Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents

Chemistry Central Journal

Paul B Fayad²  Arash Zamyadi¹  Romain Broseus¹  Michèle Prévost¹  Sébastien Sauvé² 

[1] Department of Civil, Geological and Mining Engineering, École Polytechnique de Montréal, Montreal, QC, Canada

[2] Department of Chemistry, Université de Montréal, Montreal, QC, Canada

关键词: Kinetic rate constant;    Endocrine disruptors;    LDTD-APCI-MSMS;    Steroid hormones;    Potassium permanganate;    Oxidation;   

Others  :  787909
DOI  :  10.1186/1752-153X-7-84

 received in 2013-02-15, accepted in 2013-05-10,  发布年份 2013

【 摘 要 】

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.

【 授权许可】

   
2013 Fayad et al.; licensee Chemistry Central Ltd.

【 图 表 】

Figure 1.

Figure 2.

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