Identifying the mechanisms of cation inhibition of phenol oxidation by acid birnessite

Balgooyen, Sarah; Remucal, Christina K.; Ginder‐Vogel, Matthew

doi:10.1002/jeq2.20144

Cited by 6 publications

(10 citation statements)

References 69 publications

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“…In contrast, initial E 2 :E 3 values only significantly correlate with percent changes in E 2 :E 3 ( p = 0.047), indicating that apparent molecular weight of DOM is not a major predictor of its reactivity. Furthermore, although sulfate and ionic strength may influence the reactivity of manganese oxides ,− and DOM, ,,,,, they are not correlated with measured parameters in these samples.…”

Section: Resultsmentioning

confidence: 81%

Selective Reactivity and Oxidation of Dissolved Organic Matter by Manganese Oxides

Trainer

Ginder‐Vogel

Remucal

2021

Environ. Sci. Technol.

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Dissolved organic matter (DOM) varies widely across natural and engineered systems, but little is known about the influence of DOM composition on its reactivity with manganese oxides. Here, we investigate bulk and molecular transformations of 30 diverse DOM samples after reaction with acid birnessite (MnO 2 ), a strong oxidant that may react with DOM in Mn-rich environments or engineered treatment systems. The reaction of DOM with acid birnessite reduces Mn and forms DOM that is generally more aliphatic and lower in apparent molecular weight. However, the extent of reaction depends on the water type (e.g., wastewater, rivers) and highly aromatic DOM undergoes greater changes. Despite the variability in reactivity due to the DOM composition, aqueous products attributable to the oxidation of phenolic precursors are identified in waters analyzed by highresolution mass spectrometry. The number of matched product formulas correlates significantly with indicators of DOM aromaticity, such as double-bond equivalents (p = 2.43 × 10 −4 ). At the molecular level, highly aromatic, lignin-like carbon reacts selectively with acid birnessite in all samples despite the variability in initial DOM composition, resulting in the formation of a wide range of aqueous products. These findings demonstrate that DOM oxidation occurs in diverse waters but also suggest that reactivity with acid birnessite and the composition of the resulting aqueous DOM pool are composition-dependent and linked to the DOM source and initial aromaticity.

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Section: Resultsmentioning

confidence: 81%

Selective Reactivity and Oxidation of Dissolved Organic Matter by Manganese Oxides

Trainer

Ginder‐Vogel

Remucal

2021

Environ. Sci. Technol.

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“…Taking into account that oxidation is most likely preceded by sorption of I – on the surface so that electron transfer can take place, electrostatic repulsion may hinder the interaction. δ-MnO 2 is a mineral with different pH pzc values between its edge sites and vacancy sites, 6–8 and 2–3, respectively . This would give δ-MnO 2 both localized positive and negative sites in different regions of the mineral, allowing I – to be capable of sorbing at edge sites, but perhaps not on the vacancy site, which would lead to a moderate level of I – oxidation (Figure a).…”

Section: Resultsmentioning

confidence: 99%

“…δ-MnO 2 is a mineral with different pH pzc values between its edge sites and vacancy sites, 6−8 and 2−3, respectively. 38 This would give δ-MnO 2 both localized positive and negative sites in different regions of the mineral, allowing I − to be capable of sorbing at edge sites, but perhaps not on the vacancy site, which would lead to a moderate level of I − oxidation (Figure 1a). This is consistent with electron transfer between birnessite and anions occurring exclusively on the edge sites.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Transformations and Speciation of Iodine in the Environment as a Result of Oxidation by Manganese Minerals

Szlamkowicz

Fentress

Longen

et al. 2022

ACS Earth Space Chem.

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The fate and transport of iodine in the environment is contingent upon the presence of manganese oxides and the geochemical controls they exert. The oxidation of iodide by manganese oxides, mainly α-Mn 2 O 3 , was studied in the pH range 4−6. In the case of α-Mn 2 O 3 , the oxidation of iodide (I − ) was observed to stop at iodine (I 2 ), rather than fully oxidizing to iodate (IO 3 − ). The oxidation reaction followed an observed second order kinetics and increase of ionic strength incurred a decrease in the oxidation of I − to I 2 . Additionally, the calcium sorption on α-Mn 2 O 3 does not influence the oxidation of I − , indicating that cation sorption does not interfere with the sorption of I − at the anion vacancy active sites on the mineral surface. The formation of I 2 in aqueous systems is important as it may lead to different reaction pathways for the fate and transport of iodine in the environment, such as sorption of I 2 on natural substrates, as well as the volatilization of I 2 into the atmosphere, or the formation of iodinated organic compounds. The formation of I 2 from I − is most extensive under acidic conditions. The results of the present study indicate a strong geochemical control of manganese oxides over the oxidation and subsequent fate of iodine in the environment, which needs to be considered for studies related to iodine mobility or remediation of iodine impacted systems.

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“…Anions were not considered due to repulsive electrostatic interactions between the negatively charged acid birnessite and anions. 26,28,85,86 Kinetic reactions using a nonspecific radical quencher tertbutanol 87−91 were conducted to explore the role of radicalmediated reactions in enhancing the rate of bisphenol A oxidation using water samples from DL1, DL2, and WW1. tert-Butanol (50 mM) was used as it is not likely to react with manganese oxides and does not alter the mineral surface.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…13,26−28 This trend is attributable to the stronger sorption of divalent cations to manganese oxide surfaces compared to that of monovalent cations. 13,26,31 Furthermore, divalent cations can interact with other organic compounds in solution, such as dissolved organic matter (DOM), to form complexes or increase DOM sorption to mineral surfaces (Figure S1). 32 DOM is a mixture of organic molecules found in natural and engineered systems 38−43 and can also impact phenolic compound oxidation by manganese oxides.…”

Section: ■ Introductionmentioning

confidence: 99%

Influence of Divalent Cation Inhibition and Dissolved Organic Matter Enhancement on Phenol Oxidation Kinetics by Manganese Oxides

Swenson,

Ginder-Vogel,

Remucal

2024

Environ. Sci. Technol.

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Manganese oxides can oxidize organic compounds, such as phenols, and may potentially be used in passive water treatment applications. However, the impact of common water constituents, including cations and dissolved organic matter (DOM), on this reaction is poorly understood. For example, the presence of DOM can increase or decrease phenol oxidation rates with manganese oxides. Furthermore, the interactions of DOM and cations and their impact on the phenol oxidation rates have not been examined. Therefore, we investigated the oxidation kinetics of six phenolic contaminants with acid birnessite in ten whole water samples. The oxidation rate constants of 4-chlorophenol, 4-tertoctylphenol, 4-bromophenol, and phenol consistently decreased in all waters relative to buffered ultrapure water, whereas the oxidation rate of bisphenol A and triclosan increased by up to 260% in some waters. Linear regression analyses and targeted experiments demonstrated that the inhibition of phenol oxidation is largely determined by cations. Furthermore, quencher experiments indicated that radical-mediated interactions from oxidized DOM contributed to enhanced oxidation of bisphenol A. The variable changes between compounds and water samples demonstrate the challenge of accurately predicting contaminant transformation rates in environmentally relevant systems based on experiments conducted in the absence of natural water constituents.

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Identifying the mechanisms of cation inhibition of phenol oxidation by acid birnessite

Cited by 6 publications

References 69 publications

Selective Reactivity and Oxidation of Dissolved Organic Matter by Manganese Oxides

Selective Reactivity and Oxidation of Dissolved Organic Matter by Manganese Oxides

Transformations and Speciation of Iodine in the Environment as a Result of Oxidation by Manganese Minerals

Influence of Divalent Cation Inhibition and Dissolved Organic Matter Enhancement on Phenol Oxidation Kinetics by Manganese Oxides

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