THESE Pour l’obtention du Grade de DOCTEUR DE L’UNIVERSITE DE POITIERS (ECOLE NATIONALE SUPERIEURE d’INGENIEURS de POITIERS) (Diplôme National - Arrêté du août 2006) Ecole Doctorale : Sciences pour l’Environnement Gay Lussac Secteur de Recherche : CHIMIE ET MICROBIOLOGIE DE L’EAU Présenté par : Thai Ha TRAN ************************ Adsorption and oxidation of micropollutants by Manganese oxide ************************ Soutenance prévue le 14 Décembre 2015 devant la Commission d’Examen ************************ JURY Rapporteurs : M Philippe BEHRA M Emmanuel GUILLON Examinateurs : M Patrick MAZELLIER M Sylvain OUILLON Directeurs de Thèse : M Hervé GALLARD M Jérôme LABANOWSKI ************************ ACKNOWLEDGEMENTS I wish to thanks my advisors Hervé GALLARD and Jérôme LABANOWSKI for directing their attentions forward to my work and welfare, and for allowing me freedom and flexibility in research Working with them is my honor Their advices helped me to develop scientific skills and will be useful for my future career I would also like to thank those who encouraged me to enter this work: my father, my mother, my wife and my little daughter, my whole family Their supports are always the best thing for me A number of fellow students and associates contributed to this work trough their supports, advice and friendship: Alice TAWK, Virginie SIMON, Pamela ABDALLAH, Rose-Michelle SMITH, Amal YOUSSOUF IBRAHIM, and many others I wish to thank Philippe BEHRA, Emmanuel GUILLON, Patrick MAZELLIER, Sylvain OUILLON They kindly served on my examining committees Their comments and enthusiasm were appreciated The staff of equip E1-Eaux Géochimie Santé and Platform APTEN went to great lengths to assist with whatever problems arose, especially Audrey ALLAVENA, Sylvie LIU, Marie DEBORDE Financial support from Vietnamese project 911 is gratefully appreciated ii CONTENTS List of Figures vi List of Tables x General introduction Chapter I: Literature review I.1 Fate of organic micropollutants in the environment I.2 Geochemistry and Manganese oxides mineralogy .6 I.2.1 Tunnel structure I.2.2 Layer structure I.2.2.1.Birnessite .9 I.2.2.2.Others layer structures 11 I.2.3 Other Mn oxides minerals .11 I.3 Interactions between Manganese oxides and organic compounds 12 I.3.1 Reaction Models .13 I.3.1.1.Electron-transfer with bond-formation between metal sites and organic reductant .14 I.3.1.2.Electron-transfer through formation of outer-sphere complex between metal sites and organic reductant 14 I.3.2 Transformation reactions 15 I.3.2.1.Reactions with model organic compounds 15 I.3.2.1.1.Phenols 16 I.3.2.1.2.Anilines .17 I.3.2.1.3.Low molecular weight carboxylic acids .19 I.3.2.2.Reactions with organic contaminants 19 I.3.2.2.1.Endocrine discruptors 19 iii I.3.2.2.2.Antibacterial agents and antibiotics 21 I.3.2.2.3.Other pharmaceuticals and industrial contaminants 25 I.3.2.3.Reactions with natural organic matter 26 I.3.3 Kinetic aspects and influence of reaction conditions 28 I.3.3.1.Kinetics and reaction order 28 I.3.3.2.Effect of pH 30 I.3.3.3.Effect of mineral constituents 31 I.3.4 The role of NOM in NOM – micropollutants – MnO2 system 32 I.3.4.1.Interactions between NOM and micropollutants .32 I.3.4.2.Effect of NOM on reaction of micropollutants by MnO2 34 I.4 Application in water treatment and decontamination of polluted sites 36 Chapter II: Material and methods and preliminary study 39 II.1 Manganese dioxide and reagents 39 II.1.1 Preparation of Manganese dioxide and characterization 39 II.1.2 Natural organic matters and micropollutants 40 II.2 II.2.1 Protocols 43 Kinetic experiments with MnO2 suspensions .43 II.2.2 Sorption experiments of NIS by NOM .44 II.3 Analysis of micropollutants 44 II.4 Identification of transformation products 45 II.5 Natural Organic matter characterization by Dissolved organic carbon and UV absorbance analysis and high-pressure size exclusion chromatography 46 II.6 Results from preliminary study .49 Chapter III: Adsorption and oxidation of the anthelmintic drug Niclosamide by birnessite 50 III.1 Introduction .50 iv III.2 Results and discussion 52 III.3 Conclusion 68 Chapter IV: Sorption and transformation of Pyrantel pamoate by synthetic birnessite70 IV.1 Introduction 70 IV.2 Results and discussion 71 IV.3 Conclusion .81 Chapter V: Oxidative transformation of triketone herbicide, sulcotrione, by manganese oxide: kinetic, transformation products and impact of natural organic matter 83 V.1 Introduction 83 V.2 Results and discussion 85 V.3 Conclusion 99 Chapter VI: Degradation of Sulfamethoxypyridazine and cross-coupling reactions mediated by MnO2 100 VI.1 Introduction 100 VI.2 Results and discussion 102 VI.3 Conclusion 118 GENERAL CONCLUSION 120 v List of Figures Chapter I Figure I.1 – Schematic diagram highlighting potential sources and pathways for groundwater pollution by micropollutants Adapted from [18] Figure I.2 – Cristalline structure of (A) Pyrolusite, (B) Ramsdellite, (C) Hollandite, (D) Romanecdite, and (E) Todorokite [42] Figure I.3 – Cristal structure of (A) Lithiophorite, (B) Chalcophanite, (C) Na-rich Birnessite like [42] 11 Figure I.4 – General view of transformation of organic compound by MnO2 13 Figure I.5 – Major reactions involved in the oxidation of phenols by δ-MnO2 and accumulation of reduced Mn species on the mineral surface The final aqueous products are shown in blue [32] 16 Figure I.6 – Postulated mechanism for oxidative coupling of aniline by reactions with manganese oxide The reaction proceeds from a cation radical through coupling products, which then undergo further oxidation Adapted from [77] 18 Figure I.7 – Transformation of citrate by MnO2 19 Figure I.8 – Proposed reaction pathway of oxidation of triclosan by MnO2 [63] 21 Figure I.9 – Proposed Reaction Scheme for Oxidation of FQs by MnO2 [106] 23 Figure I.10 – Proposed mechanism for the oxidative transformation of DCF by manganese oxide [112] 26 Figure I.11 – Cross-coupling of sulfamethazine with syringic acid [41] 27 Figure I.12 – Impact of NOM on oxidation and hydrolysis of micropollutant by MnO2 Adapted from [119] 34 Chapter II Figure II.1 – Zeta potential of Manganese oxide suspension for pH range 2.5 – 6.0 and ionic strengths of and 10 mM NaNO3 40 Figure II.2 – HPSEC calibration curve obtained with polystyrene sulfonate standards 47 Figure II.3 – Typical HPSEC chromatograms for the three different NOM extracts 48 Chapter III Figure III.1 – Concentration profiles of NIS after centrifugation or reduction by ascorbic acid ([NIS]o = 130 nM , 10 mM acetate buffer pH 5.0) 53 Figure III.2 – Proposed pathway for the catalytic hydrolysis of NIS by MnO2 55 Figure III.3 – Linear adsorption isotherms of Niclosamide at pH 4.0, 4.5, 5.0 and 5.5 57 Figure III.4 – First-order kinetic representation of NIS transformation for different MnO2 concentrations (pH 5.0, 10 mM acetate buffer) 59 Figure III.5 – First-order dependence with respect to MnO2 at pH 5.0 60 Figure III.6 – Dependence of k with respect to H+ (10 mM acetate buffer, 130 nM [NIS]0 and 100 µM [MnO2]0) 62 Figure III.7 – Evolution of NIS concentration in the absence and presence of CR-NOM 64 Figure III.8 – Effect of CR-NOM concentration on (a) observed rate constants of NIS transformation and (b) adsorption isotherms (pH 5.0, 175 µM MnO2 and 130 nM NIS) 65 Figure III.9 – Changes in 2D fluorescence spectra of CR-NOM with increasing NIS concentration 66 Figure III.10 – Application of Stern-Volmer model for interaction between NIS and NOM (pH 5.0±0.1 and 22±1 °C, 2.2 mg-C L-1, 255/400 nm excitation/emission wavelengths) 67 Figure III.11 – HPSEC/UV chromatograms of 2.0 mgC L-1 NOM before and after contact with 500 µM MnO2 at pH 5.0 68 vii Chapter IV Figure IV.1 – Behaviour of Pyrantel Pamoate in presence of birnessite ([MnO]2 = 500 µM, [PMA]0 = 260 nM, [PYR]0 = 260 nM 10 mM acetate buffer pH 5.0) 72 Figure IV.2 – Influence of initial concentrations of MnO2 on removal of PMA ([PMA]0 = 260 nM, pH 5.0, 10 mM acetate buffer) 73 Figure IV.3 – First-order dependence with respect to MnO2 73 Figure IV.4 – Dependence of kobs with respect to H+ concentration 75 Figure IV.5 – Effect of SR-NOM on oxidation of PMA by MnO2 76 Figure IV.6 – Proposed reaction pathway for the degradation of PMA by MnO2 77 Figure IV.7 – Concentration profile of PYR in presence of MnO2 after quenching by ascorbic acid or centrifugation 79 Figure IV.8 – Sorption isotherm of PYR by MnO2 at pH 5.0 80 Figure IV.9 – Effect of NOM on sorption kinetic of PYR by MnO2 ([MnO2]0 = mM, pH 5.0, [NOM]0 = 0.5 mgC L-1) 81 Chapter V Figure V.1 – Degradation kinetics of triketone herbicides tembotrione and sulcotrione by MnO2 85 Figure V.2 – Influence of quenching mode on kinetics of SCT oxidation by MnO2 ([MnO2]o = 217 µM; [SCT]o = 6.3 µM; pH 5.0 10 mM acetate buffer) 86 Figure V.3 – First order representation of SCT degradation for different MnO2 concentrations ([SCT]o = 6.3 µM; pH 5.0 10 mM acetate buffer) 87 Figure V.4 – First-order dependence with respect to MnO2 89 Figure V.5 – Dependence of k with respect to H+ 90 Figure V.6 – Effect of NOMs isolates on SCT transformation by MnO2 91 Figure V.7 – Effect of NOM concentration on observed rate constants of SCT transformation 92 Figure V.8 – HPSEC-UV chromatograms of SR-NOM before and after contact with birnessite 93 viii Figure V.9 – Reaction pathway for SCT transformation by MnO2 98 Chapter VI Figure VI.1 – Influence of quenching mode on the time profile of SMP in presence of MnO2 ([MnO2]0 = 250 µM; [SCT]0 = 1.2 µM; pH 5.0 10 mM acetate buffer) 102 Figure VI.2 – Logarithmic representation of SMP transformation by birnessite showing deviation from first order ([SMP]o = 1.1 µM; pH 5.0 10 mM acetate buffer) 103 Figure VI.3 – Determination of the order of the initial reaction rate of SMP degradation 106 Figure VI.4 – Retarded model fit for reaction of SMP oxidation by MnO2 109 Figure VI.5 – Effect of different concentrations of CR-NOM on transformation of SMP by MnO2 (The curves are the retarded model fit) 111 Figure VI.6 – Effect of syringic additions on SMP degradation by MnO2 113 Figure VI.7 – Proposed pathway for SMP transformation by MnO2 117 Figure VI.8 – Cross-coupling reaction between SMP and SYR mediated by MnO2 118 ix List of Tables Chapter I Table I.1 – Nomenclature and chemical formula of some manganese oxides [42] Table I.2 – Proposed methods for synthesis of Birnessite 10 Table I.3 – Summary of model phenols, anilines and low molecular weight (LMW) acids used to dissolve manganese oxides [33], [75]–[77] 15 Table I.4 – Reaction order for the transformation of various organic compounds by MnO2 29 Chapter II Table II.1 – Physico-chemical properties of micropollutants tested in this study 42 Table II.2 – Experimental conditions used in this study 43 Table II.3 – Conditions used for the analysis of micropollutants by HPLC/UV 45 Chapter III Table III.1 – MS spectra of NIS and its transformation products 56 Table III.2 – Pseudo-First order 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from degradation of PMA by MnO2 Figure S.2 – MS2 spectra of product A2 produced from PMA degradation by MnO2 Figure S.3 – MS2 spectra MS2 of product A3 produced from PMA degradation by MnO2 138 Figure S.4 – Mass spectra MS2 of product S1 of SCT degradation by MnO2 Figure S.5 – Mass spectra MS2 of product S2 of SCT degradation by MnO2 Figure S.6 – Mass spectra MS2 of product S3 of SCT degradation by MnO2 139 Figure S.7 – Mass spectra MS2 of product S4 of SCT degradation by MnO2 Figure S.8 – Mass spectra MS2 of product S5 of SCT degradation by MnO2 Figure S.9 - Mass spectra MS2 of product P1 of SMP degradation by MnO2 140 Figure S.10 - Mass spectra MS2 of product P2 of SMP degradation by MnO2 Figure S.11 - Mass spectra MS2 of product P3 of SMP degradation by MnO2 Figure S.12 - Mass spectra MS2 of product P4 of SMP degradation by MnO2 141 Figure S.13 - MS2 spectra of product P5 produced from SMP degradation by MnO2 Figure S.14 - MS2 spectra of product CrC1 of SMP-SYR coupling mediated by MnO2 Figure S.15 - MS2 spectra of product CrC1 of SMP-SYR coupling mediated by MnO2 142 [...]... methods for synthesis of Birnessite Methods Oxidation manganous hydroxide Procedure Ref of A mixture of 0.4 moles of manganous sulfate and 5.5 moles of described potassium hydroxide in two litres of water was cooled to 5°C by and oxidized by bubbling oxygen for 5 hours This produced a McKenzie black birnessite containing 9.0% K, with a surface area of 75 [50] m2g-1 Reduction of Two moles of concentrated... [59], ciprofloxacin [60] and benzoic acid [61]) Both adsorption and transformation of macrolides [62], triclosan and chlorophen [63], tetracycline [64], [65] were also reported Reduction of manganese oxides by ascorbic or oxalic acids and separation by centrifugation or filtration are used to determine the amount of organic compounds adsorbed onto MnO2 surface and transformed by MnO2 The reduction of MnO2... transformed by manganese oxides via the following steps: (1) Sorption of organic compounds onto oxide surfaces, (2) formation of a precursor surface complex, (3) hydrolysis and/ or electron transfer inside the complex to form transformation producs and Mn2+, (4) the formed product can be sorbed or desorbed and possibly further transformed by manganese oxides The sorption capacity of manganese oxides without... values of BPA were 70, 38 and 16 min respectively in presence of 15, 30 and 60 g L-1 manganese oxide- coated sand (MOCS) More than 99% of BPA was eliminated in 6 min at pH 4.5 with 800 µM birnessite suspension and 4.4 19 µM BPA [99] Pure aqueous MnO2 suspension showed faster degradation of BPA than MOCS The oxidation of BPA by MnO2 formed ten oxidation products [99] Radical coupling produced dimers and. .. 17β-estradiol (E2), estrone (E1) and estriol (E3) are also susceptible to oxidation by manganese oxides EE2 underwent oxidation by granular MnO2 in upstream bioreactors Almost 81.7% of EE2 (15 µg L-1) was removed after 40 days of treatment [102] δ-MnO2 was also capable of degrading E2, E1 and E3 at similar rates of reaction compared to EE2 [103] The oxidation of E2 by δ-MnO2 was also investigated in... to investigate the reactivity of Mn oxides [33], [78], [79] Mn oxides were well dissolved with an excess amount of phenols The reaction mechanism of the oxidation of phenols by manganese oxides is illustrated by Figure I.5 This mechanism was first described by Stone et al [33], [76], [78] and would proceed according to the following steps: (i) first step is diffusion of organics into the boundary layer... Geochemistry and Manganese oxides mineralogy Manganese is one of the most abundant elements in the earth and the second transition metal after iron present in the earth’s crust [42]–[44] Humanity has started using manganese for thousand years as pigment in cave and to clarify glass Nowadays manganese is mostly used as catalysts and for the production of battery [45] There are more than 30 Mn oxides/hydroxide... Interactions between Manganese oxides and organic compounds Manganese oxides rank among the strongest natural oxidant in soil and sediments [32], [53] The standard reduction potential of MnO2 at pH 7 and 25°C is 1.29 V [53] (equation (I.1)) With large surface area up to 270 m2 g-1 (Table I.2), manganese oxides can sorb and further transform organic micropollutants via direct oxidation [33] and/ or surface... hydrophobicity of triclosan and chlorophene may contribute to higher adsorption to manganese oxide than the related substituted phenols since previous work has shown that adsorption of chlorophenols to manganese oxide increases as the compound's Kow increases The higher adsorption to manganese oxide may lead to more surface precursor complex formation and thus faster reaction rate [63] A series of fluoroquinolone... oxides/hydroxide minerals, and many of them occur abundantly in a wide variety of geological settings In addition to being important as ores of Mn metal, they also play an active role in the environmental geochemistry at the Earth’s surface Manganese oxides and hydroxides are important constituents of the soil and sediments, and because they are highly chemically active and strong scavengers of heavy metals, ... the adsorption of NOM onto manganese oxides [120] The adsorption of NOM is the initial stage followed by the reduction of manganese oxides The electron transfer is accompanied by the formation of. .. transformation of DCF by manganese oxide [112] I.3.2.3 Reactions with natural organic matter The sorption and oxidation of Natural Organic Matter (NOM) by manganese oxides were first reported by Stone... reactivity of Mn oxides [33], [78], [79] Mn oxides were well dissolved with an excess amount of phenols The reaction mechanism of the oxidation of phenols by manganese oxides is illustrated by Figure