Destruction of dioxin and furan pollutants via electrophilic attack of singlet oxygen

Nassim Zeinali, Ibukun Oluwoye, Mohammednoor Altarawneh, Bogdan Z. Dlugogorski

    Research output: Contribution to journalArticleResearchpeer-review

    Abstract

    Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) remain of particular concern owing to their extensive toxicity towards health and accumulation in the environment. Atmospheric oxidation (by ambient oxygen molecules) of this class of persistent environmental pollutants has little to no kinetic feasibility due to very sizable activation energies in the entrance channel. The current control measures involve energy-intensive source incineration of contaminated materials at high temperatures as high as 850 °C. This study finds an alternative low-energy approach of destroying dioxin-like compounds, proposing that advanced oxidation by highly reactive singlet oxygen (O2 1Δg, originated from chemical, surface-mediated and photochemical processes) can initiate low-temperature remediation of these pollutants. This contribution completes the first milestone in mapping out the mechanisms of the electrophilic addition of singlet oxygen to unsubstituted and chlorinated dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) structures, according to density functional theory DFT-B3LYP method in conjunction with the 6–311+g(d,p) basis set, as well as energy refinements based on the approximate spin-projection scheme. The [2+2]-cycloaddition mechanism appears dominant for singlet oxidation of dibenzo-p-dioxin with a fitted rate constant of k(T) = 5.01 × 10−14 exp(-98000/RT). On the other hand, the addition of singlet oxygen to the aromatic ring of dibenzofuran primarily transpires via [4+2]-cycloaddition channel with a fitted rate constant of k(T) = 2.16 × 10−13 exp(-119000/RT). The results suggest that application of singlet oxygen can reduce the energy cost of recycling halogenated and flame retarded materials.

    Original languageEnglish
    Article number109605
    Pages (from-to)1-7
    Number of pages7
    JournalEcotoxicology and Environmental Safety
    Volume184
    DOIs
    Publication statusPublished - 30 Nov 2019

    Fingerprint

    Singlet Oxygen
    Dioxins
    Oxygen
    Cycloaddition Reaction
    Theophylline
    Cycloaddition
    Photochemical Processes
    Oxidation
    Incineration
    Rate constants
    Environmental Pollutants
    Temperature
    Recycling
    Electric current control
    Remediation
    Discrete Fourier transforms
    Density functional theory
    Toxicity
    Costs and Cost Analysis
    Activation energy

    Cite this

    Zeinali, Nassim ; Oluwoye, Ibukun ; Altarawneh, Mohammednoor ; Dlugogorski, Bogdan Z. / Destruction of dioxin and furan pollutants via electrophilic attack of singlet oxygen. In: Ecotoxicology and Environmental Safety. 2019 ; Vol. 184. pp. 1-7.
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    abstract = "Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) remain of particular concern owing to their extensive toxicity towards health and accumulation in the environment. Atmospheric oxidation (by ambient oxygen molecules) of this class of persistent environmental pollutants has little to no kinetic feasibility due to very sizable activation energies in the entrance channel. The current control measures involve energy-intensive source incineration of contaminated materials at high temperatures as high as 850 °C. This study finds an alternative low-energy approach of destroying dioxin-like compounds, proposing that advanced oxidation by highly reactive singlet oxygen (O2 1Δg, originated from chemical, surface-mediated and photochemical processes) can initiate low-temperature remediation of these pollutants. This contribution completes the first milestone in mapping out the mechanisms of the electrophilic addition of singlet oxygen to unsubstituted and chlorinated dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) structures, according to density functional theory DFT-B3LYP method in conjunction with the 6–311+g(d,p) basis set, as well as energy refinements based on the approximate spin-projection scheme. The [2+2]-cycloaddition mechanism appears dominant for singlet oxidation of dibenzo-p-dioxin with a fitted rate constant of k(T) = 5.01 × 10−14 exp(-98000/RT). On the other hand, the addition of singlet oxygen to the aromatic ring of dibenzofuran primarily transpires via [4+2]-cycloaddition channel with a fitted rate constant of k(T) = 2.16 × 10−13 exp(-119000/RT). The results suggest that application of singlet oxygen can reduce the energy cost of recycling halogenated and flame retarded materials.",
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    Destruction of dioxin and furan pollutants via electrophilic attack of singlet oxygen. / Zeinali, Nassim; Oluwoye, Ibukun; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.

    In: Ecotoxicology and Environmental Safety, Vol. 184, 109605, 30.11.2019, p. 1-7.

    Research output: Contribution to journalArticleResearchpeer-review

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    T1 - Destruction of dioxin and furan pollutants via electrophilic attack of singlet oxygen

    AU - Zeinali, Nassim

    AU - Oluwoye, Ibukun

    AU - Altarawneh, Mohammednoor

    AU - Dlugogorski, Bogdan Z.

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    AB - Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) remain of particular concern owing to their extensive toxicity towards health and accumulation in the environment. Atmospheric oxidation (by ambient oxygen molecules) of this class of persistent environmental pollutants has little to no kinetic feasibility due to very sizable activation energies in the entrance channel. The current control measures involve energy-intensive source incineration of contaminated materials at high temperatures as high as 850 °C. This study finds an alternative low-energy approach of destroying dioxin-like compounds, proposing that advanced oxidation by highly reactive singlet oxygen (O2 1Δg, originated from chemical, surface-mediated and photochemical processes) can initiate low-temperature remediation of these pollutants. This contribution completes the first milestone in mapping out the mechanisms of the electrophilic addition of singlet oxygen to unsubstituted and chlorinated dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) structures, according to density functional theory DFT-B3LYP method in conjunction with the 6–311+g(d,p) basis set, as well as energy refinements based on the approximate spin-projection scheme. The [2+2]-cycloaddition mechanism appears dominant for singlet oxidation of dibenzo-p-dioxin with a fitted rate constant of k(T) = 5.01 × 10−14 exp(-98000/RT). On the other hand, the addition of singlet oxygen to the aromatic ring of dibenzofuran primarily transpires via [4+2]-cycloaddition channel with a fitted rate constant of k(T) = 2.16 × 10−13 exp(-119000/RT). The results suggest that application of singlet oxygen can reduce the energy cost of recycling halogenated and flame retarded materials.

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