Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents

Abstract

BackgroundThis 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.ResultsThe 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.ConclusionThis 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.

A review of what is an emerging contaminant

“…For example, chlorination can generate by-products such as haloacetic acids or trihalomethanes [ 56 ]. Treatment can focus on conceptually simpler biological processes such as constructed wetlands which can nevertheless be quite efficient [ 40 ] or more complex chemical treatment such as oxidation with chloration or permanganate [ 57 ]. Ozone is often proposed as an alternative or additional treatment that could potentially reduce or eliminate such by-products but ozone itself is so reactive that it is also a major means of producing a suite of by-products, examples are given for the identification of the transformation products of antidepressor drugs [ 20 ] or for a natural estrogen [ 21 ].…”

Sodium Persulfate and Potassium Permanganate Inhibit Methanogens and Methanogenesis in Stored Liquid Dairy Manure

“…This might not be related to microbial consumption, as methanogen abundance also reduced more with increased rates of KMnO 4 than Na 2 S 2 O 8 . As a strong oxidizing agent, KMnO 4 is commonly used to remove organic matter from soil and water systems (Fayad et al, 2013; Wu et al, 2014; Naceradska et al, 2017; Rissanen et al, 2017). Its removal efficiency might also be high compared with Na 2 S 2 O 8 (Usman et al, 2017), and thus it is reasonable that KMnO 4 might have oxidized more slurry organic matter (source of methanogenic substrates) and inactivated microorganisms.…”

“…However, the toxicity of H 2 SO 4 and application of nanoparticle‐treated manure in agricultural soils may raise concerns for farm personnel and disrupt natural soil processes (Dinesh et al, 2012; Ben‐Moshe et al, 2013; Shen et al, 2015). Chemical oxidants with less harm such as sodium persulfate (Na 2 S 2 O 8 ), potassium permanganate (KMnO 4 ), and sodium hypochlorite (NaOCl), which are commonly used in the removal of organic matter from hydrocarbon‐contaminated soils and wastewaters (Fayad et al, 2013; Wu et al, 2014; Jakubauskaite et al, 2016), may oxidize slurry organic matter including microorganisms and hence can inhibit methanogenesis.…”

Photocurrent Response and Progesterone Degradation by Employing WO3 Films Modified with Platinum and Silver Nanoparticles

“…[44] In addition, surface plasmon resonance and light scattering promoted by Ag 0 and Pt 0 NPs onto WO 3 films improved the photocatalytic activity. [46] Some strategies to remove progesterone from water, such as photolysis by UVA light [47] and oxidation with potassium permanganate in wastewater effluents [48] , were reported in the literature, but electrochemically assisted photodegradation with WO 3 films has not yet been reported, to the best of our knowledge. Thus, for the n-type semiconductor, when irradiated, the electrons are driven toward the conductor substrate, enhancing charge separation.…”

“…The advantage of using the EHP technique is that it realizes faster degradation and is also inexpensive. [46] Some strategies to remove progesterone from water, such as photolysis by UVA light [47] and oxidation with potassium permanganate in wastewater effluents [48] , were reported in the literature, but electrochemically assisted photodegradation with WO 3 films has not yet been reported, to the best of our knowledge. As observed in Figure 7b, the degradation of progesterone in aqueous solution can be adjusted by pseudo-first-order kinetics.…”