Degradation of estriol (E3) and transformation pathways after applying photochemical removal processes in natural surface water.

Steroidal hormones such as estriol (E3), are resistant to biodegradation; hence their removal by conventional treatment systems (aerobic and anaerobic) facilities is limited. These substances are detected in surface water, and present risks to the aquatic ecosystem and humans via potential biological activity. Photochemical treatments can be used to remove E3; however, just a few studies have analyzed the kinetics, intermediates, and E3 degradation pathways in natural surface water. In this study, the behavior of E3 under ultraviolet irradiation associated with H2O2, O3 or TiO2 was investigated to determine the degradation potential and the transformation pathways in reactions performed with a natural surface water sample. E3 degradation kinetics (200 ppb) fitted well to the pseudo-first-order kinetics model, with kinetic constant k in the following order: kUV/O3 > kUV/TiO2 > kUV/H2O2 > kUV. The mechanism of degradation using different advanced oxidative processes seemed to be similar and 12 transformation byproducts were identified, with 11 of them being reported here for the first time. The byproducts could be formed by the opening of the aromatic ring and addition of a hydroxyl radical. A possible route of E3 degradation was proposed based on the byproducts identified, and some of the byproducts presented chronic toxicity to aquatic organisms, demonstrating the risks of exposure.

Assessing cadmium-based quantum dots effect on the gonads of the marine mussel Mytilus galloprovincialis.

This study assesses the sex-specific effects induced by CdTe QDs, on the marine mussel Mytilus galloprovincialis in comparison to its dissolved counterpart. A 14 days exposure to CdTe QDs and dissolved Cd was conducted (10 µg Cd L-1), analysing Cd accumulation, oxidative stress, biotransformation, metallothionein and oxidative damage in the gonads. Both Cd forms caused significant antioxidant alterations, whereby QDs were more pro-oxidant, leading to oxidative damage, being females more affected. Overall, biochemical impairments on gonads of M. galloprovincialis demonstrate that the reproductive toxicity induced by CdTe QDs in mussels are sex-dependent and mediated by oxidative stress and lipid peroxidation. It is crucial to acknowledge how gametes are affected by metal-based nanoparticles, such as Cd-based QDs. As well as understanding the potential changes they may undergo at the cellular level during gametogenesis, embryogenesis and larval development potentially leading to serious impacts on population sustainability and ecosystem health.

Are shallow-water shrimps proxies for hydrothermal-vent shrimps to assess the impact of deep-sea mining?

Polymetallic seafloor massive sulphide deposits are potential targets for deep-sea mining, but high concentrations of metals (including copper - Cu) may be released during exploitation activities, potentially inducing harmful impact. To determine whether shallow-water shrimp are suitable ecotoxicological proxies for deep-sea hydrothermal vent shrimp the effects of waterborne Cu exposure (3 and 10 days at 0.4 and 4 µM concentrations) in Palaemon elegans, Palaemon serratus, and Palaemon varians were compared with Mirocaris fortunata. Accumulation of Cu and a set of biomarkers were analysed. Results show different responses among congeneric species indicating that it is not appropriate to use shallow-water shrimps as ecotoxicological proxies for deep-water shrimps. During the evolutionary history of these species they were likely subject to different chemical environments which may have induced different molecular/biochemical adaptations/tolerances. Results highlight the importance of analysing effects of deep-sea mining in situ and in local species to adequately assess ecotoxicological effects under natural environmental conditions.

Impacts of in vivo and in vitro exposures to tamoxifen: Comparative effects on human cells and marine organisms.

Tamoxifen (TAM) is a first generation-SERM administered for hormone receptor-positive (HER+) breast cancer in both pre- and post-menopausal patients and may undergo metabolic activation in organisms that share similar receptors and thus face comparable mechanisms of response. The present study aimed to assess whether environmental trace concentrations of TAM are bioavailable to the filter feeder M. galloprovincialis (100 ng L-1) and to the deposit feeder N. diversicolor (0.5, 10, 25 and 100 ng L-1) after 14 days of exposure. Behavioural impairment (burrowing kinetic), neurotoxicity (AChE activity), endocrine disruption by alkali-labile phosphate (ALP) content, oxidative stress (SOD, CAT, GPXs activities), biotransformation (GST activity), oxidative damage (LPO) and genotoxicity (DNA damage) were assessed. Moreover, this study also pertained to compare TAM cytotoxicity effects to mussels and targeted human (i.e. immortalized retinal pigment epithelium - RPE; and human transformed endothelial cells - HeLa) cell lines, in a range of concentrations from 0.5 ng L-1 to 50 µg L-1. In polychaetes N. diversicolor, TAM exerted remarkable oxidative stress and damage at the lowest concentration (0.5 ng L-1), whereas significant genotoxicity was reported at the highest exposure level (100 ng L-1). In mussels M. galloprovincialis, 100 ng L-1 TAM caused endocrine disruption in males, neurotoxicity, and an induction in GST activity and LPO byproducts in gills, corroborating in genotoxicity over the exposure days. Although cytotoxicity assays conducted with mussel haemocytes following in vivo exposure was not effective, in vitro exposure showed to be a feasible alternative, with comparable sensitivity to human cell line (HeLa).

Environmental relevant levels of the cytotoxic drug cyclophosphamide produce harmful effects in the polychaete Nereis diversicolor.

Cytotoxic drugs applied in chemotherapy enter the aquatic environment after patient's metabolism and excretion, in both main compounds and their respective metabolites. The increased consumption and discharge of these drugs raise concern on the genotoxic burden to non-target aquatic species, due to their unselective action on DNA. Settlement and adsorption of cytotoxic drugs to aquatic sediments pose risks to benthic species through chronic exposure. The aim of the present study was to assess the effects induced by the anticancer drug cyclophosphamide (CP) on the polychaete Nereis diversicolor, after 14 days of exposure to environmental relevant concentrations (10, 100, 500 and 1000 ng L-1). Burrowing impairment, neurotoxicity (Acetylcholinesterase - AChE activity), oxidative stress (superoxide dismutase - SOD; catalase - CAT; glutathione peroxidases - GPXs activities), biotransformation (glutathione-S-transferases - GST), oxidative damage (lipid peroxidation - LPO) and genotoxicity (DNA damage) were assessed. Burrowing impairments were higher at the lowest CP concentrations tested. The higher CP levels tested (500 and 1000 ng L-1) induced a significant inhibition on the enzymatic antioxidant system (SOD, GPx) and on GST activity. DNA damage was also significant at these concentrations as an outcome of CP metabolism, and high levels of oxidative damage occurred. The results showed that the prodrug CP was metabolically activated in the benthic biological model N. diversicolor. In addition to the potential cytotoxic impact likely to be caused in aquatic species with similar metabolism, N. diversicolor proved to be reliable and vulnerable to the cytotoxic mode of action of CP, even at the lower doses.

Ecotoxicological assessment of the anticancer drug cisplatin in the polychaete Nereis diversicolor.

Anticancer drugs are designed to inhibit tumor cell proliferation by interacting with DNA and altering cellular growth factors. When released into the waterbodies of municipal and hospital effluents these pharmaceutical compounds may pose a risk to non-target aquatic organisms, due to their mode of action (cytotoxic, genotoxic, mutagenic and teratogenic). The present study aimed to assess the ecotoxicological potential of the alkylating agent cisplatin (CisPt) to the polychaete Nereis diversicolor, at a range of relevant environmental concentrations (i.e. 0.1, 10 and 100ngPtL-1). Behavioural impairment (burrowing kinetic impairment), ion pump effects (SR Ca2+-ATPase), neurotoxicity (AChE activity), oxidative stress (SOD, CAT and GPXs activities), metal exposure (metallothionein-like proteins - MTLP), biotransformation (GST), oxidative damage (LPO) and genotoxicity (DNA damage), were selected as endpoints to evaluate the sublethal responses of the ragworms after 14-days of exposure in a water-sediment system. Significant burrowing impairment occurred in worms exposed to the highest CisPt concentration (100ngPtL-1) along with neurotoxic effects. The activity of antioxidant enzymes (SOD, CAT) and second phase biotransformation enzyme (GST) was inhibited but such effects were compensated by MTLP induction. Furthermore, LPO levels also increased. Results showed that the mode of action of cisplatin may pose a risk to this aquatic species even at the range of ngL-1.