Destruction of Estrogens Using Fe-TAML/Peroxide Catalysis

Abstract

Endocrine disrupting chemicals (EDCs) impair living organisms by interfering with hormonal processes controlling cellular development. Reduction of EDCs in water by an environmentally benign method is an important green chemistry goal. One EDC, 17R-ethinylestradiol (EE 2 ), the active ingredient in the birth control pill, is excreted by humans to produce a major source of artificial environmental estrogenicity, which is incompletely removed by current technologies used by municipal wastewater treatment plants (MWTPs). Natural estrogens found in animal waste from concentrated animal feeding operations (CAFOs) can also increase estrogenic activity of surface waters. An iron-tetraamidomacrocyclic ligand (Fe-TAML) activator in trace concentrations activates hydrogen peroxide and was shown to rapidly degrade these natural and synthetic reproductive hormones found in agricultural and municipal effluent streams. On the basis of liquid chromatography tandem mass spectrometry, apparent half-lives for 17 R-and 17 β-estradiol, estriol, estrone, and EE 2 in the presence of Fe-TAML and hydrogen peroxide were approximately 5 min and included a concomitant loss of estrogenic activity as established by E-Screen assay.

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)–kinetics and mechanisms: A review

“…In the past several years, iron-tetraamidomacrocyclic ligand (Fe-TAML) catalysts have been developed, which in trace amounts activates hydrogen peroxide to produce reactive intermediates, Fe IV ¼ O and Fe V ¼ O (Chanda et al, 2006(Chanda et al, , 2008a(Chanda et al, , 2008bCollins, 2002;Collins et al, 2009;Ghosh et al, 2008;Tiago de Oliveira, 2007). This system was successfully applied to degrade numerous pollutants (Chahbane et al, 2007;Shappell et al, 2008). Examples include degradation of estrogens, bisphenols, and Orange II dye and inactivation of bacterial spores (Chahbane et al, 2007;Horwitz et al, 2006;Malecky et al, 2006;Shappell et al, 2008).…”

“…This system was successfully applied to degrade numerous pollutants (Chahbane et al, 2007;Shappell et al, 2008). Examples include degradation of estrogens, bisphenols, and Orange II dye and inactivation of bacterial spores (Chahbane et al, 2007;Horwitz et al, 2006;Malecky et al, 2006;Shappell et al, 2008). Toxicity tests of the oxidation reactions showed non-toxic products (Chahbane et al, 2007;Shappell et al, 2008).…”

The Impact of Surfactants on FeIII–TAML‐Catalyzed Oxidations by Peroxides: Accelerations, Decelerations, and Loss of Activity

“…[4] However, Table 4. Equilibrium and rate constants for the second k II step of Fe III -TAML-catalyzed oxidation of Sudan III by tBuOOH in micellar media, which was obtained by fitting experimental data to Equations (8), (9), and (11) at 25 8C and 0.1 m.…”

“…[3][4][5][6][7][8][9] The catalytic activity of 1 is comparable to that of enzymes that use H 2 O 2 as a source of oxidation equivalents. [4,10] Accordingly, Fe III -TAML activators are promising green oxidation catalysts, [11] which sometimes function in the presence of surfactants.…”

Chemistry and Applications of Iron–TAMLCatalysts in Green Oxidation Processes Based on Hydrogen Peroxide

“…Similarly, natural estrogens found in animal waste from concentrated animal feeding operations (CAFOs) can also increase estrogenic activity of surface waters [71]. A 1a-H 2 O 2 treatment rapidly degraded 17a-and 17b-estradiol (E 2 ), estriol (E 3 ), estrone (E 1 ) and 17a-ethinylestradiol (EE 2 ) (Scheme 3.22), with apparent half-lives of approximately 5 min, and included a concomitant loss of estrogenic activity as established by E-Screen assay [72]. The study highlights the extremely low concentrations at which Fe-TAML catalysts can function, both in the amount of catalyst required and with trace quantities of substrates.…”