Progestin Pollution in Surface Waters of a Major Southwestern European Estuary: The Douro River Estuary (Iberian Peninsula)

The concentrations and spreading of eight synthetic and two natural progestins (PGs) were investigated in surface waters from ten sites at the Douro River Estuary. Samples were filtrated and subjected to solid-phase extraction (SPE) to isolate and concentrate the target PGs. The extracts were cleaned by silica cartridges and analyzed by LC-MS/MS. The finding of biologically relevant amounts of gonanes (22.3 +/- 2.7 ng/L), progesterone derivatives (12.2 +/- 0.5 ng/L), drospirenone (4.1 +/- 0.8 ng/L), and natural PGs (9.4 +/- 0.9 ng/L) support the possibility of these compounds acting as endocrine disruptors. Despite the absence of significant differences amongst sampling sites and seasons, the principal component analysis (PCA) and the linear discriminant analysis (LDA) approaches reveal that spring and summer have different patterns of PG distribution compared to autumn and winter. The assessment of risk coefficients (RQs) and the potential concentrations of synthetic progestins in fish blood sustains that all tested compounds pose a significant risk to local biota (RQs > 1). Additionally, three progestins-norethindrone, norethindrone acetate, and medroxyprogesterone acetate-should reach human-equivalent therapeutic levels in fish plasma. Overall, the current data show PGs' presence and potential impacts in one of the most important estuaries of the Iberian Peninsula.