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Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents

BACKGROUND: This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (le...

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Autores principales: Fayad, Paul B, Zamyadi, Arash, Broseus, Romain, Prévost, Michèle, Sauvé, Sébastien
Formato: Online Artículo Texto
Lenguaje:English
Publicado: BioMed Central 2013
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3671215/
https://www.ncbi.nlm.nih.gov/pubmed/23675917
http://dx.doi.org/10.1186/1752-153X-7-84
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author Fayad, Paul B
Zamyadi, Arash
Broseus, Romain
Prévost, Michèle
Sauvé, Sébastien
author_facet Fayad, Paul B
Zamyadi, Arash
Broseus, Romain
Prévost, Michèle
Sauvé, Sébastien
author_sort Fayad, Paul B
collection PubMed
description BACKGROUND: This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. RESULTS: The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M(-1) sec(-1) in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M(-1) sec(-1) in ultrapure water and 26 to 149 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M(-1) sec(-1) in ultrapure water and 180 to 368 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L(-1) after contact times of 10 to 60 min. CONCLUSION: This work presents the first results on the permanganate-promoted oxidation of progestagens, as a function of pH, temperature as well as NOM. Progestagen concentrations used to determine rate constants were analyzed using an ultrafast laser diode thermal desorption interface coupled to tandem mass spectrometry for the analysis of water sample for progestagens.
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spelling pubmed-36712152013-06-10 Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents Fayad, Paul B Zamyadi, Arash Broseus, Romain Prévost, Michèle Sauvé, Sébastien Chem Cent J Research Article BACKGROUND: This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. RESULTS: The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M(-1) sec(-1) in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M(-1) sec(-1) in ultrapure water and 26 to 149 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M(-1) sec(-1) in ultrapure water and 180 to 368 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L(-1) after contact times of 10 to 60 min. CONCLUSION: This work presents the first results on the permanganate-promoted oxidation of progestagens, as a function of pH, temperature as well as NOM. Progestagen concentrations used to determine rate constants were analyzed using an ultrafast laser diode thermal desorption interface coupled to tandem mass spectrometry for the analysis of water sample for progestagens. BioMed Central 2013-05-15 /pmc/articles/PMC3671215/ /pubmed/23675917 http://dx.doi.org/10.1186/1752-153X-7-84 Text en Copyright © 2013 Fayad et al.; licensee Chemistry Central Ltd. http://creativecommons.org/licenses/by/2.0 This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Article
Fayad, Paul B
Zamyadi, Arash
Broseus, Romain
Prévost, Michèle
Sauvé, Sébastien
Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents
title Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents
title_full Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents
title_fullStr Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents
title_full_unstemmed Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents
title_short Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents
title_sort degradation of progestagens by oxidation with potassium permanganate in wastewater effluents
topic Research Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3671215/
https://www.ncbi.nlm.nih.gov/pubmed/23675917
http://dx.doi.org/10.1186/1752-153X-7-84
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