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12 pages, 1880 KiB

Open AccessArticle

H₂S Removal from Groundwater by Chemical Free Advanced Oxidation Process Using UV-C/VUV Radiation

by Yael Gilboa, Yuval Alfiya, Sara Sabach, Eran Friedler and Yael Dubowski

Molecules 2021, 26(13), 4016; https://doi.org/10.3390/molecules26134016 - 30 Jun 2021

Cited by 2 | Viewed by 2008

Abstract

Sulfide species may be present in groundwater due to natural processes or due to anthropogenic activity. H₂S contamination poses odor nuisance and may also lead to adverse health effects. Advanced oxidation processes (AOPs) are considered promising treatments for hydrogen-sulfide removal from [...] Read more.

Sulfide species may be present in groundwater due to natural processes or due to anthropogenic activity. H₂S contamination poses odor nuisance and may also lead to adverse health effects. Advanced oxidation processes (AOPs) are considered promising treatments for hydrogen-sulfide removal from water, but conventional AOPs usually require continuous chemical dosing, as well as post-treatment, when solid catalysts are applied. Vacuum-UV (VUV) radiation can generate ·OH in situ via water photolysis, initiating chemical-free AOP. The present study investigated the applicability of VUV-based AOP for removal of H₂S both in synthetic solutions and in real groundwater, comparing combined UV-C/VUV and UV-C only radiation in a continuous-flow reactor. In deionized water, H₂S degradation was much faster under the combined radiation, dominated by indirect photolysis, and indicated the formation of sulfite intermediates that convert to sulfate at high radiation doses. Sulfide was efficiently removed from natural groundwater by the two examined lamps, with no clear preference between them. However, in anoxic conditions, common in sulfide-containing groundwater, a small advantage for the combined lamp was observed. These results demonstrate the potential of utilizing VUV-based AOP for treating H₂S contamination in groundwater as a chemical-free treatment, which can be especially attractive to remote small treatment facilities. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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12 pages, 2670 KiB

Open AccessArticle

Multiple Steady States in the Photocatalytic Reactor for Colored Compounds Degradation

by Jakub Szyman

Molecules 2021, 26(13), 3804; https://doi.org/10.3390/molecules26133804 - 22 Jun 2021

Cited by 2 | Viewed by 1529

Abstract

The paper reports the occurrence of multiple steady-state zones in most of the constructions of fixed-bed photocatalytic reactors. Such a phenomenon has not been ever observed in a field of photocatalytic reactors. The simulation has been provided for a common case in a [...] Read more.

The paper reports the occurrence of multiple steady-state zones in most of the constructions of fixed-bed photocatalytic reactors. Such a phenomenon has not been ever observed in a field of photocatalytic reactors. The simulation has been provided for a common case in a photocatalysis—the degradation of colored compounds. The mathematical model of the photocatalytic reactor with immobilized bed has been stated by a simple ideal mixing model (analogous to the CSTR model). The solution has been continued by the two parameters—the Damköhler number and the absorption coefficient related to the inlet stream concentration. Some branches of steady states include the limit point. The performed two-parametric continuation of the limit point showed the cusp bifurcation point. Besides the numerical simulation, the physical explanation of the observed phenomenon has been provided; the multiple steady-states occurrence is controlled by light absorption–reaction rate junction. When the reaction rate is limited by the light absorption, we can say that a light barrier occurs. The dynamical simulations show that when the process is operated in a field of multiple steady states, the overall reactor efficiency is related to the reactor set-up mode. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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12 pages, 1146 KiB

Open AccessArticle

Secondary Effects of Hypochlorite Treatment on the Emerging Pollutant Candesartan: The Formation of Degradation Byproducts and Their Toxicological Profiles

by Giovanni Luongo, Lorenzo Saviano, Giovanni Libralato, Marco Guida, Antonietta Siciliano, Lucio Previtera, Giovanni Di Fabio and Armando Zarrelli

Molecules 2021, 26(11), 3422; https://doi.org/10.3390/molecules26113422 - 05 Jun 2021

Cited by 2 | Viewed by 2314

Abstract

In recent years, many studies have reported the frequent detection of antihypertensive agents such as sartans (olmesartan, valsartan, irbesartan and candesartan) in the influents and effluents of wastewater treatment plants (WWTPs) and in the superficial waters of rivers and lakes in both Europe [...] Read more.

In recent years, many studies have reported the frequent detection of antihypertensive agents such as sartans (olmesartan, valsartan, irbesartan and candesartan) in the influents and effluents of wastewater treatment plants (WWTPs) and in the superficial waters of rivers and lakes in both Europe and North America. In this paper, the degradation pathway for candesartan (CAN) was investigated by simulating the chlorination process that is normally used to reduce microbial contamination in a WWTP. Twelve isolated degradation byproducts (DPs), four of which were isolated for the first time, were separated on a C-18 column by employing a gradient HPLC method, and their structures were identified by combining nuclear magnetic resonance and mass spectrometry and comparing the results with commercial standards. On the basis of these results, a mechanism of formation starting from the parent drug is proposed. The ecotoxicity of CAN and its DPs was studied by conducting a battery of ecotoxicity tests; bioassays were performed using Aliivibrio fischeri (bacterium), Daphnia magna (planktonic crustacean) and Raphidocelis subcapitata (alga). The ecotoxicity results shed new light on the increased toxicity of DPs compared with the parent compound. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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13 pages, 3950 KiB

Open AccessArticle

Metoprolol and Its Degradation and Transformation Products Using AOPs—Assessment of Aquatic Ecotoxicity Using QSAR

by Melanie Voigt, Indra Bartels, Dorothee Schmiemann, Lars Votel, Kerstin Hoffmann-Jacobsen and Martin Jaeger

Molecules 2021, 26(11), 3102; https://doi.org/10.3390/molecules26113102 - 22 May 2021

Cited by 9 | Viewed by 2768

Abstract

Pharmaceuticals are found in waterbodies worldwide. Conventional sewage treatment plants are often not able to eliminate these micropollutants. Hence, Advanced Oxidation Processes (AOPs) have been heavily investigated. Here, metoprolol is exposed to UV irradiation, hydrogen peroxide, and ozonation. Degradation was analyzed using chemical [...] Read more.

Pharmaceuticals are found in waterbodies worldwide. Conventional sewage treatment plants are often not able to eliminate these micropollutants. Hence, Advanced Oxidation Processes (AOPs) have been heavily investigated. Here, metoprolol is exposed to UV irradiation, hydrogen peroxide, and ozonation. Degradation was analyzed using chemical kinetics both for initial and secondary products. Photo-induced irradiation enhanced by hydrogen peroxide addition accelerated degradation more than ozonation, leading to complete elimination. Degradation and transformation products were identified by high-performance liquid-chromatography coupled to high-resolution higher-order mass spectrometry. The proposed structures allowed to apply Quantitative Structure-Activity Relationship (QSAR) analysis to predict ecotoxicity. Degradation products were generally associated with a lower ecotoxicological hazard to the aquatic environment according to OECD QSAR toolbox and VEGA. Comparison of potential structural isomers suggested forecasts may become more reliable with larger databases in the future. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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12 pages, 1099 KiB

Open AccessArticle

LC and NMR Studies for Identification and Characterization of Degradation Byproducts of Olmesartan Acid, Elucidation of Their Degradation Pathway and Ecotoxicity Assessment

by Giovanni Luongo, Antonietta Siciliano, Giovanni Libralato, Sara Serafini, Lorenzo Saviano, Lucio Previtera, Giovanni Di Fabio and Armando Zarrelli

Molecules 2021, 26(6), 1769; https://doi.org/10.3390/molecules26061769 - 22 Mar 2021

Cited by 4 | Viewed by 1725

Abstract

The discovery of various sartans, which are among the most used antihypertensive drugs in the world, is increasingly frequent not only in wastewater but also in surface water and, in some cases, even in drinking or groundwater. In this paper, the degradation pathway [...] Read more.

The discovery of various sartans, which are among the most used antihypertensive drugs in the world, is increasingly frequent not only in wastewater but also in surface water and, in some cases, even in drinking or groundwater. In this paper, the degradation pathway of olmesartan acid, one of the most used sartans, was investigated by simulating the chlorination process normally used in a wastewater treatment plant to reduce similar emerging pollutants. The structures of nine isolated degradation byproducts (DPs), eight of which were isolated for the first time, were separated via chromatography column and HPLC methods, identified by combining nuclear magnetic resonance and mass spectrometry, and justified by a proposed mechanism of formation beginning from the parent drug. Ecotoxicity tests on olmesartan acid and its nine DPs showed that 50% of the investigated byproducts inhibited the target species Aliivibrio fischeri and Raphidocelis subcapitata, causing functional decreases of 18% and 53%, respectively. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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10 pages, 1520 KiB

Open AccessCommunication

Calcium Sulfite Solids Activated by Iron for Enhancing As(III) Oxidation in Water

by Minjuan Cai, Sen Quan, Jinjun Li, Feng Wu and Gilles Mailhot

Molecules 2021, 26(4), 1154; https://doi.org/10.3390/molecules26041154 - 21 Feb 2021

Cited by 3 | Viewed by 2144

Abstract

Desulfurized gypsum (DG) as a soil modifier imparts it with bulk solid sulfite. The Fe(III)–sulfite process in the liquid phase has shown great potential for the rapid removal of As(III), but the performance and mechanism of this process using DG as a sulfite [...] Read more.

Desulfurized gypsum (DG) as a soil modifier imparts it with bulk solid sulfite. The Fe(III)–sulfite process in the liquid phase has shown great potential for the rapid removal of As(III), but the performance and mechanism of this process using DG as a sulfite source in aqueous solution remains unclear. In this work, employing solid CaSO₃ as a source of SO₃²⁻, we have studied the effects of different conditions (e.g., pH, Fe dosage, sulfite dosage) on As(III) oxidation in the Fe(III)–CaSO₃ system. The results show that 72.1% of As(III) was removed from solution by centrifugal treatment for 60 min at near-neutral pH. Quenching experiments have indicated that oxidation efficiencies of As(III) are due at 67.5% to HO^•, 17.5% to SO₅^•− and 15% to SO₄^•−. This finding may have promising implications in developing a new cost-effective technology for the treatment of arsenic-containing water using DG. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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13 pages, 2208 KiB

Open AccessArticle

PFAS Degradation in Ultrapure and Groundwater Using Non-Thermal Plasma

by Davide Palma, Dimitra Papagiannaki, Manuel Lai, Rita Binetti, Mohamad Sleiman, Marco Minella and Claire Richard

Molecules 2021, 26(4), 924; https://doi.org/10.3390/molecules26040924 - 09 Feb 2021

Cited by 24 | Viewed by 5145

Abstract

Perfluoroalkyl substances (PFAS) represent one of the most recalcitrant class of compounds of emerging concern and their removal from water is a challenging goal. In this study, we investigated the removal efficiency of three selected PFAS from water, namely, perfluorooctanoic acid (PFOA), perfluorohexanoic [...] Read more.

Perfluoroalkyl substances (PFAS) represent one of the most recalcitrant class of compounds of emerging concern and their removal from water is a challenging goal. In this study, we investigated the removal efficiency of three selected PFAS from water, namely, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and pefluorooctanesulfonic acid (PFOS) using a custom-built non-thermal plasma generator. A modified full factorial design (with 2 levels, 3 variables and the central point in which both quadratic terms and interactions between couple of variables were considered) was used to investigate the effect of plasma discharge frequency, distance between the electrodes and water conductivity on treatment efficiency. Then, the plasma treatment running on optimized conditions was used to degrade PFAS at ppb level both individually and in mixture, in ultrapure and groundwater matrices. PFOS 1 ppb exhibited the best degradation reaching complete removal after 30 min of treatment in both water matrices (first order rate constant 0.107 min⁻¹ in ultrapure water and 0.0633 min⁻¹ in groundwater), while the degradation rate of PFOA and PFHxA was slower of around 65% and 83%, respectively. During plasma treatment, the production of reactive species in the liquid phase (hydroxyl radical, hydrogen peroxide) and in the gas phase (ozone, NO_x) was investigated. Particular attention was dedicated to the nitrogen balance in solution where, following to NO_x hydrolysis, total nitrogen (TN) was accumulated at the rate of up to 40 mg^N L⁻¹ h⁻¹. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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Review

Jump to: Research

20 pages, 1720 KiB

Open AccessReview

A Review of Manganese(III) (Oxyhydr)Oxides Use in Advanced Oxidation Processes

by Daqing Jia, Khalil Hanna, Gilles Mailhot and Marcello Brigante

Molecules 2021, 26(19), 5748; https://doi.org/10.3390/molecules26195748 - 22 Sep 2021

Cited by 14 | Viewed by 2754

Abstract

The key role of trivalent manganese (Mn(III)) species in promoting sulfate radical-based advanced oxidation processes (SR-AOPs) has recently attracted increasing attention. This review provides a comprehensive summary of Mn(III) (oxyhydr)oxide-based catalysts used to activate peroxymonosulfate (PMS) and peroxydisulfate (PDS) in water. The crystal [...] Read more.

The key role of trivalent manganese (Mn(III)) species in promoting sulfate radical-based advanced oxidation processes (SR-AOPs) has recently attracted increasing attention. This review provides a comprehensive summary of Mn(III) (oxyhydr)oxide-based catalysts used to activate peroxymonosulfate (PMS) and peroxydisulfate (PDS) in water. The crystal structures of different Mn(III) (oxyhydr)oxides (such as α-Mn₂O₃, γ-MnOOH, and Mn₃O₄) are first introduced. Then the impact of the catalyst structure and composition on the activation mechanisms are discussed, as well as the effects of solution pH and inorganic ions. In the Mn(III) (oxyhydr)oxide activated SR-AOPs systems, the activation mechanisms of PMS and PDS are different. For example, both radical (such as sulfate and hydroxyl radical) and non-radical (singlet oxygen) were generated by Mn(III) (oxyhydr)oxide activated PMS. In comparison, the activation of PDS by α-Mn₂O₃ and γ-MnOOH preferred to form the singlet oxygen and catalyst surface activated complex to remove the organic pollutants. Finally, research gaps are discussed to suggest future directions in context of applying radical-based advanced oxidation in wastewater treatment processes. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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25 pages, 8163 KiB

Open AccessReview

Advanced Oxidation Processes and Biotechnological Alternatives for the Treatment of Tannery Wastewater

by Néstor Andrés Urbina-Suarez, Fiderman Machuca-Martínez and Andrés F. Barajas-Solano

Molecules 2021, 26(11), 3222; https://doi.org/10.3390/molecules26113222 - 27 May 2021

Cited by 29 | Viewed by 4376

Abstract

The tannery industry is one of the economic sectors that contributes to the development of different countries. Globally, Europe and Asia are the main producers of this industry, although Latin America and Africa have been growing considerably in recent years. With this growth, [...] Read more.

The tannery industry is one of the economic sectors that contributes to the development of different countries. Globally, Europe and Asia are the main producers of this industry, although Latin America and Africa have been growing considerably in recent years. With this growth, the negative environmental impacts towards different ecosystem resources as a result of the discharges of recalcitrated pollutants, have led to different investigations to generate alternative solutions. Worldwide, different technologies have been studied to address this problem, biological and physicochemical processes have been widely studied, presenting drawbacks with some recalcitrant compounds. This review provides a context on the different existing technologies for the treatment of tannery wastewater, analyzing the physicochemical composition of this liquid waste, the impact it generates on human health and ecosystems and the advances in the different existing technologies, focusing on advanced oxidation processes and the use of microalgae. The coupling of advanced oxidation processes with biological processes, mainly microalgae, is seen as a viable biotechnological strategy, not only for the removal of pollutants, but also to obtain value-added products with potential use in the biorefining of the biomass. Full article

(This article belongs to the Special Issue Applications of Advanced Oxidation Processes for Water Treatment)

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