in line with the concept of the circular economy [31,32]. Efficient biowaste management is among the most important challenges in agrifood industries. Suggested uses for these lignocellulosic residues include their utilization as sorbents of pollutants in aqueous effluents [33,34,35] since they present very interesting physicochemical properties, such as their high surface area and the presence of a variety of functional groups that facilitate the sorption process [36,37,38]. Bioadsorptive techniques are the best ecofriendly solutions for removing contaminants because they are economical, efficient, highly selective on pollutants, and easily operable.
The most commonly used treatments for the removal of emerging contaminants, such as diclofenac, are advanced oxidation processes [39,40,41,42,43], which utilize free radical reactions to directly degrade chemical contaminants as an alternative to traditional treatments. For these oxidative treatments, it is necessary to carry out research studies that examine what the most appropriate combination of oxidizing reagents is to degrade a specific pollutant.
The main objective of this work was to carry out a comparative study of diclofenac elimination in aqueous effluents through biosorption with agrifood residues and through different advanced oxidation techniques (ultraviolet radiation (UV), sodium hypochlorite, and combinations of ultraviolet radiation with hypochlorite and with hydrogen peroxide).

2. Materials and Methods

2.1. Preparation and Characterization of Agrowaste Biomass

In preliminary studies, different agricultural wastes residues were processed and examined for their ability to remove diclofenac from a test solution. Of these, the three most interesting agrifood waste types that are abundant in the Murcia region (Spain) were chosen to be investigated in this study: artichoke agrowaste, olive-mill residues, and citrus waste from agrifood industries. Biomass samples were washed with distilled water and dried at 70 °C for 24 h before being ground and passed through a sieve with a number 18 mesh (1 mm). The different surface morphologies of each biomass were explored, and a qualitative determination of each was made using a field-emission scanning electron microscope and an energy-dispersive X-ray analyzer (SEM) (Hitachi S-3500N). FTIR measurements of the sorbents were performed in the range of 4000 to 400 cm−1 in a Thermo Nicolet 5700 (Karlsruhe, Germany). Moreover, the pH point of zero charge (pHZPC) was determined by the mass-titration method [44].

2.2. Preparation of Diclofenac Solutions

A diclofenac stock solution (1 g·L−1) was prepared using diclofenac sodium (C14H10Cl2NNaO2, ≥99%; Sigma-Aldrich, Madrid, Spain) in deionized water. The working solution (20 L) was achieved by diluting the stock solution in treated and filtered wastewater from a wastewater-treatment plant. The pH value was adjusted to 6.6 with a 0.1 mol·L−1 HCl or 0.1 mol·L−1 NaOH solution using a Metrohm 654 pH meter with a pH combination electrode. All chemicals were of analytical grade. The analytical characterization of the working solution was performed by American Public Health Association (APHA) methods [45].

2.3. Batch-Biomass Tests

Batch-biosorption experiments were performed at 25 °C under stirring in a reciprocal contact agitator with 100 mL of the diclofenac working solution at a fixed concentration (Co = 37.6 mg·L−1) and a known amount of sorbent for 24 h in a conical flask at a constant stirring speed (150 rpm). Lastly, the solutions were filtered and quantified obtaining the final concentration (Ce). The initial (Co) and final (Ce) concentrations were quantified by high-performance liquid chromatography (HPLC).
The amounts of diclofenac adsorbed at equilibrium (qe), also called diclofenac removal efficiency and expressed as mg diclofenac/g dry biomass, were determined by mass-balance equation (Equation (1)) on the basis of values of diclofenac concentration in the solution at the beginning (Co) and end (Ce) of the test:
q e   =   ( C o − C e ) ⋅ V m ,
where V is the solution volume (L) and m the sorbent dry weight (g).
The percentage of diclofenac elimination in each case was calculated by Equation (2):
%   Removal =   ( C o − C e ) C o   ×   100 ,
where Co is the initial concentration (mg·L−1) and Ce is the equilibrium concentration (mg·L−1) of diclofenac.

2.4. Diclofenac Determination

Diclofenac concentration in the water samples was determined by high-performance liquid chromatography (HPLC). A Waters modular liquid chromatography system (Waters, Milford, MA, USA) equipped with two M510 pumps, a 717 plus autosampler, and an M996 photodiode array detector (PDA) was used. HPLC was run by the data system of the Millenium 2010 Chromatography Manager. An Atlantis C18 5 µm, 25 cm × 4.6 mm i.d. (Waters) column was used. Elution was performed using a gradient between 175 mM phosphoric acid in water and 175 mM acetic acid in acetonitrile as the mobile phase. Flow rate was 0.6 mL/min. Samples, before being analyzed, were filtered using a 0.45 µm pore size cellulose acetate membrane, and the filtrate was analyzed for HPLC. Diclofenac was monitored at 270 nm. The retention time of diclofenac was about 6.4 min.

2.5. Advanced Oxidation Treatments

2.5.1. Sodium Hypochlorite

Treatment with sodium hypochlorite was performed with 1000 mL of filtered diclofenac solution. Four different amounts of available chlorine, namely, 1.0, 2.0, 3.0, and 4.0 mL of a 5% (w/v) sodium hypochlorite solution (Panreac, Barcelona, Spain) were added to each sample. Experiments were carried out in sealed glass bottles. They were incubated for 2 h until the moment of their quantification in a dark isothermal chamber at 20 °C, with slow agitation. Lastly, samples were filtered and analyzed by HPLC.

2.5.2. UV Light Treatments

UV radiation was applied using an 8 watt low-pressure UV lamp (UV-C 8 watt Strahler–Messner, Kalletal, Germany), with a flow range of 0.5 to 1.1 L·h−1 and a wavelength of 254 nm. The facility was designed to be used with 500 mL of a sample, irradiated for short periods of time of 2, 5, 10, and 15 min. According to these irradiation durations, the provided doses were 15, 37, 73, and 110 mJ·cm−2, respectively. Before each treatment, the lamp was cleaned with deionized water. After irradiation, samples were filtered with a 0.45 µm filter and analyzed by HPLC.

2.5.3. UV Radiation Combined with Sodium Hypochlorite (UV/HOCl) and Hydrogen Peroxide (UV/H2O2)

UV/HOCl and UV/H2O2 assays were conducted as batch experiments using a concentration of 5 mg·L−1 sodium hypochlorite and 5 mg·L−1 of hydrogen peroxide, respectively, which were added into the initial sample and subjected to different UV exposure times (2, 5, 10, and 15 min) before filtration and analysis of diclofenac concentration was performed by HPLC.

2.6. Chemical Oxygen Demand

Chemical oxygen demand (COD) was determined using the methods described in APHA [45]. For COD measurements, a Spectroquant Nova 30 spectrophotometer (Merck, Darmstadt, Germany) was used.

3. Results and Discussion

3.1. Characterization of Biomass Samples

The surface characteristics of the different biomass samples used in diclofenac bioadsorption studies were investigated using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), as shown in Figure 1, Figure 2 and Figure 3. SEM is considered to be one of the most widely used tools in the scientific field for studying the surface characteristics of biomass used as biosorbent [46]. In the different micrographs that were made in the SEM, important differences in the surface characteristics of the different studied agrifood waste types were observed, presenting a majority composition of carbon and oxygen in all cases.
Figure 1 shows that artichoke biomass had filamentous structures made up of fiber cells that were longitudinally aligned. This fibrous structure provides consistency, resistance, and a large surface area [47] that, together with the small channels, allows for the rapid movement of fluids through the fibers, increasing the possibility of retaining diclofenac molecules. SEM analysis also showed that it was a rough surface, with the presence of holes of irregular shape and size [47] that could improve the retention of diclofenac.
Citrus-waste biomass (Figure 2) presented an irregular surface, but with a much more compact appearance and with fewer cavities than in the previous case, although with cracks that provided a large surface for the retention of diclofenac. Olive-mill residues (Figure 3) also presented an irregular surface with a fairly compact appearance, bit with few cavities. In all cases, the presence of cavities of irregular shape and dimensions would enhance the fixation of contaminants to be retained.
FTIR analysis allowed for inferring the structure of the sorbents on the basis of the locations and shapes of the bands in the spectra (Figure 4). The three sorbents showed a broad band at 3600–3100 cm−1 that was assigned to −OH stretching vibrations of hydroxyl and carboxyl groups. A −CH aliphatic stretching vibration band was also observed at 2900–2850 cm−1 in all sorbents. Around 1630 cm−1, a band attributed to C=O stretching vibrations and typical skeletal vibrations of aromatic rings was presented. In the region of 1030–1000 cm−1, a broad band, an indication of C−O and C=C vibrational stretching, was revealed. These are, in fact, typical FTIR spectra, corresponding to nonmodified plant biomass samples, where the lignocellulosic constituents are particularly outstanding [32,47,48,49].

3.2. Diclofenac Biosorption

Table 1 shows the characterization of the working water prepared from diclofenac stock solution and filtered effluent from a treatment plant. The initial concentration (Co) of diclofenac for the different experiments was 37.6 mg·L−1 and an initial COD value of 282 mg O2·L−1.
The sorption capacities and percentages of diclofenac removal in the experiments carried out for the different used sorbents and doses (Table 2) revealed that citrus-waste biomass was the most effective. Citrus residues, with a zero point of charge of 4.2, reduced the pH of the solution during the sorption process to 5.7 by the end of the experiment. These pH reductions were less pronounced in the olive-mill-residue (pHZPC = 5.4) and in the artichoke-agrowaste (pHZPC = 4.8) sorption tests, of which the final pH values were 6.4 and 6.1, respectively. In all cases, the modifications in pH were very slight, hardly affecting the solubility of the adsorbate and sorption-capacity values. The biomass of artichoke agrowaste showed the least capacity to retain diclofenac. In the case of citrus waste, for a dose of 2 g/L, all the diclofenac is retained, obtaining a sorption capacity (qe) of 9 mg·g−1. Olive-mill residues had intermediate and very similar retention values regardless of the dose used in the experiments.
The results of this study revealed that the reuse of raw lignocellulosic biomass from agrifood waste for the sorption of diclofenac may be an efficient and common method of wastewater treatment. The sorption capacities of diclofenac obtained in this study were lower than those reported for microalgae biomass (20–28 mg·g−1) [29] and grape bagasse (24 mg·g−1) [49], but comparable for that shown with activated carbon from olive stones (11 mg·g−1) [50]. In the present investigation, the agrifood waste used as sorbent was not previously modified or subjected to any thermal treatment. The obtained results in the present investigation reveal that this is a new line of research that is worth further exploring, and it may be of interest to test some cost-effective activation mechanism that enhances the bioadsorptive capacity of waste to specific contaminants. In this context, future studies will be made in application in real systems, where fixed-bed citrus-waste adsorbers can be implemented for the treatment of wastewater with diclofenac.

3.3. Advanced Oxidation Treatments

As summarized in Table 3, when the working solution (Co = 37.6 mg·L−1) was exposed to different exposure times of UV radiation ranging from 2 to 15 min, significant reductions in the initial diclofenac concentration were achieved, ranging from 9.78% removal for 2 min of exposure and 88.49% removal for 15 min of exposure, without being able to achieve total removal. A significant reduction in COD values was also achieved, in a similar way to that in other reported investigations [51].
In the treatment with sodium hypochlorite and a contact time of 2 h (Table 4), for a dose of 4 mg·L−1, all diclofenac present in the starting sample was eliminated. As the dose of hypochlorite was increased, greater elimination was achieved. The reduction in COD was also quite significant.
In the treatment that combined UV radiation with the addition of sodium hypochlorite (Table 5), practically all the diclofenac (93.59%) was eliminated for a radiation time of 10 min. When exposure time was increased (15 min), it was possible to eliminate it completely. In addition, the unreacted chlorine in this process provided residual protection for water reuse purposes [52]. Comparable reductions in COD were achieved as those with previous treatments. For the treatment in which UV radiation was combined with hydrogen peroxide (Table 6), the initial diclofenac was eliminated for all treatments. For an exposure time of 2 min of UV radiation, 99.20% of the initial diclofenac was degraded. The achieved elimination of COD was quite comparable in all performed treatments.
It is scientifically accepted that advanced oxidation processes are highly effective novel methods that accelerate the oxidation and the degradation of a wide range of organic and inorganic pollutants that are resistant to conventional treatment methods [53]. In our experiments, diclofenac was 88% by UV-C degraded irradiation; when the wastewater was treated for a time as short as 15 min, this result verified that this compound absorbs UV irradiation well at 254 nm and can be easily photolyzed [54]. When UV-C irradiation treatment was combined with 5 mg·L−1 of sodium hypochlorite, the degradation of diclofenac was increased to 100%. Nevertheless, UV/H2O2 was the most efficient oxidation process, combining the immediate UV effect and the action of the HO˙ radicals produced from the homolytic disruption of H2O2. The levels of diclofenac degradation under the adopted experimental conditions were higher than the values reported in the literature for oxidation processes, such as ozonation (32%) and UV/H2O2 (39%), after 39 min treatment [55]. The use of hypochlorite to degrade diclofenac in aqueous effluents was also reported with successful results [56]. Recent research in a Fenton-like system with FeCeOx–H2O2 achieved 84% degradation of diclofenac within 40 min [57]. All these results are in accordance with those obtained in our experimental design and confirm the feasibility of the tested methods. A significant reduction in chemical oxygen demand (COD) (40–48%) was also achieved with these oxidation treatments, although there was no direct relationship between the percentage of diclofenac degradation and the decrease in COD.

4. Conclusions

This paper offers a comparative study between the application of biosorption and advanced oxidation techniques to remove diclofenac from wastewater at high concentrations.
Artichoke agrowaste, olive-mill residues, and citrus waste were used as low-cost biosorbents to remove diclofenac from aqueous effluents. Citrus-waste biomass, at a sorbent dosage of 2 g·L−1, showed the highest sorption capacity (9 mg·g−1). This value was achieved with raw biomass without being subjected to any chemical or thermal activation process. The obtained results highlight the sustainable reutilization of agrifood waste for producing cost-effective sorbents, providing additional income for the agroindustrial sector. Waste valorization can efficiently help in reducing environmental stress by decreasing unwarranted pollution and promoting economy circularization.
UV-driven advanced oxidation treatments were effective in the degradation of diclofenac in wastewater. The UV/H2O2 (5 mg·L−1) oxidation process was faster than UV/HOCl (5 mg·L−1) to reach the same degradation rate. Chemical oxygen demand (COD) was considerably reduced (40–48%) with these oxidation treatments.
The obtained results in this study confirm biosorption as a low-cost and environmentally sustainable technique, and the high efficiency demonstrated by advanced oxidation techniques, may lead to applying specifically designed techniques that combine biosorption and advanced oxidation to eliminate specific emerging contaminants in aqueous effluents.

Author Contributions

Conceptualization, J.M.A. and J.A.F.-L.; methodology, J.M.A. and M.J.R.; formal analysis, J.M.A. and J.A.F.-L.; investigation, M.J.R.; writing—original-draft preparation, J.M.A.; writing—review and editing, J.A.F.-L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Technical University of Cartagena (UPCT), grant number ACI B.

Acknowledgments

This research is part of the Environmental Engineering R&D group. The excellent technical assistance of the Technical Research Support Service of the UPCT is greatly acknowledged.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Dalecka, B.; Oskarsson, C.; Juhna, T.; Rajarao, G.K. Isolation of fungal strains from municipal wastewater for the removal of pharmaceutical substances. Water 2020, 12, 524. [Google Scholar] [CrossRef] [Green Version]
  2. Geisen, V.; Mol, H.; Klumpp, E.; Umlauf, G.; Nadal, M.; Van der Ploeg, M.; van de Zee, S.E.A.T.M.; Ritsema, C.J. Emerging pollutants in the environment: A challenge for water resource management. Int. Soil Water Conserv. Res. 2015, 3, 57–65. [Google Scholar] [CrossRef]
  3. Sauvé, S.; Desrosiers, M. A review of what is an emerging contaminant. Chem. Cent. J. 2014, 8, 15. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  4. López-Doval, J.C.; Montagner, C.C.; de Alburquerque, A.F.; Moschini-Carlos, V.; Umbuzeiro, G.; Pompeo, M. Nutrients, emerging pollutants and pesticides in a tropical urban reservoir: Spatial distributions and risk assessment. Sci. Total Environ. 2017, 575, 1307–1324. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  5. Margenat, A.; Matamoros, V.; Díez, S.; Cañameras, N.; Comas, J.; Bayona, J.M. Ocurrence of chemical contaminants in peri-urban agricultural irrigation waters and assesment of their phytotoxicity and crop productivity. Sci. Total Environ. 2017, 599, 1140–1148. [Google Scholar] [CrossRef] [PubMed]
  6. Tran, N.; Drogui, P.; Brar, S.K. Sonochemical techniques to degrade pharmaceutical organic pollutants. Environ. Chem. Lett. 2015, 13, 251–268. [Google Scholar] [CrossRef]
  7. Carmalin, A.; Lima, E. Removal of emerging contaminants from the environment by adsorption. Ecotoxicol. Environ. 2018, 150, 1–17. [Google Scholar]
  8. Munthe, J.; Brorstrom-Lunden, E.; Rahmberg, M.; Posthuma, L.; Alterburger, R.; Brack, W.; Bunke, D.; Engelen, G.; Gawlik, B.; Gils, J.; et al. An expanded conceptual framework for solution-focused management of chemical pollution in European waters. Environ. Sci. Eur. 2017, 29, 1072. [Google Scholar] [CrossRef] [Green Version]
  9. Richardson, S.D.; Kimura, S.Y. Emerging environmental contaminants: Challenges facing our next generation and potential engineering solutions. Environ. Technol. Innov. 2017, 8, 40–56. [Google Scholar] [CrossRef]
  10. 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]
  11. Petrovic, M.; Solé, M.; López, M.; Barceló, D. Endocrine disruptors in sewage treatment plants, receiving river waters, and sediments: Integration of chemical analysis and biological effects of feral carp. Environ. Toxic. Chem. 2002, 21, 2146–2156. [Google Scholar] [CrossRef]
  12. Esplugas, S.; Bila, D.M.; Krause, L.G.T.; Dezotti, M. Ozonation and advanced oxidation technologies to remove endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) in water effluents. J. Hazard. Mater. 2007, 149, 631–642. [Google Scholar] [CrossRef] [PubMed]
  13. Richardson, S.D. Environmental mass spectrometry: Emerging contaminants and current issues. Anal. Chem. 2012, 84, 747–778. [Google Scholar] [CrossRef] [PubMed]
  14. Richardson, S.D.; Kimura, S.Y. Water analysis: Emerging contaminants and current issues. Anal. Chem. 2016, 88, 546–582. [Google Scholar] [CrossRef]
  15. Blanco, M.; Pérez-Albadalejo, E.; Piña, B.; Kuspilic, G.; Milun, V.; Lille-Langoy, R. Assessing the environmental quality of sediments from Split coastal area (Croatia) with a battery of cell-based bioassays. Sci. Total Environ. 2018, 624, 1640–1648. [Google Scholar]
  16. Boehler, S.; Strecker, R.; Heinrich, P.; Prochazka, E.; Northcott, G.L.; Ataria, J.M. Assessment of urban stream sediment pollutants entering estuaries using chemical analysis and multiple bioassays to characterize biological activities. Sci. Total Environ. 2017, 593, 498–507. [Google Scholar] [CrossRef]
  17. Abbas, M.; Adil, M.; Ehtisham-ul-Haque, S.; Munir, B.; Yameen, M.; Ghaffar, A.; Abbas Shar, G.; Asif Tahir, M.; Iqbal, M. Vibrio fischeri bioluminescence inhibition assay for ecotoxicity assessment: A review. Sci. Total Environ. 2018, 626, 1295–1309. [Google Scholar]
  18. Schereiber, B.; Fischer, J.; Schiwy, S.; Hollert, H.; Schulz, R. Towards more ecological relevance in sediment toxicity testing with fish: Evaluation of multiple bioassays with embryos of the benthic weatherfish (Misgurnus fossilis). Sci. Total Environ. 2018, 619, 391–400. [Google Scholar] [CrossRef]
  19. Sang, Z.; Jiang, Y.; Tsoi, Y.-K.; Leung, K.S. Evaluating the environmental impact of artificial sweeteners: A study of their distributions, photodegradation ant toxicities. Water Res. 2014, 52, 260–274. [Google Scholar] [CrossRef]
  20. Funke, J.; Prasse, C.; Eversloh, C.L.; Ternes, T.A. Oxypurinol-A novel marker for wastewater contamination of the aquatic environment. Water Res. 2015, 74, 257–265. [Google Scholar]
  21. Lonappan, L.; Brar, S.K.; Das, R.K.; Verma, M.; Rao, Y. Diclofenac and its transformation products: Environmental occurrence and toxicity. Environ. Int. 2016, 96, 127–138. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  22. Grandclément, C.; Piram, A.; Petit, M.E.; Seyssiecq, I.; Laffont-Schwob, I.; Vanot, G.; Tiliacos, N.; Roche, N.; Doumenq, P. Biological removal and fate assessment of diclofenac using Bacillus subtilis and Brevibacillus laterosporus strains and ecotoxicological effects of diclofenac and 4′-hydroxy-diclofenac. J. Chem. 2020, 2020, 9789420. [Google Scholar] [CrossRef]
  23. Vieno, N.; Silanpää, M. Fate of diclofenac in municipal wastewater treatment plants—A review. Environ. Int. 2014, 69, 28–39. [Google Scholar] [CrossRef] [PubMed]
  24. Langford, K.H.; Reid, M.; Thomas, K.V. Multi-residue screening of prioritised human pharmaceuticals, illicit drugs and bactericides in sediments and sludge. J. Environ. Monit. 2011, 13, 2284–2291. [Google Scholar] [CrossRef] [PubMed]
  25. Kunkel, U.; Radke, M. Fate of pharmaceuticals in rivers: Deriving a benchmark dataset at favorable attenuation conditions. Water Res. 2012, 46, 5551–5565. [Google Scholar] [CrossRef]
  26. Gil, A.; Santamaría, L.; Korili, S.A. Removal of caffeine and diclofenac from aqueous solution by adsorption on multiwalled carbon nanotubes. Coll. Interf. Sci. Commun. 2018, 22, 25–28. [Google Scholar] [CrossRef]
  27. Mabrouki, H.; Akretche, D.E. Diclofenac potassium removal from water by adsorption on natural and pillared clay. Des. Water Treatm. 2016, 57, 6033–6043. [Google Scholar] [CrossRef]
  28. Thi Minh Tam, N.; Liu, Y.; Bashir, H.; Yin, Z.; He, Y.; Zhou, X. Efficient removal of diclofenac from aqueous solution by potassium ferrate-activated porous graphitic biochar: Ambient condition influences and adsorption mechanism. Int. J. Environ. Res. Public Health 2020, 17, 291. [Google Scholar] [CrossRef] [Green Version]
  29. Coimbra, R.N.; Escapa, C.; Vázquez, N.C.; Noriega-Hevia, G.; Otero, M. Utilization of non-living microalgae biomass from two different strains for the adsorptive removal of diclofenac from water. Water 2018, 10, 1401. [Google Scholar] [CrossRef] [Green Version]
  30. Li, Y.; Taggart, M.A.; McKenzie, C.; Zhang, Z.; Lu, Y.; Pap, S.; Gibb, S. Utilizing low-cost natural waste for the removal of pharmaceuticals from water: Mechanisms, isotherms and kinetics at low concentrations. J. Clean. Prod. 2019, 227, 88–97. [Google Scholar] [CrossRef] [Green Version]
  31. Yusuf, M.; Elfghi, F.M.; Zaidi, S.A.; Abdullah, E.C.; Khan, M.A. Applications of graphene and its derivatives as an adsorbent for heavy metal and dye removal: A systematic and comprehensive overview. RSC Adv. 2015, 5, 50392–50420. [Google Scholar] [CrossRef]
  32. Rosique, M.; Angosto, J.M.; Guibal, E.; Roca, M.J.; Fernández-López, J.A. Factorial design methodological approach for enhanced cadmium ions bioremoval by Opuntia biomass. CLEAN Soil Air Water 2016, 44, 959–966. [Google Scholar] [CrossRef]
  33. Ben-Othman, S.; Jõudu, I.; Bhat, R. Bioactives from agri-food wastes: Present insights and future challenges. Molecules 2020, 25, 510. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  34. Nowicki, P.; Kazmierczak-Razna, J.; Pietrzak, R. Physico-chemical and adsorption properties of carbonaceous sorbents prepared by activation of tropical fruit skins with potassium carbonate. Mater. Des. 2016, 90, 579–585. [Google Scholar] [CrossRef]
  35. Castrica, M.; Rebucci, R.; Giromini, C.; Tretola, M.; Cattaneo, D.; Baldi, A. Total phenolic content and antioxidant capacity of agri-food waste and by-products. Ital. J. Anim. Sci. 2019, 18, 336–341. [Google Scholar] [CrossRef]
  36. Manna, S.; Toy, D.; Adhikari, B.; Thomas, S.; Das, P. Biomass for water defluoridation and current understanding on biosorption mechanisms: A review. Environ. Prog. Sustain. Energy 2018, 37, 1560–1572. [Google Scholar] [CrossRef]
  37. Ummartyotin, S.; Pechyen, C. Strategies for development and implementation of bio-based materials as effective renewable resources of energy: A comprehensive review on adsorbent technology. Renew. Sustain. Energy Rev. 2016, 62, 654–664. [Google Scholar] [CrossRef]
  38. Arief, V.O.; Trilestari, K.; Sunarso, J.; Indraswati, N.; Ismadji, S. Recent progress on biosorption of heavy metals from liquids using low cost biosorbents: Characterization, biosorption parameters and mechanism studies. CLEAN Soil Air Water 2008, 36, 937–962. [Google Scholar] [CrossRef]
  39. Ternes, T.; Stüber, J.; Herrmann, N.; McDowell, D.; Ried, A.; Kampmann, M.; Teiser, B. Ozonation: A tool for removal of pharmaceuticals, contrast media and musk fragrances from wastewater? Water Res. 2003, 37, 1976–1982. [Google Scholar] [CrossRef]
  40. Cerreta, G.; Roccamante, M.A.; Oller, I.; Malato, S.; Rizzo, L. Contaminants of emerging concern removal from real wastewater by UV/free chlorine process: A comparison with solar/free chlorine and UV/H2O2 at pilot scale. Chemosphere 2019, 236, 124354. [Google Scholar]
  41. Lee, Y.; von Gunten, U. Oxidative transformation of micropollutants during municipal wastewaters treatment: Comparison of kinetic aspects of selective (chlorine, chlorine dioxide, ferrate VI and ozone) and non-selective oxidants (hydroxyl radicals). Water Res. 2010, 39, 555–566. [Google Scholar] [CrossRef] [PubMed]
  42. Kanakaraju, D.; Glass, B.D.; Oelgemöller, M. Titanium dioxide photocatalysis for pharmaceutical wastewater treatment. Environ. Chem. Lett. 2014, 12, 27–47. [Google Scholar] [CrossRef]
  43. Jiang, J.; Pang, S.Y.; Ma, J.; Liu, H. Oxidation of phenolic endocrine disrupting chemicals by potassium permanganate in synthetic and real waters. Environ. Sci. Technol. 2012, 46, 1774–1781. [Google Scholar] [CrossRef]
  44. Fiol, N.; Villaescusa, I. Determination of sorbent point zero charge: Usefulness in sorption studies. Environ. Chem. Lett. 2009, 7, 79–84. [Google Scholar] [CrossRef]
  45. Eaton, A.D.; American Public Health Association; American Water Works Association; Water Environment Federation. Standard Methods for the Examination of Water and Wastewater, 21st ed.; APHA-AWWA-WEF: Washington, DC, USA, 2005. [Google Scholar]
  46. Amiri, H.; Karimi, K. Improvement of acetone, butanol, and ethanol production from woody biomass using organosolv pretreatment. Bioproc. Biosyst. Eng. 2015, 38, 1959–1972. [Google Scholar] [CrossRef] [PubMed]
  47. Saavedra, M.I.; Doval Miñarro, M.; Angosto, J.M.; Fernández-López, J.A. Reuse potential of residues of artichoke (Cynara scolymus L.) from industrial canning processing as sorbent of heavy metals in multimetallic effluents. Ind. Crops Prod. 2019, 141, 111751. [Google Scholar] [CrossRef]
  48. Mahato, N.; Sharma, K.; Sinha, M.; Baral, E.R.; Koteswararao, R.; Dhyani, A.; Cho, M.H.; Cho, S. Bio-sorbents, industrially important chemicals and novel materials from citrus processing waste as a sustainable and renewable bioresource: A review. J. Adv. Res. 2020, 23, 61–82. [Google Scholar] [CrossRef] [PubMed]
  49. Antunes, M.; Esteves, V.I.; Guégan, R.; Crespo, J.S.; Fernandes, A.N.; Giovanela, M. Removal of diclofenac sodium from aqueous solution by Isabel grape bagasse. Chem. Eng. J. 2012, 192, 114–121. [Google Scholar] [CrossRef] [Green Version]
  50. Larous, S.; Meniai, A.-H. Adsorption of diclofenac from aqueous solution using activated carbon prepared from olive stones. Int. J. Hydrog. Energy 2016, 41, 10380–10390. [Google Scholar] [CrossRef]
  51. Plauta, M.; Tisler, T.; Toman, M.J.; Pintar, A. Efficiency of advanced oxidation processes in lowering bisphenol A toxicity and oestrogenic activity in aqueous samples. Arch. Ind. Hyg. Toxicol. 2014, 65, 77–87. [Google Scholar]
  52. Zhao, Q.; Shang, C.; Zhang, X.; Ding, G.; Yang, X. Formation of halogenated organic byproducts during medium-pressure UV and chlorine coexposure of model compounds, NOM and bromide. Water Res. 2011, 45, 6545–6554. [Google Scholar] [CrossRef] [PubMed]
  53. Stasinakis, A. Use of selected advanced oxidation processes (AOPs) for wastewater treatment—A mini review. Glob. NEST J. 2008, 10, 376–385. [Google Scholar]
  54. De la Cruz, N.; Giménez, J.; Esplugas, S.; Grandjean, D.; de Alencastro, L.F.; Pulgarín, C. Degradation of 32 emergent contaminants by UV and neutral photo-fenton in domestic wastewater effluent previously treated by activated sludge. Water Res. 2012, 46, 1947–1957. [Google Scholar] [CrossRef] [PubMed]
  55. Vogna, D.; Marotta, R.; Napolitano, A.; Andreozzi, R.; d’Ischia, M. Advanced oxidation of the pharmaceutical drug diclofenac with UV/H2O2 and ozone. Water Res. 2004, 38, 414–422. [Google Scholar] [CrossRef] [PubMed]
  56. Luongo, G.; Guida, M.; Siciliano, A.; Libralato, G.; Saviano, L.; Amoresano, A.; Previtera, L.; Di Fabio, G.; Zarrelli, A. Oxidation of diclofenac in water by sodium hypochlorite: Identification of new degradation by-products and their ecotoxicological evaluation. J. Pharmac. Biomed. Anal. 2020, 113762. [Google Scholar] [CrossRef] [PubMed]
  57. Chong, S.; Zhang, G.; Zhang, N.; Liu, Y.; Huang, T.; Chang, H. Diclofenac degradation in water by FeCeOx catalyzed H2O2: Influencing factors, mechanism and pathways. J. Hazard. Mat. 2017, 334, 150–159. [Google Scholar] [CrossRef]
Water 12 03567 g001 550
Figure 1. SEM image and EDS analysis of artichoke-agrowaste biomass.
Figure 1. SEM image and EDS analysis of artichoke-agrowaste biomass.
Water 12 03567 g001
Water 12 03567 g002 550
Figure 2. SEM image and EDS analysis of citrus-waste biomass.
Figure 2. SEM image and EDS analysis of citrus-waste biomass.
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Water 12 03567 g003 550
Figure 3. SEM image and EDS analysis of olive-mill residue biomass.
Figure 3. SEM image and EDS analysis of olive-mill residue biomass.
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Water 12 03567 g004 550
Figure 4. FTIR spectra between 4000 and 400 cm−1 for sorbent samples.
Figure 4. FTIR spectra between 4000 and 400 cm−1 for sorbent samples.
Water 12 03567 g004
Table
Table 1. Initial composition of working solution. COD, chemical oxygen demand.
Table 1. Initial composition of working solution. COD, chemical oxygen demand.
ParameterValue
pH6.6 ± 0.2 *
Conductivity (µS·cm−1)12.5 ± 2.5
TSS (mg/L)98.2 ± 8.6
Turbidity (NTU)4.7 ± 0.3
NO3− (mg·L−1)16.8 ± 2.7
PO43− (mg·L−1)5.6 ± 1.1
BOD (mg O2·L−1)113.3 ± 10.2
COD (mg O2·L−1)282.0 ± 15.0
Diclofenac initial (mg·L−1)37.6
* mean ± SD of 3 determinations.
Table
Table 2. Elimination of diclofenac for different biomass samples.
Table 2. Elimination of diclofenac for different biomass samples.
BiomassSorbent Dosage
(g·L−1)		Removal %qe
(mg·g−1)
Artichoke agrowaste118.7 ± 2.4 *3.9 ± 0.5
219.9 ± 3.14.2 ± 0.4
Olive-mill residues146.4 ± 4.44.2 ± 0.6
246.3 ± 5.84.2 ± 0.8
Citrus-waste187.1 ± 5.77.8 ± 1.1
299.7 ± 0.59.0 ± 0.3
* mean ± SD of 3 determinations.
Table
Table 3. Treatment with ultraviolet (UV) radiation.
Table 3. Treatment with ultraviolet (UV) radiation.
Contact Time
(min)		Diclofenac
(mg·L−1)		Removed Diclofenac % COD
Reduction %
233.9 ± 2.8 *9.8 ± 2.444.3 ± 3.6
516.6 ± 2.155.9 ± 3.962.1 ± 3.5
106.1 ± 1.183.8 ± 4.662.4 ± 4.1
154.3 ± 0.988.5 ± 3.866.3 ± 3.9
* mean ± SD of 3 determinations.
Table
Table 4. Treatment with sodium hypochlorite (contact time 2 h).
Table 4. Treatment with sodium hypochlorite (contact time 2 h).
Hypochlorite Concentration
(mg·L−1)		Diclofenac
(mg·L−1)		Removed Diclofenac % COD
Reduction %
114.4 ± 3.3 *61.7 ± 4.724.1 ± 2.3
24.4 ± 1.288.4 ± 5.138.3 ± 2.8
33.3 ± 0.991.3 ± 4.444.0 ± 2.6
4n.d. †10044.7 ± 1.8
* mean ± SD of 3 determinations; † not detected.
Table
Table 5. Ultraviolet radiation treatment combined with sodium hypochlorite (5 mg·L−1).
Table 5. Ultraviolet radiation treatment combined with sodium hypochlorite (5 mg·L−1).
Contact Time
(min)		Diclofenac
(mg·L−1)		Removed Diclofenac % COD
Reduction %
229.1 ± 2.2 *22.6 ± 2.814.2 ± 1.9
513.5 ± 1.864.2 ± 3.122.0 ± 2.4
102.4 ± 0.593.6 ± 4.845.0 ± 3.8
15n.d. †10047.9 ± 3.4
* mean ± SD of 3 determinations; † not detected.
Table
Table 6. UV radiation treatment combined with H2O2 (5 mg·L−1).
Table 6. UV radiation treatment combined with H2O2 (5 mg·L−1).
Contact Time
(min)		Diclofenac
(mg·L−1)		Removed Diclofenac %COD
Reduction %
20.3 ± 0.1 *99.2 ± 4.423.4 ± 1.7
5n.d. †10025.9 ± 2.3
10n.d.10036.5 ± 2.0
15n.d.10040.1 ± 3.1
* mean ± SD of 3 determinations; † not detected.
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Angosto, J.M.; Roca, M.J.; Fernández-López, J.A. Removal of Diclofenac in Wastewater Using Biosorption and Advanced Oxidation Techniques: Comparative Results. Water 2020, 12, 3567. https://doi.org/10.3390/w12123567

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Angosto JM, Roca MJ, Fernández-López JA. Removal of Diclofenac in Wastewater Using Biosorption and Advanced Oxidation Techniques: Comparative Results. Water. 2020; 12(12):3567. https://doi.org/10.3390/w12123567

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Angosto, José M., María J. Roca, and José A. Fernández-López. 2020. "Removal of Diclofenac in Wastewater Using Biosorption and Advanced Oxidation Techniques: Comparative Results" Water 12, no. 12: 3567. https://doi.org/10.3390/w12123567

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