17α-ethinylestradiol (EE2), a synthetic oestrogen in oral contraceptives, is one of many pharmaceuticals found in inland waterways worldwide as a result of human consumption and excretion into wastewater treatment systems. At low parts per trillion (ppt), EE2 induces feminisation of male fish, diminishing reproductive success and causing fish population collapse. Intended water quality standards for EE2 set a much needed global precedent. Ozone and activated carbon provide effective wastewater treatments, but their energy intensities and capital/operating costs are formidable barriers to adoption. Here we describe the technical and environmental performance of a fast- developing contender for mitigation of EE2 contamination of wastewater based upon small- molecule, full-functional peroxidase enzyme replicas called “TAML activators”. From neutral to basic pH, TAML activators with H2O2 efficiently degrade EE2 in pure lab water, municipal effluents and EE2-spiked synthetic urine. TAML/H2O2 treatment curtails estrogenicity in vitro and substantially diminishes fish feminization in vivo. Our results provide a starting point for a future process in which tens of thousands of tonnes of wastewater could be treated per kilogram of catalyst. We suggest TAML/H2O2 is a worthy candidate for exploration as an environmentally compatible, versatile, method for removing EE2 and other pharmaceuticals from municipal wastewaters.
The presence of plastic cosmetic microbeads in the environment due to their extensive use in society and inevitable dispersal into wastewater is concerning. Therefore, it is vital to understand the processes of microplastic uptake and elimination by aquatic organisms, and to further assess their potential to cause harmful effects and wider impacts. We therefore investigated the short-term (48-h) and long-term (21-d) uptake, elimination, and effects of exposure to polyethylene microbeads (a mixture of fragments and spheres extracted from commercially available facial scrubs) on the freshwater snail, Biomphalaria glabrata. We found fast uptake in the short-term (75 μg/g/h) and the long-term (6.94 μg/g/h) in B. glabrata exposed to 800 particles/200-mL and 80 particles/200-mL, respectively. Irregular fragments were more easily ingested and egested compared to spheres (ANOVA, p < 0.05) in both 48-h and 21-d exposures. The mean size of the fragments in B. glabrata tissues (413 ± 16 μm) after 48-h exposure was significantly larger than that of the standard sample (369 ± 26 μm) (ANOVA, F3,20 = 3.339, p = 0.033), suggesting that aggregation in the gut may occur. Floating feces containing microbeads were observed in the long-term exposure, which could alter the fate, behavior, and bioavailability of egested microbeads. No significant effects on survival and growth were shown within 48-h or 21-d exposure periods. Thus, further studies on the specific features of microplastics (e.g., their shape and size) influencing uptake and elimination, as well as toxic molecular mechanisms, should be explored in future ecotoxicological studies.
In vertebrates, the steroidogenesis enzyme 5α-reductase converts testosterone to the more potent androgen 5α-dihydrotestosterone. Homologues of 5α-reductase genes have been identified in molluscs. However, recent findings suggest that vertebrate-type steroid androgens are not utilised in molluscan reproductive development. Genomic searches have revealed that molluscs do not possess many of the steroidogenic enzymes required to make testosterone, nor a nuclear androgen receptor. Consequently, the role of 5α-reductase in molluscs presents a mystery. Here, developmental exposures ofBiomphalaria glabratato selective pharmaceutical 5α-reductase inhibitors elicited a strong, highly reproducible phenotypic response characterised by the development of elongated “banana-shaped” shell morphology. In comparison to untreated snails, the shells are open-coiled and the whorls are unattached. Dutasteride (5α-reductase inhibitor) is approximately 10-times more potent at provoking the banana-shaped shell phenotype than finasteride, paralleling the pharmaceuticals’ efficacy in humans. Other enzyme inhibitors with different modes of action were tested to investigate the specificity of the phenotype. However, only the pharmaceutical 5α-reductase inhibitors provoked the response. Dutasteride elicited the same phenotype in a second gastropod,Physella acuta. In the absence of evidence forde novoandrogen steroidogenesis in molluscs, these findings suggest that novel substrates for 5α-reductase exist in gastropods, lending support to the contention that molluscan endocrinology differs from the well-characterised vertebrate endocrine system.