M. G. Rasteiro

Toxicity and genotoxicity of organic and inorganic nanoparticles to the bacteria Vibrio fischeri and Salmonella typhimurium

The present work aimed at evaluating the toxicity and genotoxicity of two organic (vesicles composed of sodium dodecyl sulphate/didodecyl dimethylammonium bromide—SDS/DDAB and of monoolein and sodium oelate—Mo/NaO) and four inorganic (titanium oxide—TiO2, silicon titanium—TiSiO4, Lumidot™-CdSe/ZnS, and gold nanorods) nanoparticles (NP), suspended in two aqueous media (Milli Q® water and American Society for Testing and Materials (ASTM) hardwater), to the bacteria Vibrio fischeri (Microtox® test) and Salmonella typhimurium-his− (Ames® test with strains TA98 and TA100). Aiming a better understanding of these biological responses physical and chemical characterization of the studied NP suspensions was carried out. Results denoted a high aggregation state of the NP in the aqueous suspensions, with the exception of SDS/DDAB and Mo/NaO vesicles, and of nanogold suspended in Milli Q water. This higher aggregation was consistent with the low values of zeta potential, revealing the instability of the suspensions. Regarding toxicity data, except for nano TiO2, the tested NP significantly inhibited bioluminescence of V. fischeri. Genotoxic effects were only induced by SDS/DDAB and TiO2 for the strain TA98. A wide range of toxicity responses was observed for the six tested NP, differing by more than 5 orders of magnitude, and suggesting different modes of action of the tested NP.

Screening evaluation of the ecotoxicity and genotoxicity of soils contaminated with organic and inorganic nanoparticles: The role of ageing

This study aimed to evaluate the toxicity and genotoxicity of soils, and corresponding elutriates, contaminated with aqueous suspensions of two organic (vesicles of sodium dodecyl sulphate/didodecyl dimethylammonium bromide and of monoolein and sodium oleate) and five inorganic nanoparticles (NPs) (TiO(2), TiSiO(4), CdSe/ZnS quantum dots, Fe/Co magnetic fluid and gold nanorods) to Vibrio fischeri and Salmonella typhimurium (TA98 and TA100 strains). Soil samples were tested 2h and 30 days after contamination. Suspensions of NPs were characterized by Dynamic Light Scattering. Soils were highly toxic to V. fischeri, especially after 2h. After 30 days toxicity was maintained only for soils spiked with suspensions of more stable NPs (zeta potential>30 mV or <-30 mV). Elutriates were particularly toxic after 2h, except for soil spiked with Fe/Co magnetic fluid, suggesting that ageing may have contributed for degrading the organic shell of these NPs, increasing the mobility of core elements and the toxicity of elutriates. TA98 was the most sensitive strain to the mutagenic potential of soil elutriates. Only elutriates from soils spiked with gold nanorods, quantum dots (QDs) and TiSiO(4) induced mutations in both strains of S. typhimurium, suggesting more diversified mechanisms of genotoxicity.

Toxicity of organic and inorganic nanoparticles to four species of white-rot fungi

The rapid development of nanoparticles (NP) for industrial applications and large-volume manufacturing, with its subsequent release into the environment, raised the need to understand and characterize the potential effects of NP to biota. Accordingly, this work aimed to assess sublethal effects of five NP to the white-rot fungi species Trametes versicolor, Lentinus sajor caju, Pleurotus ostreatus, and Phanerochaete chrysosporium. Each species was exposed to serial dilutions of the following NP: organic-vesicles of SDS/DDAB and of Mo/NaO; gold-NP, quantum dot CdSe/ZnS, and Fe/Co. Fungi growth rate was monitored every day, and at the end of assay the mycelium from each replicate was collected to evaluate possible changes in its chemical composition. For all NP-suspensions the following parameters were characterized: hydrodynamic diameter, surface charge, aggregation index, zeta potential, and conductivity. All tested NP tended to aggregate when suspended in aqueous media. The obtained results showed that gold-NP, CdSe/ZnS, Mo/NaO, and SDS/DDAB significantly inhibited the growth of fungi with effects on the mycelium chemical composition. Among the tested NP, gold-NP and CdSe/ZnS were the ones exerting a higher effect on the four fungi. Finally to our knowledge, this is the first study reporting that different types of NP induce changes in the chemical composition of fungi mycelium.

Biochemical and metabolic effects of a short-term exposure to nanoparticles of titanium silicate in tadpoles of Pelophylax perezi (Seoane)

This study aimed to evaluate sublethal effects of a short-term exposure (96 h) to titanium silicate nanoparticles (TiSiO(4)-NP) on Pelophylax perezi tadpoles. Tadpoles were exposed to five concentrations of TiSiO(4)-NP (8.2, 10.2, 12.8, 16 and 20 mg/L) plus a control. Effect criteria were: mortality, cholinesterases, glutathione S-transferases, lactate dehydrogenase, and catalase activities, and alanine and lactate contents. Light scattering was used for physical characterization of TiSiO(4)-NP suspensions, revealing a high aggregation state of the NP, consistent with low z-potential values (<30 mV). Mortality among TiSiO(4)-NP treatments was <11%. Significant differences relatively to the control were observed at the biochemical level (for CAT and LDH) and in lactate and alanine contents, which may end-up in increased oxidative stress. Overall, some of the monitored endpoints suggest metabolic alterations in TiSiO(4)-NP exposed tadpoles, highlighting the potential of TiSiO(4)-NP long-term effects on these organisms.

Applying LDS to Monitor Flocculation in Papermaking

Flocculation of fines and fillers is important in the papermaking industry. To fulfill the need for accurate control of flocculation, laser diffraction spectroscopy (LDS) was selected to supply the floc size distribution. LDS allowed the detection of different flocculation mechanisms depending on the flocculant characteristics. The analysis relied mainly on the collection of two parameters: the size distribution of the flocs, characterized by its median, and their fractal dimension. Floc resistance to shear was assessed and related to the floc structure through the analysis of the fractal dimension. For the lower charge density, flocs grow faster, becoming less compact and, thus, less resistant. LDS proved to be a valuable technique to monitor flocculation processes. However, to obtain significant results, a close control of obscuration in the measuring cell is required.

A virtual platform to teach separation processes

In this article the Unit Operations and Separation Processes area of a virtual platform called LABVIRTUAL(http://labvirtual.eq.uc.pt) is presented aiming to support the autonomous study of undergraduate students engaged in a Chemical Engineering degree, especially in Portuguese‐speaking countries. The main features, subjects, computational applications, and examples in the platform are described, as well as a first assessment by the students.

Nanoparticle Characterization by PCS: The Analysis of Bimodal Distributions

Photon correlation spectroscopy (PCS) is widely used for nanoparticle characterization, being particularly suited for the analysis of narrow distributions. However, because of its simplicity, it would be important to extend it to other situations, namely to wide particle size distributions and to bimodal samples. In this work an evaluation of the discriminating capability of the most common algorithms used in PCS to deconvolute the measured auto-correlation function, when analyzing bimodal samples, was performed. The results show that the CONTIN algorithm enables a better description of bimodal mixtures, though its performance is dependent on the characteristics of the sample and on operating conditions such as the sampling time. Additionally, a close analysis of the auto-correlation function revealed the existence of systematic deviations in the slope of the first section of that function when a bimodal sample is compared with the equivalent monomodal one (same average diameter). The results obtained indicate that the inspection of the first part of the auto-correlation function produces important information that can reveal the presence of more than one peak when an unknown sample is analyzed. This feature is rather important since the inversion process may mask one of the peaks due to the ill-conditioned nature of the problem. This prior information can be useful to alert the user to the need for an iterative adjustment of the parameters of the inversion process in order to better reveal all the peaks in the sample.

Polyurethane-based microparticles : Formulation and influence of processes variables on its characteristics

This study reports the development of polyurethane-based microparticles and the influence of some processes variables on its characteristics. These microparticles were prepared by emulsion polymerization, using poly(caprolactone) diol (PCL) and poly(propylene glycol), tolylene 2,4-diisocyanate terminated (TDI) or poly(propylene oxide)-based tri-isocyanated pre-polymer (TI). The reaction of polymerization was confirmed by attenuated total internal reflection Fourier transformed infrared spectroscopy (ATR-FTIR). Their thermal characteristics were investigated by dynamical mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). For good microparticles formation, formulation 80/20 (mass ratio isocyanate/PCL) was the most indicated. Their spherical shape and smooth surface were observed by optical and scanning electron microscopy (SEM). Zeta potential measurements suggest that ionized carbonyl groups existent at the surface can be responsible for the negative potentials obtained. Respecting size and size distribution of the particles, measured by laser diffraction spectroscopy (LDS), the stirring speed and type were the process variables that most influenced it.

Ecotoxicity of titanium silicon oxide (TiSiO4) nanomaterial for terrestrial plants and soil invertebrate species.

The huge evolution of nanotechnology and the commercialization of nanomaterials (NMs) positively contributed for innovation in several industrial sectors. Facing this rapid development and the emergence of NMs in the market, the release of this nanometric sized materials in the environment and the possible impact on different ecosystem components attracted the attention of researchers in the last few years. In our study we aimed to assess the impact of titanium silicon oxide nanomaterial (nano-TiSiO4) on soil biota to estimate a risk limit for this material. In the present research a battery of standardized ecotoxicological assays aimed at evaluating a wide range of endpoints (avoidance and reproduction of earthworms and collembolans, emergence/growth of four selected terrestrial plants) were carried out, using OECD artificial soil as test substrate spiked with aqueous suspension of different concentrations of nano-TiSiO4. The results showed a maximum avoidance percentage of 40% for earthworms (Esenia andrei) at the highest concentration tested (1000mgkg(-1) soildw of nano-TiSiO4). No significant effect on the reproductive function of both invertebrate species was recorded. Nevertheless, significant phytotoxic data was registered at least for the growth of dicotyledonous plant species (Lactuca sativa and Lycopersicon lycopersicum) with EC20 values ranging between 236 and 414 mg kg(-1) soildw of nano-TiSiO4 for L. sativa dry mass and fresh mass, respectively. Further, the characterization of nano-TiSiO4 in suspensions used to spike the soil, performed by Dynamic Light Scattering, showed the formation of aggregates with important average size diameter, thus demonstrating that the toxic effects observed were likely not size dependent. A deterministic PNEC (predicted no effect concentration) for this NM of 10.02mg kg(-1) soildw of nano-TiSiO4, is suggested, while no more ecotoxicological information exists.

Impact of organic nano-vesicles in soil: The case of sodium dodecyl sulphate/didodecyl dimethylammonium bromide.

Aiming at contributing new insights into the effects of nanomaterials (NMs) in the terrestrial ecosystem, this study evaluated the impacts of organic nano-vesicles of sodium dodecyl sulphate/didodecyl dimethylammonium bromide (SDS/DDAB) on the emergence and growth of plant seeds, and on the avoidance and reproduction of soil invertebrates. For this purpose several ecotoxicological assays were performed with different test species (terrestrial plants: Zea mays, Avena sativa, Brassica oleracea and Lycopersicon esculentum; soil invertebrates: Eisenia andrei and Folsomia candida). A wide range of SDS/DDAB concentrations were tested, following standard protocols, and using the standard OECD soil as a test substrate (5% of organic matter). The aqueous suspensions of SDS/DDAB, used to spike the soils, were characterised by light scattering techniques for hydrodynamic size of the vesicles, aggregation index, polydispersity index, zeta potential and surface charge. The SDS/DDAB concentrations in the test soil were analysed by HPLC-UV at the end of the assays. Invertebrate species were revealed to be sensitive to nano-SDS/DDAB upon immediate exposure to freshly spiked soils. However, the degradation of SDS/DDAB nano-vesicles in the soil with time prevented the occurrence of significant reproduction effects on soil invertebrates. Plants were not particularly sensitive to SDS/DDAB, except B. oleracea (at concentrations above 375 mg kg(-1)dw). The results gathered in this study allowed a preliminary determination of a risk limit to nano-SDS/DDAB. The low toxicity of SDS/DDAB nano-vesicles could be explained by its high and fast degradation in the soil. The soil microbial community could have an important role in the fate of this NM, thus it is of remarkable importance to improve this risk limit by taking into account specific data addressing this community.