Khalil Hanna

Ecole Nationale Supérieure de Chimie de Rennes · Environmental Chemistry

Predicting the fate and transport of pharmaceuticals in terrestrial environments requires knowledge of their interactions with complex mineral assemblages. To advance knowledge along this front, we examined the reactivity of pipemidic acid (PIP), a typical quinolone antibiotic, with quartz particles coated with a mixture of manganese oxide (MnO2) a...

In this study, changes in the reactivity of nanoscale zerovalent iron (NZVI) in five different groundwater (GW) systems under anoxic and oxic conditions were examined over a wide range of aging time (0−60 d). p-nitrophenol (p-NP) was used as a redox-sensitive probe, whereas nalidixic acid (NA), a typical antibiotic found in the natural environment,...

Fluoroquinolones and tetracyclines are frequently detected antibiotics in aquatic sediments. In this study, the transport of ciprofloxacin (CIP) and tetracycline (TET) was investigated in sediments from the Seine Estuary (France), under nitrate reducing conditions. Dynamic flow experiments showed that although TET and CIP strongly interacted with t...

The increasing production and broad application of engineered nanoparticles (ENPs) have led to a substantial release of ENPs into natural systems. Despite their different utilization prospects, ENPs such as nanoscale zero-valent iron (NZVI) and silver nanoparticles (AgNPs) have been co-found in aquatic environments. This study comprehensively exami...

Although the oxidative capacity of manganese oxides has been widely investigated, potential changes of the surface reactivity in dynamic anoxic/oxic environments have been often overlooked. In this study, we showed that the reactivity of layer structured manganese oxide (birnessite) was highly sensitive to variable redox conditions within environme...

Magnetite (Fe(III)2Fe(II)O4) nanoparticles are fascinating nanoparticulate minerals for their electronic, magnetic and chemical properties. Ubiquitous, in the environment, they are also among the most used ferromagnetic nanomaterials in environmental, industrial and biomedical applications. Their intriguing structural and reactivity features do not...

Fenton-based treatments have received tremendous attention in recent decades as viable strategies for soil decontamination. Historically contaminated soils are characterized by particular contamination types, pollution composition patterns, soil constituents, and complex soil-pollutant interactions arising due to long-term pollutant aging. These ma...

Although the ability of iron/sulfite system for decontamination purposes has been investigated, the complex reactive species generated and the underlying transformation mechanisms remain elusive. Here, we have comprehensively examined the transformation of iopamidol (IPM), a representative of iodinated X-ray contrast media, by iron catalyzed sulfit...

The crucial role of manganese(III) species in the oxidative and catalytic reactivity of manganese oxides have been widely reported. However, the direct activation of radical precursors by Mn(III) oxides is still a matter of discussion. In this work, the ability of Mn(III)-bearing oxide (Mn2O3) for activation of peroxydisulfate (PS) and peroxymonosu...

Dissolved silicate ions in wet and dry soils can determine the fate of organic contaminants via competitive binding. While fundamental surface science studies have advanced knowledge of binding in competitive systems, little is still known about the ranges of solution conditions, the time dependence, and the molecular processes controlling competit...

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 per‐ oxymonosulfate (PMS) and peroxydisulfate (PDS) in water. The crystal...

Although silicates are the most common anions in aquatic systems, little is known on the roles they play on the transport of emerging contaminants, such as antibiotics. Using dynamic column experiments, we revealed the controls of Si loadings on goethite (α-FeOOH) coated sands on the transport of a widely used quinolone antibiotic, here focusing on...

Despite the widespread presence of hydrogen peroxide (H2O2) in surface water and groundwater systems, little is known about the impact of environmental levels of H2O2 on the redox activity of minerals. Here we demonstrate that environmental concentrations of H2O2 can alter the reactivity of birnessite-type manganese oxide, an earth-abundant functio...

Magnetite nanoparticles, commonly found in subsurface environments, are extensively used in various applications such as environmental remediation, catalysis, electronics and medicine. However, the oxidative transformation of magnetite (mixed-valent Fe-oxide) into maghemite (Fe(III)-oxide) that drastically affects magnetic, catalytic and redox prop...

In this paper, the degradation of three endocrine-disrupting chemicals (EDCs): bisphenol A (BPA), 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) by manganite (γ-MnOOH) activated peroxymonosulfate (PMS) was investigated. Preliminary optimisation experiments showed that complete degradation of the three EDCs was achieved after 30 min of reaction u...

Development of new tools to improve the efficiency of iron minerals in promoting Fenton oxidation for environmental remediation is a highly promising field. Here, we examine for the first time the role of ascorbic acid (AA) in improving the magnetite (Fe3O4)-mediated Fenton oxidation to remove pentachlorophenol (PCP) in a historically contaminated...

Caffeine (CAF) is a stimulant commonly found in beverages and employed as the main component for producing prescription drugs. The discharging of CAF into the environment poses a threat to the aquatic environment and population health. Traditional water treatment technologies show a minimal effect on CAF removal. Therefore, it is necessary to devel...

We studied the charging of inert surfaces (polytetrafluoroethylene, i.e., PTFE; graphite; graphene; and hydrophobic silica) using classical colloid chemistry approaches. Potentiometric titrations showed that these surfaces acquired less charge from proton-related reactions than oxide minerals. The data from batch-type titrations for PTFE powder did...

Although redox reactions are recognized to fractionate iron (Fe) isotopes, the dominant mechanisms controlling the Fe isotope fractionation and notably the role of organic matter (OM) are still debated. Here, we demonstrate how binding to organic ligands governs Fe isotope fractionation beyond that arising from redox reactions. The reductive biodis...

Birnessite is a layered MnO2 mineral capable of intercalating nanometric water films in its bulk. With its variable distributions of Mn oxidation states (MnIV, MnIII, and MnII), cationic vacancies, and interlayer cationic populations, birnessite plays key roles in catalysis, energy storage solutions, and environmental (geo)chemistry. We here report...

Use of antimicrobials in the treatment and prevention of COVID-19, caused by novel coronavirus SARS-CoV-2, is on the rise. The increased use of antimicrobials can have serious consequences on the environment. Antibiotics have had a reasonable role in bacterial co-infections with regards to the management of COVID-19. However, recent evidences sugge...

While the oxidative capacity of nanostructured birnessite-type manganese oxide has been widely investigated, no comprehensive work exists on the combined effects of dissolved Mn(II), pH and inorganic anions on sorption and redox reactions of organic contaminants with MnO2. Herein, we have showed how molecular interactions of two contrasting organic...

Despite the extensive use of nanoscale zerovalent iron (NZVI) in water and soil remediation, no data exist on the reactivity of secondary iron minerals formed upon the NZVI corrosion. Herein, we investigated the oxidation kinetics of NZVI by monitoring the variations of pH, oxidation–reduction potential (ORP) and dissolved Fe(II) concentration, and...

The fractionation of natural organic matter (NOM) and its impact on the binding of quinolones to mineral surfaces and transport behaviour under flow-through conditions have been scarcely investigated. In this study, the sorption and transport of a widely used quinolone antibiotic, Nalidixic acid (NA), were investigated in goethite-coated sand (GCS)...

Although the use of ferrate (VI), an emerging green oxidant, has been widely investigated to remove organic pollutants in water, its ability to remediate contaminated soils has been scarcely evaluated. Here, we explore the use of ferrate (VI) to degrade a polychlorinated persistent compound, the pentachlorophenol (PCP), in aqueous solution and in a...

In this study, a novel peroxymonosulfate (PMS) activation method, which combines a solid waste (i.e., red mud, RM) and a reducing agent (i.e., hydroxylamine, HA), for the oxidative degradation of fluoroquinolones (FQs; i.e., flumequine (FLU) and ciprofloxacin (CIP)) in hospital wastewater (HW) was developed. The addition of HA into the PMS/RM suspe...

In this study, we examined the removal kinetics of two fluoroquinolones (FQs), flumequine (FLU) and ciprofloxacin (CIP), in synthetic (SWW) and real hospital wastewaters (RHW) using FeOx thin films, peroxymonosulfate (PMS) and visible light. Nano-sized iron oxides (FeOx) supported on polyester textile (PES) were synthesized by a novel high-power im...

Existence of SARS-CoV-2 in wastewater has potential implications for environmental transmission of COVID-19 particularly in developing communities. ............................................................................................................................................. Full text of this article has been provided below.

Manganese oxides have been proposed as promising geomedia to remove trace organic contaminants in both natural soils and artificial infiltration systems. Although MnO x -based redox processes have been largely investigated, little is known on the effects of water flow and dissolved MnII on manganese-mediated redox reactions in saturated porous medi...

While the use of transition metal oxides in catalyzing advanced oxidation reactions has been widely investigated, very few reports have focused on how the preliminary contact of oxides with target compounds may affect the succession of reaction. In this study, we examined the adsorption and electron transfer reactions of two fluoroquinolones, flume...

Removal of two widely used antibiotics, flumequine (FLU) and ciprofloxacin (CIP), in synthetic and real hospital wastewaters was investigated using Fe-doped zinc oxide (Fe-ZnO) and UVA irradiation. The Fe-ZnO was supported on cellulose acetate membrane and integrated in a recirculation reactor system, designed for continuous oxidative treatment of...

It is shown here that ZVI-Fenton is a suitable technique to achieve effective degradation of ibuprofen and phenol under several operational conditions. Degradation of ibuprofen was possible in the pH interval 3-6 in both synthetic laboratory systems and actual wastewater (secondary treatment effluent), but operation at the higher pH values required...

The mobility of pharmaceuticals in environmental systems is under great scrutiny in the scientific literature and in the press. Still, very few reports have focused on redox-driven transformations when these compounds are bound to mineral surfaces, and how their transport is affected under flow-through conditions. In this study, we examined the ads...

In Situ Chemical Oxidation (ISCO) can be applied to soils contaminated by polyaromatic hydrocarbons (PAHs). PAH degradation yields are often rather low, because of different obstacles not clearly understood. These include the low availability of PAHs, the type and age of soil organic matter and the carbonate content of the soil. The aim of this wor...

Processes based on chemical oxidation are widely used for environmental remediation. Analysis of environmental samples such as soils often requires a freeze-drying step prior to the measurement of the concentration of contaminants. However, the effect of freezing on the quantification of the removal efficiency is poorly known. Here we studied the r...

Atmospheric water vapor binding to soils is a key process driving water availability in unsaturated terrestrial environments. Using a representative hydrophilic iron oxyhydroxide, this study highlights key mechanisms through which water vapor (i) adsorbs and (ii) condenses at mineral surfaces coated with Leonardite humic acid (LHA). Microgravimetry...

Heterogeneous catalysts for the oxidation of toxic compounds are extremely important for many applications including environmental remediation. Here, we assessed the ability of Ti-substituted magnetite, i.e., titanomagnetite (Fe III(2-2x) Fe II(1+x) Ti x O 4 ) to promote Fenton-like heterogeneous reactions. Two titanomagnetites with x values respec...

The assessment of antibiotics mobility under seawater conditions has been rarely studied, since an accurate description of such multicomponent systems is quite challenging. In this study, the adsorption of a widely used quinolone antibiotic in aquaculture, Oxolinic acid (OA), to a synthetic goethite (α-FeOOH) was examined in presence of major (e.g....

Nanoscale zerovalent iron (NZVI) is one of the most extensively studied nanomaterials in the fields of wastewater treatment and remediation of soil and groundwater. However, rapid oxidative transformations of NZVI can result in reduced NZVI reactivity. Indeed, the surface passivation of NZVI is considered one of the most challenging aspects in succ...

Oil hydrocarbons are widespread pollutants in sub-surface sediments with serious threats to terrestrial and aquatic environment. However, very limited data is available about remediation of historically contaminated sediments. This study reports the use of magnetite-catalyzed chemical oxidation (H2O2 and Na2S2O8) to degrade oil hydrocarbons in aged...

Ferrate (Fe(VI)) has emerged as an efficient oxidant to treat organic pollutants in aqueous solution. However, its application has never been assessed to remediate the contaminated soils. Here, we report the first study to use Fe (VI) for chemical oxidation of PCBs in historically contaminated soils obtained from an industrial wasteland. The first...

Nanoparticle (NP) stability in aqueous environments is dependent upon many parameters including environmental conditions, NP concentrations as well as NP intrinsic characteristics. In this study, the effects of pH and surface modifications on the colloidal and chemical stabilities of nanosized magnetite (Fe3O4), maghemite (γ-Fe2O3) and hematite (α-...

While the magnetite stoichiometry (i.e. Fe(II)/Fe(III) ratio) has been extensively studied for the reductive transformation of chlorinated or nitroaromatic compounds, no work exists examining the influence of stoichiometry of magnetite on its binding properties. This study, for the first time, demonstrates that the stoichiometry strongly affects th...

Although several emerging contaminants (e.g. fluoro(quinolones) (FQs)) have been simultaneously detected in environmental systems, there is very limited information on their elimination from contaminated waters in multi-component systems. In this study, removal of three FQs including flumequine (FLU), ciprofloxacin (CIP) and norfloxacin (NOR) were...

Although there is a growing interest in Fenton oxidation processes based on natural catalysts, the use of laterite soil to promote sequential adsorption/oxidation treatments of fluoroquinolone antibiotics has been scarcely investigated. In this work, the ability of an african laterite containing goethite and hematite to remove flumequine (FLU), use...

Magnetite is one of the most well characterized and facilitated iron oxide in a variety of research and industrial fields. Especially, its easy separation by magnetism has attracted a great attention to use as a support material for various noble metallic catalysts. Here, we report for the first time that bare polycrystalline magnetite can show a r...

Although emerging contaminants rarely exist individually in environmental contaminated systems, only limited information on their adsorption mechanisms in multi-components solutions is currently available. To address this shortcoming, this work examines for the first time the accuracy of a surface complexation model in predicting the cooperative ad...

The catalytic properties of nanoparticles (e.g., nano zero valent iron, nZVI) have been used to effectively treat a wide range of environmental contaminants. Emerging contaminants such as endocrine disrupting chemicals (EDCs) are susceptible to degradation by nanoparticles. Despite extensive investigations, questions remain on the transformation me...

The emergence of antibiotic and anti-inflammatory agents in aquatic and terrestrial systems is becoming a serious threat to human and animal health worldwide. Because pharmaceutical compounds rarely exist individually in nature, interactions between various compounds can have unforeseen effects on their binding to mineral surfaces. This work demons...

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg(-1)) and γ-HCH (lindane, 25 mg kg(-1)) was sampled from former lindane waste storage site. Efficiency of following treatments was tested...

Although there is a growing interest in environmentally friendly catalytic processes based on magnetic solids, the reactivity of titanomagnetite (Fe3-xTixO4) having a “tunable” solid-state Fe(II)/Fe(III) ratio for reductive transformation of nitroaromatic compounds has been never investigated. This study, for the first time, comprehensively examine...

In this research, magnetite and ethylenediamine-N,N′-disuccinic acid (EDDS) are used in a heterogeneous photo-Fenton system in order to find a new way to remove organic contaminants from water. Influence of different parameters including magnetite dosage, EDDS concentration, H2O2 concentration, and pH value were evaluated. The effect of different r...

In this study the oxidation of pentachlorophenol (PCP) in an aged contaminated soil was performed under both water-unsaturated and water-saturated conditions using potassium permanganate (PM), potassium persulfate (PS) and hydrogen peroxide (HP). Overall, the results of PCP removal extent and oxidant decomposition indicated that the water content i...

Fenton oxidation constitutes a viable remediation strategy to remove polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. This review is intended to illustrate major limitations associated with this process like acidification, PAH unavailability, and deterioration of soil quality along with associated factors, followed by a critical descr...

In this study, the activation of persulfate induced by Fe(III) species, including 5 kinds of iron oxhydroxides (IOs) and dissolved Fe³⁺ under dark condition were investigated. Ferrihydrite (FH) and akaganeite (AK) showed the highest activity in 4-tert-butylphenol (4tBP) removal. The 4tBP degradation rate constant decreased as the solution pH increa...

The paper of Zhu et al. [1] is of great interest, since it reported adsorption data of Eu(III) onto pyrrhotite, an uninvestigated solid surface to date. We are of the opinion that the system is of relevance in the context of nuclear waste disposal in deep repositories. In the study, Eu(III) is used as an analogue for trivalent actinides and pyrrhot...

The vulnerability of Zero-Valent Iron (ZVI) to passivation, which significantly decreases its surface reactivity, limits its use as a reducing agent in environmental remediation applications (e.g., permeable reactive barriers). Passivation of ZVI occurs rapidly in ambient environments due to the presence of oxygen and water, as well as during the r...

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe0, Fe/Ni, Fe3O...

Background: The activated sludge treatments combined to the addition of ferric chloride is commonly used to eliminate nitrate and phosphate from waste water in urban area. These processes that need costly infrastructures are not suitable for rural areas and passive treatments (lagoons, reed bed filters…) are more frequently performed. Reed bed filt...

The reduction of p-Nitrophenol (p-NP) to p-Aminophenol (p-AP) by nanoscale zero-valent iron (NZVI)/NaBH4 system in an oxygen environment was studied by means of liquid chromatography, spectroscopy (vibration and X-ray photoelectron), solid analyses (transmission electron microscopy and X-ray diffraction) and density functional theory (DFT) calculat...

The reduction of p-Nitrophenol (p-NP) to p-Aminophenol (p-AP) by nanoscale zero-valent iron (NZVI)/NaBH4 system in an oxygen environment was studied by means of liquid chromatography, spectroscopy (vibration and X-ray photoelectron), solid analyses (transmission electron microscopy and X-ray diffraction) and density functional theory (DFT) calculat...

Oxolinic acid (OA) is a widely used quinolone antibiotic in aquaculture. In this study, its interactions with synthetic goethite (-FeOOH) and akaganéite (-FeOOH) particle surfaces were monitored to understand the potential fate of OA in marine sediments where these phases occur. Batch sorption experiments, liquid chromatography (LC) analyses of s...

This is the premier study designed to evaluate the impact of thermal pre-treatment on the availability of polycyclic aromatic hydrocarbons (PAHs) for successive removal by chemical oxidation. Experiments were conducted in two soils having different PAH distribution originating from former coking plant sites (Homécourt, H, and Neuves Maisons, NM) lo...

In this study the activation of persulfate induced by Fe(III)-ethylenediamine-N,N'-disuccinic acid (EDDS) under dark and irradiation conditions and the reactivity of the generated sulfate radical (SO4●-) under a wide range of experimental conditions were investigated by means of experimental kinetic analyses and modelling. The Fe(III)-EDDS induced...

Adsorption of antibiotics at mineral surfaces has been extensively studied over the past 20 years, yet much remains to be learned on their interfacial properties and transformation mechanisms. In this study, interactions of Ciprofloxacin (CIP), a fluoroquinolone antibiotic with two sets of synthetic nanosized hematite particles, with relatively smo...

While most published studies used buffers to maintain the pH, there is limited knowledge regarding the reactivity of nanoscale zero-valent iron (NZVI) in poorly buffered pH systems to date. In this work, the effect of pH and Fe(II) dissolution on the reactivity of NZVI was investigated during the reduction of 4-nitrophenol (4-NP) in unbuffered pH s...