Estrogenic compounds in seawater and sediment from Halifax Harbour, Nova Scotia, Canada

Abstract-Samples of seawater and surface sediment were collected from seven locations around Halifax Harbour, Nova Scotia, Canada, and analyzed for the presence of the organic estrogenic contaminants, bisphenol A (BPA), 17beta-estradiol (E2), and 17alpha-ethinylestradiol (EE2). Samples were extracted using solid phase extraction (seawater) or sonication (sediments), followed by fractionation on a two-layer alumina/silica gel column prior to analysis by liquid chromatography-tandem mass spectrometry (LCMS/MS) with negative-ion electrospray ionization. Levels of the three compounds consistently ranked as BPA > E2 > EE2. The least potent compound and plasticizer BPA reached levels of up to 2.6 ng/L in seawater and 9.5 ng/g in sediments; the natural product E2 was detected at concentrations up to 0.57 ng/L and 0.86 ng/g; while the synthetic estrogen EE2 was in most cases below the method detection limit (0.14 ng/L and 0.28 ng/g). The highest levels were observed in the influent of a secondary treatment plant that discharges into the harbor, with concentrations of 32.4 ng/L for BPA and 5.3 ng/L for E2. Overall, the results indicate that these compounds readily associate with suspended particles rather than remaining in the soluble phase. Measurement of the octanol-water partition coefficient (log K(OW)) confirmed these results, with values of 3.41, 3.89, and 4.16 for BPA, E2, and EE2, respectively. Partitioning experiments using spiked field samples further confirmed these findings, with sorption directly related to sediment total organic content and following the order EE2 > E2 > BPA.