METHOD FOR THE ANALYSIS OF NATURAL AND SYNTHETIC STEROIDAL HORMONES IN SURFACE WATER AND SOIL

Natural and synthetic steroidal hormones are recognized as potent endocrine disruptors for many organisms at nanogram per liter levels. Methods for the analysis of four natural steroidal hormones (estrone (E1), 17-α-estradiol, 17-β-estradiol, and estriol) and three synthetic steroidal hormones (progesterone, melengestrol-acetate, and 17-α-ethinylestradiol) in surface water and soil were developed. Accelerated solvent extraction was used to recover analyte residue from soil samples and the performance of different extraction solvents and temperatures were evaluated. Solid phase extraction (SPE) was employed to extract and clean up analytes from both water samples and soil extracts. Sample pH, cartridge conditioning, wash and elution steps were optimized. Post extraction derivatization with dansyl chloride was necessary and was evaluated for analytical rigor. Analytes were subsequently detected by liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The composition of the SPE wash step was an important factor in reducing the effect of the co-extracted matrix components on method recovery, and as a result 20% acetone in water (V:V) was chosen in the final method. Method recoveries for all analytes are greater than 77% for surface water and 61% for soil. Calculated method detection limits for surface water and soil are from 0.04-1.80 ng L^-1 and 0.01-0.08 ng g^-1, respectively. Surface water samples from several waterways in Northwest Ohio impacted by both agricultural and urban runoff were used to validate the SPE method. Many of the targeted hormones were frequently detected, with the concentration of E1 being the highest at 41.28 ng L^-1. The surface water and soil methods will subsequently be used to help determine the sorption characteristics of these steroidal hormones to a sandy loam soil being used as the substrate in a constructed wetland microcosm study.