RESUMEN

As a proxy for pollutants that may be simultaneously present in urban wastewater streams, the effects of two microplastics-polystyrene (PS; 10, 80 and 230 µm diameter) and polymethylmethacrylate (PMMA; 10 and 50 µm diameter)-on fertilisation and embryogenesis in the sea urchin Arbacia lixula with co-exposure to the pyrethroid insecticide cypermethrin were investigated. Synergistic or additive effects were not seen for plastic microparticles (50 mg L-1) in combination with cypermethrin (10 and 1000 µg L-1) based on evaluation of skeletal abnormalities or arrested development and death of significant numbers of larvae during the embryotoxicity assay. This behaviour was also apparent for male gametes pretreated with PS and PMMA microplastics and cypermethrin, where a reduction in sperm fertilisation ability was not evidenced. However, a modest reduction in the quality of the offspring was noted, suggesting that there may be some transmissible damage to the zygotes. PMMA microparticles were more readily taken up than PS microparticles, which could suggest surface chemical identity as potentially modulating the affinity of larvae for specific plastics. In contrast, significantly reduced toxicity was noted for the combination of PMMA microparticles and cypermethrin (100 µg L-1), and may be related to less ready desorption of the pyrethroid than PS, as well as cypermethrin activating mechanisms that result in reduced feeding and hence decreased ingestion of microparticles.

Asunto(s)

Arbacia , Insecticidas , Piretrinas , Contaminantes Químicos del Agua , Animales , Masculino , Microplásticos/toxicidad , Plásticos , Insecticidas/farmacología , Polímeros/farmacología , Polimetil Metacrilato/farmacología , Contaminantes Químicos del Agua/toxicidad , Semen , Erizos de Mar , Desarrollo Embrionario , Piretrinas/farmacología

RESUMEN

Silver nanoparticles represent a threat to biota and have been shown to cause harm through a number of mechanisms, using a wide range of bioassay endpoints. While nanoparticle concentration has been primarily considered, comparison of studies that have used differently sized nanoparticles indicate that nanoparticle diameter may be an important factor that impacts negative outcomes. In considering this, the aim of the present study was to determine if different sizes of silver nanoparticles (AgNPs; 10, 20, 40, 60 and 100 nm) give rise to similar effects during embryogenesis of Mediterranean sea urchins Arbacia lixula and Paracentrotus lividus, or if nanoparticle size is a parameter that can modulate embryotoxicity and spermiotoxicity in these species. Fertilised embryos were exposed to a range of AgNP concentrations (1−1000 µg L−1) and after 48 h larvae were scored. Embryos exposed to 1 and 10 µg L−1 AgNPs (for all tested sizes) showed no negative effect in both sea urchins. The smaller AgNPs (size 10 and 20 nm) caused a decrease in the percentage of normally developed A. lixula larvae at concentrations ≥50 µg L−1 (EC50: 49 and 75 µg L−1, respectively) and at ≥100 µg L−1 (EC50: 67 and 91 µg L−1, respectively) for P. lividus. AgNPs of 40 nm diameter was less harmful in both species ((EC50: 322 and 486 µg L−1, for P. lividus and A. lixula, respectively)). The largest AgNPs (60 and 100 nm) showed a dose-dependent response, with little effect at lower concentrations, while more than 50% of larvae were developmentally delayed at the highest tested concentrations of 500 and 1000 µg L−1 (EC50(100 nm); 662 and 529 µg L−1, for P. lividus and A. lixula, respectively. While AgNPs showed no effect on the fertilisation success of treated sperm, an increase in offspring developmental defects and arrested development was observed in A. lixula larvae for 10 nm AgNPs at concentrations ≥50 µg L−1, and for 20 and 40 nm AgNPs at concentrations >100 µg L−1. Overall, toxicity was mostly ascribed to more rapid oxidative dissolution of smaller nanoparticles, although, in cases, Ag+ ion concentrations alone could not explain high toxicity, indicating a nanoparticle-size effect.

Asunto(s)

Arbacia , Nanopartículas del Metal , Paracentrotus , Animales , Masculino , Nanopartículas del Metal/toxicidad , Plata/toxicidad , Tamaño de la Partícula , Semen , Desarrollo Embrionario

RESUMEN

As nanoparticles have been found to cause a range of harmful impacts in biota, understanding processes and transformations which may stabilize and increase their persistence time in the environment are of great importance. As nanoparticles carried in riverine or wastewaters will eventually reach estuaries, understanding their behavior and transport potential in this transition zone from fresh to marine waters is essential, particularly as estuaries are sensitive ecological zones, oftentimes encompassing ornithologically important areas. In this direction, we report on the influence of combined gradients of riverine and marine natural organic matter (NOM) on the temporal stability of biocorona-encapsulated silver nanoparticles in terms of ion release kinetics. In parallel, salinity, pH and oxygen saturation were simultaneously varied to create a model to mimic the complex estuarine environment. While humic acid (HA) and alginate (Alg) disrupted the stabilizing ability of the nanoparticle protein corona to a greater and lesser degree, respectively, they slowed the rate of ion release in freshwater at pH 6.6 and in saltwater at pH 8, respectively, while oxygen saturation was also found to be an important factor. Thus, as the type of NOM changes with pH along a salinity gradient in an estuary, conditions required to increase the persistence time of nanoparticles are serendipitously met, with greater colloidal stability achieved in cases where there is more rapid replacement of HA with Alg. Despite the strong gradients in ionic strength, pH and oxygen saturation, the protein corona was not sufficiently disrupted at the nanoparticle surface to be substituted by NOM indicating the greater adsorption energy of the protein's hydrophobic domains. Ultimately, it is the specific NOM profile of individual estuaries that may provide the best indicator for predicting the stability and persistence of silver nanoparticles as they transition from fresh to salt water environments.

RESUMEN

Silver nanoparticles (AgNPs) are the most exploited nanomaterial in agriculture and food production, and their release into the environment raises concern about their impact on plants. Since AgNPs are prone to biotransformation, various surface coatings are used to enhance their stability, which may modulate AgNP-imposed toxic effects. In this study, the impact of AgNPs stabilized with different coatings (citrate, polyvinylpyrrolidone (PVP), and cetyltrimethylammonium bromide (CTAB)) and AgNO3 on photosynthesis of tobacco plants as well as AgNP stability in exposure medium have been investigated. Obtained results revealed that AgNP-citrate induced the least effects on chlorophyll a fluorescence parameters and pigment content, which could be ascribed to their fast agglomeration in the exposure medium and consequently weak uptake. The impact of AgNP-PVP and AgNP-CTAB was more severe, inducing a deterioration of photosynthetic activity along with reduced pigment content and alterations in chloroplast ultrastructure, which could be correlated to their higher stability, elevated Ag accumulation, and surface charge. In conclusion, intrinsic properties of AgNP coatings affect their stability and bioavailability in the biological medium, thereby indirectly contributing changes in the photosynthetic apparatus. Moreover, AgNP treatments exhibited more severe inhibitory effects compared to AgNO3, which indicates that the impact on photosynthesis is dependent on the form of Ag.

RESUMEN

Boc-L-DOPA(OBn)2-OH is a simple synthetic molecule that promotes hydrogelation through electrostatic and π-π stacking interactions. Hydrogelation can occur in alkaline conditions by the use of triggers. Four hydrogels were prepared varying the base, NaOH or Na2CO3, and the trigger, GdL or CaCl2. When the hydrogel formed in the presence of Na2CO3 and CaCl2, the concomitant production of CaCO3 crystals occurred, generating an organic/inorganic composite material. It was observed that the hydrogel once self-assembled preserved its status even if the trigger, the calcium ions, was removed. The viscoelastic behavior of the hydrogels was analyzed through rheological experiments, which showed a solid-like behavior of the hydrogels. The corresponding xerogels were analyzed mainly by scanning electron microscopy (SEM) and synchrotron X-ray diffraction analysis (XRD). They showed differences in structure, morphology, and fiber organization according to their source. This research presents a hydrogel system that can be applied as a soft biomaterial for tissue engineering, cosmetics, food, and environmental science. Moreover, it represents a model for biomineralization studies in which the hydrogel structure can act as an analogue of the insoluble matrix that confines the calcification site, provides Ca2+, and preserves its structure.