Catalytic oxidative degradation of 17α-ethinylestradiol by FeIII-TAML/H2O2: Estrogenicities of the products of partial, and extensive oxidation

Chen, Jian Lin; Ravindran, Shanthinie; Swift, Simon; Wright, L. James; Singhal, Naresh

doi:10.1016/j.watres.2012.09.012

Cited by 28 publications

(20 citation statements)

References 45 publications

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“…By comparing the 1 H NMR spectrum of the intermediate mixture with the measured spectra of purchased 3 , 4 and 5 and the reported data for 7 / 8 (produced via a screening TAML/peroxide EE2 oxidation)28, structural assignments were made. While ∆-9(11)-EE2 3 was present in the mixture, ∆-8(9)-EE2 4 and ∆-6(7)-EE2 5 were not.…”

Section: Resultsmentioning

confidence: 99%

Removal of ecotoxicity of 17α-ethinylestradiol using TAML/peroxide water treatment

Mills

Arias-Salazar

Baynes

et al. 2015

Sci Rep

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17α-ethinylestradiol (EE2), a synthetic oestrogen in oral contraceptives, is one of many pharmaceuticals found in inland waterways worldwide as a result of human consumption and excretion into wastewater treatment systems. At low parts per trillion (ppt), EE2 induces feminisation of male fish, diminishing reproductive success and causing fish population collapse. Intended water quality standards for EE2 set a much needed global precedent. Ozone and activated carbon provide effective wastewater treatments, but their energy intensities and capital/operating costs are formidable barriers to adoption. Here we describe the technical and environmental performance of a fast- developing contender for mitigation of EE2 contamination of wastewater based upon small- molecule, full-functional peroxidase enzyme replicas called “TAML activators”. From neutral to basic pH, TAML activators with H2O2 efficiently degrade EE2 in pure lab water, municipal effluents and EE2-spiked synthetic urine. TAML/H2O2 treatment curtails estrogenicity in vitro and substantially diminishes fish feminization in vivo. Our results provide a starting point for a future process in which tens of thousands of tonnes of wastewater could be treated per kilogram of catalyst. We suggest TAML/H2O2 is a worthy candidate for exploration as an environmentally compatible, versatile, method for removing EE2 and other pharmaceuticals from municipal wastewaters.

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Section: Resultsmentioning

confidence: 99%

Removal of ecotoxicity of 17α-ethinylestradiol using TAML/peroxide water treatment

Mills

Arias-Salazar

Baynes

et al. 2015

Sci Rep

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show abstract

“…The TP9* (m/z 314; RI 15-55%) can result from the direct attack of hydroxyl radical at position C-10 of the linked saturated ring on the EE2 structure forming monohydroxylate-derivative [33]. Chen et al [36] reported that the frontier electron density value was higher for the carbon atoms at positions 3 and 10 of the aromatic ring of EE2, with carbon at position 10 having the highest value of electron density of all the atoms in EE2. This finding is in perfect agreement with the value of the frontier electron density estimated by Ohko et al [37], on the structurally similar E2 molecule.…”

Section: Formation Of Tps and Proposed Transformation Pathways Of Ee2mentioning

confidence: 99%

UV and simulated solar photodegradation of 17α-ethynylestradiol in secondary-treated wastewater by hydrogen peroxide or iron addition

et al. 2015

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Please cite this article in press as: Z. Frontistis, et al., UV and simulated solar photodegradation of 17␣-ethynylestradiol in secondarytreated wastewater by hydrogen peroxide or iron addition, Catal. Today (2014), http://dx. a b s t r a c tThe extensive use of estrogens and their release, through various pathways, into the environment, constitutes an emerging environmental problem that poses serious threats onto public health. In this work the efficiency of UVC/H 2 O 2 and solar/Fe 2+ treatment to degrade 17␣-ethynylestradiol (EE2) in environmentally relevant concentrations of 100 g/L in secondary-treated wastewater matrices was investigated. Also, photolytic treatment was performed under different irradiation sources, namely UVC, UVA and simulated solar light. The effect of H 2 O 2 (0-20 mg/L) and Fe 2+ (0-15 mg/L) concentration was investigated and, at optimal operating parameters, EE2 removal was 100% after 15 min of UVC/H 2 O 2 treatment, while EE2 removal reached 86% after 60 min of solar/Fe 2+ treatment. In addition, the effect of water matrix and pH was studied. Total organic carbon (TOC) and yeast estrogen screening (YES) measurements showed the formation of stable intermediate products during EE2 treatment and an attempt to elucidate the reaction pathways and mechanisms through the identification of transformation products (TPs) by means of UPLC-MS/MS was made. Several TPs, including quinone methide and 1,2-quinone derivatives, were identified and competing pathways were suggested, in which hydroxylation, alkylation, dealkylation, demethylation and dehydroxylation, amongst others were described as major transformation mechanisms.

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“…Several known EDCs, such as E2 and EE2 (Shappell et al, 2008;Chen et al, 2012), fenitrothion (Chanda et al, 2006), and chlorpyrifos (Kundu et al, 2012), are reported to undergo facile degradation employing this process. Catalytic oxidation of the strong estrogenic compound EE2 with Fe-TAML (A 1 )/H 2 O 2 resulted in the epimeric intermediates 17α-ethynyl-1,4-estradiene-10α,17β-diol-3-one, and 17α-ethynyl-1,4-estra-diene-10β,17β-diol-3-one (Fig.…”

Section: Catalytic Oxidation Processesmentioning

confidence: 99%

“…Catalytic oxidation of the strong estrogenic compound EE2 with Fe-TAML (A 1 )/H 2 O 2 resulted in the epimeric intermediates 17α-ethynyl-1,4-estradiene-10α,17β-diol-3-one, and 17α-ethynyl-1,4-estra-diene-10β,17β-diol-3-one (Fig. Both the epimers were further degraded to unidentified products, which showed no estrogenicity (Chen et al, 2012;Shappell et al, 2008 Treatment of an anti-androgenic organophosphorus pesticide fenitrothion with Fe-TAML (A 2 )/H 2 O 2 resulted in partial mineralization and formation of nontoxic small molecules as end products (Fig. Both the epimers were further degraded to unidentified products, which showed no estrogenicity (Chen et al, 2012;Shappell et al, 2008 Treatment of an anti-androgenic organophosphorus pesticide fenitrothion with Fe-TAML (A 2 )/H 2 O 2 resulted in partial mineralization and formation of nontoxic small molecules as end products (Fig.…”

Section: Catalytic Oxidation Processesmentioning

confidence: 99%

Green Chemistry Principles in the Designing and Screening for Safe Chemicals and Remediation of EDCs

Khetan¹

2014

Endocrine Disruptors in the Environment

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Catalytic oxidative degradation of 17α-ethinylestradiol by FeIII-TAML/H2O2: Estrogenicities of the products of partial, and extensive oxidation

Cited by 28 publications

References 45 publications

Removal of ecotoxicity of 17α-ethinylestradiol using TAML/peroxide water treatment

Removal of ecotoxicity of 17α-ethinylestradiol using TAML/peroxide water treatment

UV and simulated solar photodegradation of 17α-ethynylestradiol in secondary-treated wastewater by hydrogen peroxide or iron addition

Green Chemistry Principles in the Designing and Screening for Safe Chemicals and Remediation of EDCs

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