Steroid Hormone Profiles of Urban and Tidal Rivers Using LC/MS/MS Equipped with Electrospray Ionization and Atmospheric Pressure Photoionization Sources

Abstract

A highly sensitive and uncomplicated method of analyzing steroidal hormones in river and estuarine water samples was developed using a liquid chromatography tandem mass spectrometer equipped with an electrospray ionization (ESI) source and atmospheric pressure photoionization (APPI) source. Steroidal hormones included not only estrogen but also androgen and conjugates of these two. APPI displayed greater sensitivity than ESI for most of the unconjugated steroids examined, with very high sensitivity for testosterone and 4-androstene-3,17-dione in particular. For conjugated hormones, in contrast, ESI was more effective. The method developed was applied to the determination of hormones in the rivers of Osaka City and their estuaries, where the hormones detected were affected by the effluent from municipal wastewater treatment plants (WWTPs), and hormone concentration values were comparable to those reported in previous studies of such effluent. Because of the two-way flow and stagnancy of streams and watercourses, continuous input of steroidal hormones from WWTPs seems to bring about local accumulation. Levels of androgen were 1 order of magnitude lower than those of estrogen. Estrone, estrone 3-sulfate, and 4-androstene-3,17-dione were detected in almost all water samples, with maxima of 51, 5.1, and 6.4 ng L(-1), respectively.

Trace Analysis of Fifteen Androgens in Environmental Waters by LC-ESI-MS-MS Combined with Solid-Phase Disk Extraction Cleanup

“…Alternative methods include the implementation of highperformance liquid chromatography MS (LC-MS) methodology where derivatization is often not needed. Recent examples reported in the literature include the analysis of androgens in waste water and surface water samples [8,9]. Although LC-MS(-MS) has been viewed as a potential method for analyzing a broad range of these compounds, matrix interference has been proven to cause potential problems.…”

Integrated multi-omics analyses reveal the biochemical mechanisms and phylogenetic relevance of anaerobic androgen biodegradation in the environment

“…Steroid hormones have been frequently detected in various environmental matrices, including soil, groundwater, surface water and sediments (Ying et al, 2002). These substances were often found at nanograms to micrograms per liter concentrations in surface water (Ternes et al, 1999;Baronti et al, 2000;Kolodziej et al, 2003;Yamamoto et al, 2006;Chen et al, 2010;Chang et al, 2011;Fan et al, 2011). Quantifying five classes of steroid hormones in the surface waters of Beijing (China) revealed that androgens (up to 1.9 μg l − 1 ) were the most abundant steroids in urban rivers (Chang et al, 2009).…”

Assessment of the Occurrence and Potential Effects of Pharmaceuticals and Personal Care Products in South Florida Waters and Sediments

“…In particular APPI was shown to be able to detect steroid hormones down to several ng/L and had been proven to have much higher sensitivity than ESI. (Yamamoto et al, 2006;Viglino et al, 2008). Atmospheric pressure photoionization is the ionization of choice for PAHs and showed results comparable to gas chromatography mass spectrometry (Itoh et al, 2006;Cai et al, 2009).…”

“…suggested that APPI could be considered as a more universal ionization method since APPI was able to ionized more compounds, with greater structural diversity, than ESI and APCI (Cai et al, 2005). Because of the capacity of APPI to ionize compounds with various polarities, it has been successfully applied frequently to environmental and pharmaceutical samples (Cai et al, 2005;Yamamoto et al, 2006;Viglino et al, 2008;Garcia-Ac et al, 2011).…”

“…The application and principle of APPI have been reviewed and the rapidly growing number of publications in this area clearly demonstrates the advantages of APPI (Hanold et al, 2004;Bos et al, 2006). Atmospheric pressure photoionization has proven to be a valuable tool for analytes, which are poorly or not ionized by ESI and APCI or in the presence of complex analytical condition (Itoh et al, 2006;Yamamoto et al, 2006;Viglino et al, 2008;Cai et al, 2009).…”