Natural estrogens are present in high concentrations in livestock slurries, which are often applied to agricultural fields in large quantities. As such, the export of slurry-derived natural estrogens from tile-drained fields is a potential source for estrogenic pollution in surface waters. Yet despite the abundance of tile-drained fields in Central Europe, export of natural estrogens from agricultural fields receiving livestock slurries is rarely studied in this region. In an effort to fill this knowledge gap, here we applied natural estrogens to Swiss experimental fields in the form of cattle slurry, pig slurry or dissolved in water, and quantified them in flow-proportionally collected drainage water over 18 months. After pig and cattle slurry applications, concentration maxima in drainage water of 73, 8, 37, and 60 ng L-1 for 17α-estradiol (E2α), 17β-estradiol (E2β), estrone (E1), and estriol (E3), respectively, were observed shortly after rain events. The exported fractions of individual natural estrogens to tile drains were on average 0.26% (ranging from 0.08 to 0.41%) after cattle, and 0.18% (0.03-0.40%) after pig slurry applications. Such numbers were higher than expected from the leaching potential based on substance properties, and comparable to those of more mobile micropollutants previously studied on the same fields. Natural estrogens were mainly exported to tile drains through preferential flow. Exported fractions were lower when applied in aqueous solution than when applied in slurry, pointing to particle-facilitated transport to tile drains when applied in slurry. In Switzerland, the estimated 6.3, 0.6, 7.4, and 7.7 g of E2α, E2β, E1, and E3, respectively, exported through the tile-drained agricultural area per year contribute little to the total natural estrogen load received by surface waters. However, after slurry applications in highly drained catchments, natural estrogen emissions to tile drains can cause short term (i.e. less than 1 week) estrogenic exposure in nearby streams.

Natural estrogens act as endocrine disruptors. However, the fate of livestock farming derived natural estrogens (17α-estradiol, 17β-estradiol, estrone, and estriol) in slurry is not well understood. In this study, we assessed the effects of on farm-storage on natural estrogen concentrations in slurry. Furthermore, we monitored pig and cattle slurry pits from major agricultural areas in Switzerland and determined natural estrogen concentrations therein. They were relatively stable over time, and mean concentrations ranged from 138 to 861 and 54 to 244 ng/L for cattle and pig slurries, respectively. 17α-Estradiol and estriol were the most prevalent estrogens in cattle and pig slurries, respectively. Based on livestock numbers, agricultural area, and estrogen concentrations in slurry, the estimated annual load of total natural estrogens applied on agricultural area amounted to 36 mg/ha. Our results indicate that slurry application is a relevant source of natural estrogens in the environment.

Natural estrogens such as 17α-estradiol (E2α), 17β-estradiol (E2β), estrone (E1), and estriol (E3), released to surface waters from both urban and agricultural sources, are endocrine disrupting for fish. Here, we assess the prevalence of livestock farming derived natural estrogens in tributaries and ponds in the agriculturally dominated catchment of Lake Baldegg, Switzerland. Passive samplers were deployed in the main tributary and daily time-proportional water samples were collected in five tributaries for 30 days at the beginning of the vegetation period. Furthermore, we took grab samples of 12 ponds in the catchment. Aqueous samples were liquid-liquid extracted, derivatized, and analysed with LC-MS/MS and stream water samples additionally with ERα-CALUX, a bioassay for assessing total estrogenic activity. Natural estrogens were regularly detected, with mean concentrations ranging from below the limit of detection to 0.55 ng L-1 for E2β and E1, respectively, and passive sampling and bioassay results largely confirmed these findings. Monte Carlo simulated mean natural estrogen concentrations underestimated measured ones by a factor of three to 11. An agricultural area's hydrological contribution and connectivity to surface waters seemed to be more important for the development of estrogen concentrations in streams than livestock densities in a catchment or the actual loads of slurry applied. Pond water occasionally contained natural estrogens in concentrations up to 8.6 ng L-1 for E2α. The environmental quality standards of the European Union (0.4 ng L-1 for E2β and 3.6 ng L-1 for E1) were never exceeded for longer than a day in tributaries, but E1 reached critical concentrations for aquatic organisms in ponds.

Biodegradable polyesters have a large potential to replace persistent polymers in numerous applications and to thereby reduce the accumulation of plastics in the environment. Ester hydrolysis by extracellular carboxylesterases is considered the rate-limiting step in polyester biodegradation. In this work, we systematically investigated the effects of polyester and carboxylesterase structure on the hydrolysis of nanometer-thin polyester films using a quartz-crystal microbalance with dissipation monitoring. Hydrolyzability increased with increasing polyester-chain flexibility as evidenced from differences in the hydrolysis rates and extents of aliphatic polyesters varying in the length of their dicarboxylic acid unit and of poly(butylene adipate-co-terephthalate) (PBAT) polyesters varying in their terephthalate-to-adipate ratio by Rhizopus oryzae lipase and Fusarium solani cutinase. Nanoscale nonuniformities in the PBAT films affected enzymatic hydrolysis and were likely caused by domains with elevated terephthalate contents that impaired enzymatic hydrolysis. Yet, the cutinase completely hydrolyzed all PBAT films, including films with a terephthalate-to-adipate molar ratio of one, under environmentally relevant conditions (pH 6, 20 °C). A comparative analysis of the hydrolysis of two model polyesters by eight different carboxylesterases revealed increasing hydrolysis with increasing accessibility of the enzyme active site. Therefore, this work highlights the importance of both polyester and carboxylesterase structure to enzymatic polyester hydrolysis.