Overlooked Formation of H2O2 during the Hydroxyl Radical-Scavenging Process When Using Alcohols as Scavengers.

Hydroxyl radical (•OH) is an active species widely reported in studies across many scientific fields, and hence, its reliable analysis is vitally important. Currently, alcohols are commonly used as scavengers for •OH determination. However, the impacts of alcohols on the reliability of •OH detection remain unknown. In this study, we found that adding different types and different amounts of alcohols in water samples treated with ultraviolet irradiation undesirably produced substantial amounts of hydrogen peroxide (H2O2), which is a known •OH precursor. This means that the conventional •OH determination method using alcohols is likely unreliable or even misleading. Through careful investigation, we revealed an overlooked reaction pathway during H2O2 and •OH transformations. Varying oxygen concentrations, pHs, alcohol dosages, and types altered H2O2 formation, which can affect •OH determination accuracy. Among alcohols, n-butanol is the best scavenger because it quenches •OH rapidly but re-forms little H2O2.

[1]  Min Sik Kim,et al.  Occurrence of unknown reactive species in UV/H2O2 system leading to false interpretation of hydroxyl radical probe reactions. , 2021, Water research.

[2]  Liuyan Yang,et al.  Photodegradation of carbon dots cause cytotoxicity , 2021, Nature communications.

[3]  Baiyang Chen,et al.  Generation of hydroxyl radicals during photodegradation of chloroacetic acids by 254 nm ultraviolet: A special degradation process revealed by a holistic radical determination methodology. , 2020, Journal of hazardous materials.

[4]  J. D. de Gouw,et al.  Satellite isoprene retrievals constrain emissions and atmospheric oxidation , 2020, Nature.

[5]  A. Thompson,et al.  Iron-mediated organic matter decomposition in humid soils can counteract protection , 2020, Nature Communications.

[6]  Jun Ma,et al.  Some issues limiting photo(cata)lysis application in water pollutant control: A critical review from chemistry perspectives. , 2020, Water research.

[7]  Jun Ma,et al.  Understanding and modeling the formation and transformation of hydrogen peroxide in water irradiated by 254 nm ultraviolet (UV) and 185 nm vacuum UV (VUV): Effects of pH and oxygen. , 2019, Chemosphere.

[8]  S. Zou,et al.  DBP alteration from NOM and model compounds after UV/persulfate treatment with post chlorination. , 2019, Water research.

[9]  D. Sedlak,et al.  The Role of Reactive Nitrogen Species in Sensitized Photolysis of Wastewater-Derived Trace Organic Contaminants. , 2019, Environmental science & technology.

[10]  D. Bahnemann,et al.  Modeling and Optimization of the Photocatalytic Reduction of Molecular Oxygen to Hydrogen Peroxide over Titanium Dioxide , 2018, ACS Catalysis.

[11]  Qian-Yuan Wu,et al.  Potential risks from UV/H2O2 oxidation and UV photocatalysis: A review of toxic, assimilable, and sensory-unpleasant transformation products. , 2018, Water research.

[12]  Juan Gao,et al.  Contribution of alcohol radicals to contaminant degradation in quenching studies of persulfate activation process. , 2018, Water research.

[13]  Guan Zhang,et al.  A Comparison of Photodegradation Kinetics, Mechanisms, and Products between Chlorinated and Brominated/Iodinated Haloacetic Acids in Water , 2017 .

[14]  Baiyang Chen,et al.  A Facile, Nonreactive Hydrogen Peroxide (H2O2) Detection Method Enabled by Ion Chromatography with UV Detector. , 2017, Analytical chemistry.

[15]  Yanbin Li,et al.  Role of Free Radicals/Reactive Oxygen Species in MeHg Photodegradation: Importance of Utilizing Appropriate Scavengers. , 2017, Environmental science & technology.

[16]  M. Stefan Advanced Oxidation Processes for Water Treatment - Fundamentals and Applications , 2017 .

[17]  Xuhong Guo,et al.  Carbon dioxide radical anion-based UV/S2O82−/HCOOH reductive process for carbon tetrachloride degradation in aqueous solution , 2017 .

[18]  H. Kjaergaard,et al.  Hydroxyl radical-induced formation of highly oxidized organic compounds , 2016, Nature Communications.

[19]  L. Wojnárovits,et al.  The influence of radical transfer and scavenger materials in various concentrations on the gamma radiolysis of phenol , 2016 .

[20]  W. Mitch,et al.  Halogen radicals contribute to photooxidation in coastal and estuarine waters , 2016, Proceedings of the National Academy of Sciences.

[21]  S. Gligorovski,et al.  Environmental Implications of Hydroxyl Radicals ((•)OH). , 2015, Chemical reviews.

[22]  Henry J Sun,et al.  Evidence for photochemical production of reactive oxygen species in desert soils , 2015, Nature Communications.

[23]  Shuwen Yan,et al.  Photochemically induced formation of reactive oxygen species (ROS) from effluent organic matter. , 2014, Environmental science & technology.

[24]  Arlene M. Fiore,et al.  Atmospheric chemistry: No equatorial divide for a cleansing radical , 2014, Nature.

[25]  Chao Tai,et al.  Methylmercury photodegradation in surface water of the Florida Everglades: importance of dissolved organic matter-methylmercury complexation. , 2014, Environmental science & technology.

[26]  Xianliang Qiao,et al.  Estimation of Aqueous‐Phase Reaction Rate Constants of Hydroxyl Radical with Phenols, Alkanes and Alcohols , 2009 .

[27]  L. Sanche Biological chemistry: Beyond radical thinking , 2009, Nature.

[28]  Janina A. Rosso,et al.  Thermally activated peroxydisulfate in the presence of additives: a clean method for the degradation of pollutants. , 2009, Chemosphere.

[29]  S. Goldstein,et al.  Photolysis of aqueous H2O2: quantum yield and applications for polychromatic UV actinometry in photoreactors. , 2007, Environmental science & technology.

[30]  M. D. Gurol,et al.  Degradation of tert-butyl alcohol in dilute aqueous solution by an O3/UV process. , 2004, Environmental science & technology.

[31]  Yikui Du,et al.  The Measure of TiO2 Photocatalytic Efficiency and the Comparison of Different Photocatalytic Titania , 2003 .

[32]  H. Schuchmann,et al.  Photolysis of ozone in aqueous solutions in the presence of tertiary butanol. , 2003, Environmental science & technology.

[33]  André M. Braun,et al.  Vacuum-UV (172 nm) Actinometry. The Quantum Yield of the Photolysis of Water , 1998 .

[34]  A. Puchalski,et al.  Quenching of triplet ketones by alcohol hydroxy bonds , 1980 .

[35]  C. Sonntag,et al.  Hydroxyl radical-induced oxidation of 2-methyl-2-propanol in oxygenated aqueous solution. A product and pulse radiolysis study. [Gamma radiation] , 1979 .

[36]  D. Schulte‐Frohlinde,et al.  The Bimolecular Decay of the α - Hydroxymethylperoxyl Radicals in Aqueous Solution , 1978 .

[37]  A. Henglein,et al.  Pulse radiolytic study of the site of hydroxyl radical attack on aliphatic alcohols in aqueous solution , 1973 .

[38]  J. Weeks,et al.  The Primary Quantum Yield of Hydrogen Peroxide Decomposition1 , 1956 .