Oxidation Processes in Water Treatment PDF

Oxidation processes in water treatment: matrix effects – pollutant degradation – microbial interactions Holger Lutze et al. 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 1  Students meet Business Was/what: Kontaktbörse für Studierende und Unternehmen Get together with f...

Oxidation processes in water treatment: matrix effects – pollutant degradation – microbial interactions Holger Lutze et al. 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 1  Students meet Business Was/what: Kontaktbörse für Studierende und Unternehmen Get together with firms Wann/when: Dienstag, 11. Juni 2024 um 15:00 Uhr Tuesday, 11. June 2024 at 15:00 Wo/were: altes BI-Gebäude (Lichtwiese) L5|01 in Raum 32 Old Engineering Building (Lichtwiese) Weber Ingenieure Evonik L5|01 in Raum 32 Hydroingenieure Skion Hochschule Darmstadt Fachschafft 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 2  Holger Lutze Work experiences Since 2008 Scientific advisor at IWW Water Centre Mülheim a. d. Ruhr 2008 – 2020 Researcher at University Duisburg-Essen PhD in Chemistry at University Duisburg- Essen (2013) 2013-2020 Head of the research group “Oxidation Processes” at Instrumental Analytical Chemistry department at University Duisburg-Essen 2013 PhD in Chemistry 2007 MSc Eawag Aquatic Research/ CH 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 3  Holger V. Lutze Expert committees Since 2022: Head of the main committee fundamentals and applications Water Chemistry Society 2013-2019: Organization of the conference „Wasser“ Annual meeting of the Water Chemistry Society Topics (Presentations and Posters (1. Dez. 2023) Wastewater treatment processes Drinking water treatment and distribution Analytical methods Detection/occurrence of nanoparticles and microplastics Hygiene and microbiology Modern bioanalytical procedures Detection/occurrence of natural/anthropogenic (pollutant) substances River systems, lakes/dams and groundwater (Eco)toxicological methods/studies Climate change: impact on water management Marine chemistry https://www.wasserchemische-gesellschaft.de Standardization 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 4  Holger V. Lutze Expert committees Since 2022: Head of the main committee fundamentals and applications Water Chemistry Society 2013-2019: Organization of the conference „Wasser“ Annual meeting of the Water Chemistry Society Topics (Presentations and Posters (1. Dez. 2023) Wastewater treatment processes Drinking water treatment and distribution Analytical methods Detection/occurrence of nanoparticles and microplastics Hygiene and microbiology Modern bioanalytical procedures Detection/occurrence of natural/anthropogenic (pollutant) substances River systems, lakes/dams and groundwater (Eco)toxicological methods/studies Climate change: impact on water management Marine chemistry https://www.wasserchemische-gesellschaft.de Standardization 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 5 Water Chemistry Society 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 6 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 7 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 8 The group Environmental Analytics and Pollutants started at February 2020 Picture, Sommer 2023 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 9  Connections 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 10  Oxidation processes in water treatment a success story 2012 Persistent Chemicals Persitent compounds: PFAS PFAS, Pesticides and their metabolites von Gunten, U. (2008). Can the quality of drinking water be taken for granted? Eawag News, 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 11 65e, 4–7. (modified) Pollutant, Environment and water chemistry https://www.scinexx.de/ https://scitechdaily.com/ 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 12  Pollutant, Environment and water chemistry Good guess Identified compounds Wang et al (2021) https://doi.org/10.1021/acs.est.0c05984 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 13  Perfluorinated compounds https://www.sueddeutsche.de/gesundheit/pfas-umwelt-gift- 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 14 jahrhundertgift-lobbyismus-pfas-verbot-1.5773961?reduced=true Perfluorinated compounds Lipophob Hydrophob Dirt repellant Surfactant Chemically highly inert Features Water/dirt/lipid repellant e.g., in textiles Fire fighting foams Non sticking coating (dishes, paper, food container and many more)) Waxes (Ski) Pesticide formulations Applications Persistent, bioaccumulative, potentially toxic Problem 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 15 PFC release form Düsseldorf airport 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 16  Announcement of the ministry of environment in Düsseldorf Perfluorinated compounds are present in ground water in low concentrations, but above the recommended standard of 100 ngL-1 No direct toxic risk Drinking water not affected Usage of groundwater for garden watering may cause PFC to enrich in soil, plants, fruits, crops. Chronic exposure may affect human health The free use of ground water is forbidden until 30.4.2034 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 18 The Research Wheel Aim Apply Correct Learn 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 19 The Research Wheel Aim A sophisticated Apply product Coatings (Chemically organic Surfactants compound Wetting agents Repels water, dirt, color, lipids) Corrective Learn action Spread into the Water Replacement whole, with Persistent Soil polyfluorinated Bioaccumlative Atmosphere compounds Toxic Biota Food Breast milk Blood serum 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 20 PFC replacements Degrade in the environment Perfluortelomers form 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 21 perffluorinated carboxylic acids The Research Wheel Apply Coatings Aim Surfactants Degradable) Wetting agents Corrective action Learn Forms PFC ??? Hi again… It may become your task to find a solution 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 22  Concentrations Trace pollutants are in the µg L-1 range and below They may still have an effect at that concentration. At traces pollutants can be found nearly everywhere 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 23  Experimental Lake Area (ELA) 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 24  Addition of Ethinylestradiol to experimental lakes 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 25 Impact of Micropollutants: test of estrotenic effect of 17-ethinylestradiol (EE2) Experimental Lake Area (Canada) 17-Ethinylestradiol (EE2) Increase of production of vitellogenin (VTG) mRNA Female → VTG gene is present in males and activated by EE2 → VTG gene activity is enhanced in female upon EE2 addition → Proof of estrogenic activity of EE2 → Estrogenic activity reduces chances of reproduction (intersex) Male Dickkopfelritze (https://de.wikipedia.org/wiki/Pimephales_promelas) 05.06.2024 | Fachbereich 13 | InstitutKaren IWAR A. | Prof. KiddDr. etLutze | 26 al. PNAS 2007;104:21:8897-8901 Impact of Micropollutants: Fish Feminization in a Canadian Lake CPUE: Trap-net catch- per-unit-effort Or: Catch of each fishing trip divided by fishing hours → Fishing efficiency (A) reference Lake 442 (B) Lake 260 (amended with 5–6 ng·L−1 of EE2 in 2001–2003) during the fall of 1999–2005. Karen A. Kidd et al. PNAS 2007;104:21:8897-8901 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 27  A Coruña Spain; MCPA from roof run-off Trace pollutants in small natural waters Wastewater marker (treated or untreated) 30 0,60 Average concentration / µgL-1 Number of positive samples 25 0,50 Marker for 20 untreated wastewater 0,40 15 0,30 10 0,20 5 0,10 0 Terbuthylazine-… Terbuthylazine-… 0,00 Chloridazon-… Chloridazon-… Dimethachlor… Metazachlor Carbamazepine Caffeine Diuron Mecoprop Terbutryn Metazachlor-ESA Bromacil Dimethenamid-P Tebuconazole Imidacloprid Metazachlor-OA MCPA Isoproturon Metribuzin 1,2,3-Benzotriazole Metamitron-desamino Diclofenac Icaridine acid Trace pollutants Rossbach; Land use mainly agriculture, point sources; Stormwater discharge and 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 28 wastewater effluent; Auslaugungsexperimente; Herkunft von MCPA 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 29  30 Ozonation of wastewater in NRW (decision in progress) since 2009 Conventional treatment Ozonation Nutrient control Pollutant control DU-Vierlinden Schwerte Bad Sassendorf Trade of in oxidaton processes Pro Contra Disinfection By-products (bromate, Color removal Nitrosamines in case of Pollutant control ozone) Transformation products Costs 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 31  Advanced wastewater ozonation Diclofenac 1,2 20 Trace compound / c/c0 Bromate / µg-1 1 15 0,8 0,6 10 0,4 5 0,2 0 0 0 0,2 0,4 0,6 0,8 1 Ozone dose [mgO3/mgDOC] O3 (k = 6.8 × 105 M-1 s-1; pH 7) Sein et al. 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 32  Advanced wastewater ozonation Diclofenac 4-Methylbenzotriazole 1,2 20 1,2 20 Trace compound / c/c0 Bromate / µg-1 Trace compound/ c/c0 Bromate / µg-1 1 1 15 15 0,8 0,8 0,6 10 0,6 10 0,4 0,4 5 5 0,2 0,2 0 0 0 0 0 0,2 0,4 0,6 0,8 1 0 0,2 0,4 0,6 0,8 1 Ozone dose [mgO3mgDOC) Ozone dose [mgO3/mgDOC] O3 (k = 2.5 × 103 M-1 s-1) 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 33  Advanced wastewater ozonation Diclofenac 4-Methylbenzotriazole 1,2 20 1,2 20 Trace compound / c/c0 Bromate / µg-1 Trace compound/ c/c0 Bromate / µg-1 1 1 15 15 0,8 0,8 0,6 10 0,6 10 0,4 0,4 5 5 0,2 0,2 0 0 0 0 0 0,2 0,4 0,6 0,8 1 0 0,2 0,4 0,6 0,8 1 Ozone dose [mgO3mgDOC) Ozone dose [mgO3/mgDOC] O3 (k = 3 × 105 M-1 s-1) Carbamazepine 1,2 20 Spurenstoff / c/c0 Bromate / µg-1 1 15 0,8 0,6 10 0,4 5 0,2 0 0 0 0,2 0,4 0,6 0,8 1 Ozone dose [mgO3/mgDOC] 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 34  Advanced wastewater ozonation No reactive structure towards ozone, Degradation via intrinsic formation of Secondary oxidant Org. hydroxyl radicals possible O3 matter O3 - OH NOM +O2 O3 O2 - Fluconazole 1,5 20 Bromate / µg-1 Trace compound /c/c0 15 1 10 0,5 5 0 0 0 0,2 0,4 0,6 0,8 1 Ozone dose / mgO3/mgDOC 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 35  Transformation processes Precursor /Parent compound Transformation Product Feature Change in structure, not in New feature Does not fly well the material Can fly Toxicity 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 36  Transformation processes Precursor /Parent compound Transformation Product Feature Change in structure, not in New feature Does not fly well the material Can fly Taste & Odor 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 37  Transformation processes Precursor /Parent compound Transformation Product Feature Change in structure, not in New feature Does not fly well the material Can fly Biodegradability Biological processes 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 38  Transformation processes Precursor /Parent compound Transformation Product Feature Change in structure, not in New feature Does not fly well the material Can fly Biodegradability Chemical oxidation 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 39 Treatment, degradation: e.g., Taste and odor compounds e.g., Cucumber odor e.g., fruity odor trace concentrations Increased solubility in water Trace concentrations cannot be percepted 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 40  Effects of transformation: Endocrines pH < 5 Removal of endocrine activity 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 41 41 Knoop, O., Woermann, M. Lutze, H. V., Sures, B., Schmidt, T.C.- HAZMAT Toxic transformation products: NDMA, a strong carcinogenic compound O O CH3 S N H3C N CH3 S CCl2F Biological transformation carcinogen Dimethylsulfaminde N-nitrosodimethylamine (NDMA) (Drinkingwater standard 10 ng L-1) (von Gunten et al., (2010) ES&T 44(15), 5762-5768. (Schmidt & Brauch (2008) ES&T 42(17), 6340-6346 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 42 Toxic NDMA in a real drinking water treatment plant (Schmidt & Brauch (2008) ES&T 42(17), 6340-6346 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 43  Oxidative wastewater treatment Todays challenges in wastewater treatment Anthropogenic pollutants Pathogens Bromate BDOC carbonyls Wastewater Environment Ozonation Transformation- and byproducts 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 44 44  Oxidative wastewater treatment Todays challenges in wastewater treatment Anthropogenic pollutants Pathogens ClO2- Carbonyls Wastewater Environment Transformation- and ClO2 byproducts 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 45 45  Model compounds k / M-1 s-1 Atenolol (Ateno) ClO2 ≈ 1 O3 = 104 Metoprolol (Meto) ClO2 ≈ 1 O3 = 2 × 104 Dimethyl-1H- Benzotriazole ClO2 = 0.5 (DMBT) O3 ≈ 104 ClO2 =1 × 103 Sulfamethoxazole O3 = 5 × 105 (SMX) 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 46 Lee & von Gunten (2010), Terhalle et al. (2018) Wastewater ozonation Wastewater parameters: DOC: 8.3 mg L-1 pH: 7.8 Bromide: 225 µg L-1 Compound degradation: > 80% O3-dose: (0.5 g O3) / (g DOC) Bromate formation: below 10 µg L-1 (drinking water standard) Treatment with ozone was successful Terhalle 05.06.2024 et al.(2018)13ES&T | Fachbereich 52(17), | Institut IWAR | 9964-9971. Prof. Dr. Lutze | 47  ClO2 treatment of wastewater DOC: 8.3 mg L-1 pH: 7.8 Bromide: 225 µg L-1 k(SMX + ClO2) = 103 M-1 s-1 k(ClO2 + Atenolol & Metoprolol) < 1 M-1 s-1 k(ClO2 + Dimethylbenzotriazole)< 1 M-1 s-1 ClO2 NOM k(HOCl) = 104 M-1 s-1 (pH 7) Atenolol (& Metoprolol) Terhalle 05.06.2024 et al.(2018)13ES&T | Fachbereich 52(17), | Institut IWAR | 9964-9971. Prof. Dr. Lutze | 48  Reactions of chlorine dioxide with organic matter ClO2 k ≈ 105 M-1 s-1 HOCl? k < 6 M-1 s-1 k ≈ 101 -102 M-1 s-1 k < 5 M-1 s-1 Kinetics from: Abdighahroudi et al. (2021). 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 49 Comprehensive Analytical Chemistry. 92: 51-83. Reaction of phenol with chlorine dioxide k = 0.5 M-1 s-1 k = 107 M-1 s-1 100 y = -0.5x + 91 Concentration [µM] 80 60 40 20 0 0 20 40 60 80 100 120 140 chlorine dioxide dose [µM] phenol Stoichiometry: 2 ClO2 consumed per 1 phenol degraded Wajon et. al. (1982) 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 50 Reaction of phenol with chlorine dioxide k = 0.5 M-1 s-1 k = 107 M-1 s-1 100 y = -0.5x + 91 y = 0.5x – 2.6 Concentration [µM] 80 60 40 20 0 0 20 40 60 80 100 120 140 chlorine dioxide dose [µM] chlorit phenol Stoichiometry: 2 ClO2 consumed per 1 phenol degraded Chlorite yield: 1 Chlorite per 2 ClO2 consumed (50% yield) Wajon et. al. (1982) 05.06.2024 | Fachbereich 13 | Institut IWAR | Prof. Dr. Lutze | 51  Determination of intrinsic free chlorine using a selective scavenger Determination by ion UV-signal at 352 nm chromatography (ε = 26000 M-1 cm-1) Excess RNHCl + 3I- + H+ → RNH2 + Cl- + I3- Abdighahroudi et al., 2020 05.06.2024 | Fachbereich Analytical 13 | Institut IWAR | and Bioanalytical Prof. Dr. Lutze | 52 Chemistry 412(28):  Addition of ClO2 Chlorat DOC: 5 mgL-1 (SRNOM) FAC pH : 7 120 ClO22 2/% Chlorid Chlorit Phosphate buffer: 5 mM addedClO ClO 100 abreagierten Nearly Ideal ratio 1:1 Chlorite : HOCl proadded 80 40% 60 >90% of ClO2 reacted with chlorine forming per moieties (probably methyl phenols) per Ausbeute 40 %Yield 60%