Research Article

Received: 11 October 2011 Revised: 22 December 2011 Accepted: 23 December 2011 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jctb.3742

Electrolysis of progesterone with conductive-diamond electrodes

Mara Jose Martn de Vidales, Cristina Saez, Pablo Canizares and Manuel Andres Rodrigo
Abstract
BACKGROUND: Progesterone is considered an endocrine disruptor chemical. It can be found in industrial discharges, municipal wastewaters, and, in some instances, even in treated efuents at the level of ng dm3 . RESULTS: Conductive diamond electrolysis can be used to remove progesterone from aqueous solutions. Increases in current density lead to less efcient processes, indicating mass transfer control of the process rate. Occurrence of chlorides in the electrolytic media favors the depletion of progesterone compared with sulphates, although it does not affect the mineralization rate. Independently of the solubilizing agent used, the process behaves similarly during a rst stage of the electrolysis (at the four ranges of pollutant concentration studied). However, in a second stage, the rate changes abruptly due to reduced action of hydroxyl radicals in methanol media. CONCLUSIONS: Progesterone can be removed efciently by conductive diamond electrolysis from aqueous solutions within the range of initial concentrations 102 to 102 mg dm3 . The process efciency increases with the current density. Removal rate does not depend on the nature of the electrolyte, but this parameter affects the intermediates formed during the experiment. When pure methanol is used as solubilizing agent, only direct electro-oxidation takes place. c 2012 Society of Chemical Industry Keywords: conductive diamond; electrochemical oxidation; hormone; wastewater; progesterone

INTRODUCTION
Progesterone belongs to a class of hormones called progestogens, and it is the major naturally occurring human progestogen. This type of hormone is widely used in human and veterinary medicine because it is strongly related to the estrous cycle. From the environmental point of view, the occurrence of this compound in water is undesirable because it is considered an endocrine disruptor chemical (EDC) and, consequently, it is related to many potential hazards for aquatic organisms, including feminization, hermaphroditism and decrease in fertility. In general, EDCs are known to interfere with the mode of action of hormones in the normal physiological system, and much evidence indicates links between compounds that act as EDCs and many sex hormone sensitive diseases/disorders. Occurrence of progesterone in water used to be related to industrial discharges and to municipal wastewaters, in some instances even in treated efuents. From these sources, it can be found in various aquatic environments, affecting surface and ground water reservoirs of drinking water.1 At this point, it is worth stating that progesterone has been detected in low concentration (at the level of ng dm3 ) in the efuents of municipal wastewater treatment facilities2 and in drinking water sources such as river water.3 Its removal has been studied by ozonation,4,5 photocatalysis,6 or solar photo-Fenton,7 but to the authors knowledge no studies involving the electrochemical treatment have been carried out. Conductive-diamond electrochemical oxidation (CDEO) is considered by many authors8 22 as a very robust and effective

technology to remove many types of organics. It can achieve very efcient removal of the organics contained in water or in wastewater, even at very different ranges of concentration. It provides complete mineralization of the organic, usually in a very strong oxidation process in which intermediates production is not promoted and in which oxidation-refractory compounds are not produced. This signicant oxidation-potential is usually explained in terms of the effect of hydroxyl radicals (and hence, it is considered an advanced oxidation technology), but it is also explained in terms of the synergistic effect of different oxidation mechanisms including mediated oxidation by electrogenerated oxidants such as peroxosulphates, peroxophosphates, ozone, etc. With this background, the goal of this work is to determine if CDEO is a proper technology for the degradation of progesterone from waters and wastewaters at different concentration ranges, and also to study the main parameters inuencing the degradation process in order to obtain information about the characteristics of the system.

Correspondence to: Manuel Andr s Rodrigo, Department of Chemical Engie neering, Edicio Enrique Costa, Campus Universitario s/n. 13071 Ciudad Real, Spain. E-mail: manuel.rodrigo@uclm.es Department of Chemical Engineering, Edicio Enrique Costa, Campus Universitario s/n. 13071 Ciudad Real, Spain

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1 [Progesterone] / [Progesterone]0

MATERIALS AND METHODS

Chemicals Two types of progesterone were used in this work: watersoluble progesterone (WSP) or progesterone/2-hydroxypropyl-cyclodextrin (7/93), where 2-hydroxypropyl--cyclodextrin is a stabilizing agent,23 and pure progesterone (>99.6% purity). Both reagents were supplied by Sigma-Aldrich Laborchemikalien GmbH (Steinheim, Germany). Anhydrous sodium sulphate and sodium chloride used as supporting electrolytes were analytical grade purchased from Fluka. All solutions were prepared with high-purity water obtained from a Millipore Milli-Q system, with resistivity >18 M cm at 25 C. Sulphuric acid and sodium hydroxide used to adjust the solution pH were analytical grade and supplied by Panreac Qumica S.A. (Barcelona, Spain). Analytical procedures The total organic carbon (TOC) concentration was monitored using a Shimadzu TOC-5050 analyzer. Measurements of pH and conductivity were carried out with an InoLab WTW pH meter and a GLP 31 Crison conductimeter, respectively. The concentrations of the compounds were quantied by HPLC (Agilent 1100 series). The detection wavelength used to detect progesterone was 248 nm. The column temperature was 25 C. Volume injection was set to 50 L. The analytical column used was Phenomenex Gemini 5 m C18. Solvent A was composed of 25 mmol L1 of formic acid water solution, and Solvent B was acetonitrile. A linear gradient chromatographic elution was obtained by initially running 10% of Solvent B ascending to 100% in 40 min. Samples extracted from electrolyzed solutions were ltered with 0.20 m nylon lters before analysis. Electrochemical cells Electrolyses were carried out in a single compartment electrochemical ow cell working in a batch-operation mode9 . A conductive-diamond electrode (p-Siboron-doped diamond) was used as anode and stainless steel (AISI 304) as cathode. Both electrodes were circular (100 mm diameter) with a geometric area of 78 cm2 and an electrode gap of 9 mm. Boron-doped diamond lms were provided by Adamant Technologies (Neuchatel, Switzerland) and synthesized by the hot lament chemical vapour deposition technique (HF CVD) on single-crystal p-type Si <100>; wafers (0.1 cm, Siltronix). The boron content of the electrodes was 500 ppm and the sp3 /sp2 ratio was 194. Experimental procedures Bench-scale electrolyses of 600 cm3 of wastewater were carried out under galvanostatic conditions. The concentration of progesterone was ranged from 0.1 to 100 ppm, and 0.035 mol L1 Na2 SO4 or NaCl was used as supporting electrolyte. The current density employed ranged from 15100 mA cm2 . The cell voltage did not vary during each electrolysis, indicating that conductive-diamond layers did not undergo appreciable deterioration or passivation. Prior to use in galvanostatic electrolysis assays, the electrode was polarized for 10 min in a 0.035 mol L1 Na2 SO4 (pH = 2) solution at 15 mA cm2 to remove any kind of impurity from its surface. The wastewater was stored in a glass tank and circulated through the electrolytic cell by means of a centrifugal pump (ow rate 21.4 dm3 h1 ). A heat exchanger coupled with a controlled thermostatic bath (Digiterm 100, JP Selecta, Barcelona, Spain) was used to maintain the temperature at the desired set point (25 C).

0.1
K / min-1 0.1

0.01 0.01

1 100 [Progesterone]0 / mg dm-3

0.01 0 50 100 150 Time / min 200 250

Figure 1. Changes in the concentration during the electrolysis of progesterone at four different initial concentrations 100 mg dm3 10 mg dm3 1 mg dm3 0.1 mg dm3 ; j = 15 mA cm2 ; electrolyte: 0.035 mol L1 Na2 SO4 ; solution medium: 2-hydroxypropyl--cyclodextrin. Inset: effect of the initial concentration of progesterone on the pseudorst-order kinetic constant.

RESULTS AND DISCUSSION

Figure 1 shows the changes in the concentration of progesterone during electrolyses of synthetic wastes polluted with different concentrations of this specie, covering a four order-of-magnitude concentrations range: from a very high concentration, which can be found only in an industrial efuent of a pharmaceutical industry,24 down to the value in which it can be typically found in the efuent of a municipal wastewater treatment plant (some g dm3 )1 . Semilogarithmic scales are used to compare clearly the different experiments, due the huge differences in the concentration ranges used. At this point it is worth mentioning that solubility of progesterone is very small. In order to get solutions in this wide range of concentrations, a special product named water soluble progesterone (WSP) was used. As is known, this is not a pure product but it corresponds to a mixture (7/93) Progesterone/2-hydroxypropyl-cyclodextrin where 2-hydroxypropyl--cyclodextrin is a stabilizing agent23 that increases solubility of progesterone. This mixture behaves as a single product in aqueous solution (just one HPLC peak is observed), and it permits concentrations as high as 100 mg dm3 of progesterone in aqueous solution. In every case, the supporting electrolyte consists of 5000 mg dm3 of sodium sulphate. This electrolyte was used in order to increase the ionic conductivity of the reaction media to the values required for an efcient electrolysis. It was chosen because of its assumed nil effect on the electrolyte product distribution (contrary to what it is expected in a chloride media), and because it is one of the salts typically contained in the efuents of pharmaceutical processes. Concerning Fig. 1, it can be clearly observed that progesterone is removed efciently in the four electrolyses. Data follow a linear trend in semi-logarithmic scale, which initially may suggest a rstorder kinetic with respect to the concentration of progesterone. This would be easily explained in terms of a mass transfer control of the process, taking into account the small concentrations of the pollutant, even in the 100 mg dm3 case which is many times below the limit concentration at the current density applied. However, the slope of this linear trend (kinetic constant) depends on the particular electrolysis and, consequently, on the initial concentration of WSP, being smaller at larger concentration, as can be observed in the inset of the gure. This behavior has previously been observed for other species such as metoprolol and sulphame-

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100 90 [Progesterone] / mg dm-3 80 70 60 50 40 30 20 10 0 0 20 40 Q / Ah dm-3 60 100 90 80 TOC removal / %
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Figure 2. Effect of the supporting electrolyte (0.035 mol L1 NaCl or Na2 SO4 ) on the removal of progesterone and TOC at high concentration C0 = 100 ppm; j = 30 mA cm2 ; solution medium: 2-hydroxypropyl-cyclodextrin. progesterone Na2 SO4 progesterone NaCl TOC Na2 SO4 TOC NaCl.

Figure 3. Intermediates found by HPLC during the electrolyses of a highly concentration solution of soluble progesterone in 0.035 mol L1 sodium sulphate ( i1 (27.8 min)) and 0.035 mol L1 sodium chloride ( i1 (27.8 min) i2 (31.0 min) i3 (36.7 min)) supporting electrolyte media. j = 30 mA cm2 .

toxazole in previous work. It may be explained assuming the existence of indirect oxidation mechanisms with electro-generated oxidants, and a second-order kinetic model k [oxidant][organic]. At this point, it is known that many oxidants are produced during the electrolysis with conductive-diamond anodes of aqueous solutions, including not only conventional oxidants such as persulphates, ozone or hydrogen peroxide but also powerful radicals such as the hydroxyl radical. The pseudo-stationary concentration of these oxidants (difference at the steady-state between the oxidant produced electrolytically and the oxidant spent in the oxidation of organics) decreases with the concentration of organics, explaining the decrease in the term k[oxidant] which behaves as the observed pseudo-rst-order kinetic constant. Figure 2 shows the effect of the supporting electrolyte (sulphate or chloride) on the concentration of progesterone and on the TOC. It can be clearly observed that chloride anions favor the rapid depletion of progesterone compared with sulphate, the process being more than ten times faster. However, the mineralization rate is nearly the same with both electrolytes as both concentration curves vs. Q overlap. This suggests that chloride only promotes the production of intermediates, the complete removal of the pollutant by conversion into carbon dioxide being as efcient as in the case of electrolysis with sulphate. Therefore, the mineralization rate is similar in both media, and the oxidation of progesterone in chlorine media is not directly to carbon dioxide. In both media, the formation of oxidants from oxidation of the anions, hypochlorite in the case of chloride25 and peroxosulphate in the case of sulphates9 is well documented Hence, these oxidant species should help to explain the results. Moreover, the production of many chlorinated intermediates during chemical oxidation of organics with chlorine is well known, while, conversely, the dosing of persulphate leads to a more direct mineralization of the organics and, consequently, to a smaller amount of intermediates. Figure 3 shows the concentration of intermediates found in the electrolyses of soluble progesterone in sulphate- and chloridesupporting electrolytes. HPLC detects only one intermediate in the case of electrolysis in sulphate media. This intermediate appears at 27.8 min, which it is the same time at which a peak appears for pure 2-hydroxypropyl--cyclodextrin. This peak is also obtained in the case of chloride media, and supports the release of some 2-hydroxypropyl--cyclodextrin (from the complex

100 90 [Progesterone] / mg dm-3 80 70 60

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100 90 80 60 50 40 30
0 50 100 150

50 40 30 20 10 0 0 20

0.03 0.02 0.01 0 j / mA cm-2

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40 Q / Ah dm-3

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Figure 4. Effect of current density on the removal of a highly loaded solution of water soluble progesterone (100 mg dm3 ), with sodium sulphate (0.035 mol L1 ) as supporting electrolyte. Current densities: 15 mA cm2 ; 30 mA cm2 ; 100 mA cm2 .

progesterone/2-hydroxypropyl--cyclodextrin) with the oxidation of progesterone. This species clearly behaves as an intermediate, and it is removed during electrolysis. In the case of the electrolyses in the chloride media, two additional intermediates (three reaction intermediates in total with cyclodextrin) are found using HPLC at 31.0 and 36.7 min. It is possible that these compounds are formed by the attack of ClO , generated electrochemically by oxidation of Cl25 to progesterone and 2-hidroxypropyl--cyclodextrin, compound that accompanies progesterone. In order to check this fact, a solution of 0.035 mol L1 of Ca(ClO)2 was added to two solutions with 100 mg dm3 of progesterone and 100 mg dm3 of 2-hidroxypropyl--cyclodextrin, respectively. After 2 h, the nal samples were analyzed by HPLC. Two peaks with the same retention time that the intermediates formed in the electrolyses with NaCl as electrolyte were found. Therefore, these compounds may be explained in terms of the result of chlorination of progesterone and 2-hidroxypropyl--cyclodextrin molecules by attack of the anodically electrogenerated ClO . Figure 4 shows the effect of current density on the removal of progesterone and on the mineralization of the synthetic waste. Within the range 15 to 100 mA cm2 , progesterone is completely

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www.soci.org depleted and mineralization is almost complete. The higher the current density, the lower the efciency of the process. This can be clearly observed in the graph: lower current densities lead to the same removal for smaller current charges applied. On the contrary, the kinetic constant increases with the current density almost linearly, as is shown in the inset of the gure. This behavior is characteristic of a process in which mass transfer limitations play a key role. At this point, it is worth stating that the current density applied is signicantly over the limit current density calculated for the hydrodynamic conditions of the electrochemical cell. The product used in the previous studies to evaluate the oxidation of progesterone was a mixture of progesterone and 2-hidroxypropyl--cyclodextrin, because the solubility of pure progesterone in water is very low, unless this species is combined with a solubilizing agent. Like progesterone, 2-hidroxypropyl-cyclodextrin was also found to be removed during electrolysis over the complete range of concentrations applied, and in fact, it was detected separately in the electrolytic solution during the process behaving as an intermediate. To study the inuence of the solubilizing agent on the removal of progesterone, pure progesterone was dissolved in methanol and in water methanol solutions. Solubility of progesterone in methanol is very high and over the 100 mg dm3 concentration used in this work. From a practical point of view, the ratio methanol/progesterone to assure complete dissolution of progesterone in an aqueous solution is around (250 cm3 )/(100 mg dm3 ) (determined experimentally). This means that to get an aqueous solution with 100 mg dm3 of progesterone it is necessary that this solution will be 25% (v/v) in methanol. Figure 5 compares the electrolysis of solutions with high concentrations of progesterone (100 mg dm3 ) in aqueous media using 2-hidroxypropyl--cyclodextrin and methanol as solubilizing agents. In addition, this gure also reports the results of the electrolysis of progesterone in non-aqueous media (pure methanol) for comparison purposes. Electrolyses in aqueous media shows no differences for the removal of progesterone when using methanol or 2-hidroxypropyl--cyclodextrin as solubilizing agents during a rst stage of the electrolyses in which the same rate is observed for both electrolysis. Then, this rate decreases signicantly for the electrolysis with methanol as solubilizing
(a) 10

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[Progesterone] / mg dm-3

0.1

0.01 0 10 20 Q / Ah dm-3 (b) 1 30 40

[Progesterone] / mg dm-3

0.1

0.01 0 5 10 Q / Ah dm-3
Figure 6. Inuence of concentration on the effect of the solubilizing agent, of progesterone, and of the reaction media on the electrolysis of progesterone solutions. Current density: 15 mA cm2 . Part a: initial concentration of progesterone 10 mg dm3 ; water soluble progesterone in water; progesterone in methanol/water 2.5%(v/v); progesterone in methanol. Part b: initial concentration of progesterone 1 mg dm3 ; water soluble progesterone in water; progesterone in methanol/water 0.25 %(v/v); progesterone in methanol.

15

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0.01 0 10 20 Q / Ah dm-3
Figure 5. Effect of the solubilizing agent of progesterone and of the reaction media on the electrolysis of highly loaded progesterone solutions. water soluble progesterone in water progesterone in methanol/water 25% (v/v); progesterone in methanol. Current density 15 mA cm2 .

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agent, but it is still maintained in the case of the WSP, which still decreases at the high rate two orders of magnitude more. Another important observation, it is the behaviour of the electrolysis of progesterone in pure methanol. A linear trend is obtained, the reaction rate being smaller than in the other two cases studied. This means that although progesterone competes with methanol during oxidation, this oxidation occurs at a high efciency even in pure methanol. This also suggests that competition between methanol and progesterone oxidation is not responsible for the change of slope observed during the electrolysis of progesterone in methanolwater solutions, although it should play an important role in the oxidation process. The same behavior can be observed in the electrolysis of progesterone at smaller concentrations, as can clearly be seen in Fig. 6, in which results of electrolysis of solutions with 10 and 1 mg dm3 of progesterone are shown. The rst zone with similar rates for the removal of progesterone in water/methanol solutions and with 2-hidroxypropyl--cyclodextrin as solubilizing agent can be clearly discerned in both graphs, although they correspond to different orders magnitude orders. The change in the rate in the case of the use of methanol as solubilizing agent in aqueous solutions can also be seen, which should be interpreted

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CONCLUSIONS
From this work the following conclusions can be drawn: Progesterone can be removed effciently from aqueous solutions within the range of initial concentrations 102 to 102 mg dm3 . Decay follows a pseudo-rst-order kinetics (linear tting in semilogarithmic plot) during each electrolysis with a kinetic constant that decreases with the initial concentration of progesterone. Increases in current density lead to less efcient processes, indicating mass transfer control of the process rate. However, mediated electro-oxidation plays an important role not in the mineralization rate but in the mechanisms. Compared with sulphates, chlorides promote the rapid depletion of progesterone and the formation of the same intermediates occurring during the chemical dosing of hypochlorite. During a rst stage of the electrolyses (at the different ranges of pollutant concentration studied), there are no differences when methanol is used as solubilizing agent instead of 2-hidroxypropyl--cyclodextrin but then, the rate changes abruptly down to a value that it is even lower than the rate obtained in pure methanol electrolysis. This observation can be explained in terms of the inhibiting effect of methanol on hydroxyl radicals action, which it is not observed in pure methanol electrolysis because in those electrolyses only direct electro-oxidation occurs.

0.01 K / min-1

0.001

0.0001

0.00001 1 10 [Progesterone]0 / mg dm-3

Figure 7. First-order kinetic constant of the electrochemical degradation of progesterone in aqueous media ( rst stage of methanol and WSP; second stage of methanol) and in pure methanol media ( ).

100

in terms of an inhibiting effect of methanol on the action of hydroxyl radicals, once a particular ratio progesterone/methanol is reached during the electrolyses. Thus, the main difference between the experiments with pure methanol and with methanol/water is the potential formation of hydroxyl radicals in this last case. Figure 7 shows the kinetic constants (rst-order approach) obtained by mathematical tting during the rst and second stage of the electrolysis in methanol/water (rst stage matches according to the previously described behavior of WSP) and in pure methanol. This last constant does not depend on the progesterone concentration, indicating a real rst-order process. Alternatively it could be explained in terms of an order lower than rst (moving towards zeroth) simply because oxidizing agents become the limiting reactant at high progesterone concentrations. However, the other two tting kinetic-constants decrease with progesterone concentration, suggesting pseudo-rst-order kinetic processes instead of a real rst-order process. Differences between the rate of electrolysis in pure methanol and the oxidation rate found in the electrolysis in aqueous media become more signicant at smaller initial progesterone concentrations for the rst stage, as can be observed in Fig. 7. This can be easily explained in terms of the smaller concentration of methanol required to solubilize progesterone at smaller concentrations, and conrms the existence of competition between methanol and progesterone to be oxidized at these conditions. Concerning the second stage rate in the electrolysis in methanol/water medium, it is clearly observed that oxidation rate is below the value obtained in pure methanol, and also that the differences are higher for higher progesterone concentration, which also means higher concentration of methanol. This may suggest some sort of protective effect against oxidation of methanol at these particular conditions. As this effect is not observed in pure methanol electrolysis, an inhibitory effect of methanol on the hydroxyl radicals effect (which are not produced in pure methanol) is the lone reasonable explanation for this observation, although more work has to be done in order to clarify this point.

ACKNOWLEDGEMENTS
The authors acknowledge funding support from the national Spanish Ministry of Education and Science (Project CSD2006-00044 CONSOLIDER INGENIO 2010 TRAGUA project).

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