Deconjugation characteristics of natural estrogen conjugates by acid-catalyzed solvolysis and its application for wastewater samples

Abstract

Deconjugation reactions of natural estrogen conjugates were studied here by three different solutions of 1 M hydrochloric acid (HCl) in methanol. Estrogen sulfates could be easily deconjugated even at low temperature, while deconjugation conditions of estrogen glucuronides required a higher temperature and longer time. For 1 M HCl in methanol with 8% water, the deconjugation efficiencies of the three studied estrogen glucuronides were below 59.4% at 80 °C for 360 min, while the corresponding deconjugation efficiencies were above 80.6% for anhydrous HCl methanol at 80 °C for 210 min, which suggested trace water in the solution of 1 M HCl methanol retarded the deconjugation rates of estrogen glucuronides. On the other hand, their corresponding deconjugation rates increased with the addition of ethyl acetate, and their corresponding deconjugation efficiencies were above 86.7% at 80 °C for 120 min. As water is a highly polar solution, and the polarity of ethyl acetate is lower than that of methanol, this may suggest that a low polar substance would favor the reaction, while a highly polar solution would prohibit the reaction. All reactions were in pseudo first-order, and higher temperature increased the reaction rate. Finally, a GC-MS method for simultaneous analysis of free estrogens and estrogen conjugates in wastewater with acid-catalyzed solvolysis was developed, and satisfactory recovery efficiencies were obtained by spiking the standard target chemicals into the influent and effluent of one municipal wastewater treatment plant (WWTP), which demonstrated the feasibility of the developed method. Compared with enzymatic hydrolysis, the acid-catalyzed solvolysis method developed here to deconjugate estrogen conjugates is cost effective and time-saving, giving it a greater potential for use with environmental samples.