Effects of CeO2 Nanoparticles on Terrestrial Isopod Porcellio scaber: Comparison of CeO2 Biological Potential with Other Nanoparticles.

Nano-sized cerium dioxide (CeO2) particles are emerging as an environmental issue due to their extensive use in automobile industries as fuel additives. Limited information is available on the potential toxicity of CeO2 nanoparticles (NPs) on terrestrial invertebrates through dietary exposure. In the present study, the toxic effects of CeO2 NPs on the model soil organism Porcellio scaber were evaluated. Nanotoxicity was assessed by monitoring the lipid peroxidation (LP) level and feeding rate after 14-days exposure to food amended with nano CeO2. The exposure concentration of 1000 µg of CeO2 NPs g-1 dry weight food for 14 days significantly increased both the feeding rate and LP. Thus, this exposure dose is considered the lowest observed effect dose. At higher exposure doses of 2000 and 5000 µg of CeO2 NPs g-1 dry weight food, NPs significantly decreased the feeding rate and increased the LP level. Comparative studies showed that CeO2 NPs are more biologically potent than TiO2 NPs, ZnO NPs, CuO NPs, CoFe2O4 NPs, and Ag NPs based on feeding rate using the same model organism and experimental setup. Based on comparative metal oxide NPs toxicities, the present results contribute to the knowledge related to the ecotoxicological effects of CeO2 NPs in terrestrial invertebrates exposed through feeding.

Synthesis of bioactive ß-TCP coatings with tailored physico-chemical properties on zirconia bioceramics.

The objective of this work was to develop a synthesis procedure for the deposition of ß-TCP coatings with tailored physico-chemical properties on zirconia bioceramics. The synthesis procedure involved two steps: (i) a rapid wet-chemical deposition of a biomimetic CaP coating and (ii) a subsequent post-deposition processing of the biomimetic CaP coating, which included a heat treatment between 800 and 1200 °C, followed by a short sonication in a water bath. By regulating the heating temperature the topography of the ß-TCP coatings could be controlled. The average surface roughness (Ra) ranged from 42 nm for the coating that was heated at 900 °C (TCP-900) to 630 nm for the TCP-1200 coating. Moreover, the heating temperature also affected the dissolution rate of the coatings in a physiological solution, their protein-adsorption capacity and their bioactivity in a simulated body fluid.

Influence of bacterial lysate quality on growth of two bacterioplankton species.

All physico-chemical parameters that affect bacterial growth rate will also affect bacterial molecular composition, which in turn influences the chemical composition of bacterial lysate and its turnover rate in the ecosystem. To produce qualitatively different lysates, Vibrio sp. cells were grown under different pH, salt, or temperature conditions in rich growth media and then washed and lysed by autoclaving. Both the absolute concentrations and the ratios between elements in the lysates varied with different growth conditions, implying differences in lysate quality. Either Pseudoalteromonas sp. or Vibrio sp. was grown on the lysates at non-limiting lysate concentrations. Different lysates supported growth rates of Pseudoalteromonas sp. in the range from 0.25 to 1.53 h(-1). On the other hand, growth rates of Vibrio sp. grown on its own lysates were around 0.4 h(-1) and were not dependent on lysate quality. Two orders of magnitude decrease in Zn concentration in Vibrio sp. cells grown on different lysates as compared to cells grown on rich growth medium suggested that Zn might be a factor limiting growth. In the simple microbial loop studied, the initial difference in lysate quality was preserved in Pseudoalteromonas sp., whereas Vibrio sp. decreased the initial differences in lysate quality, thereby neutralizing the primary effect of environmental conditions on carbon turnover.

Crystal structure of a new polymorph of Li2FeSiO4.

We report on the crystal structure of a new polymorph of Li(2)FeSiO(4) (prepared by annealing under argon at 900 degrees C and quenching to 25 degrees C) characterized by electron microscopy and powder X-ray and neutron diffraction. The crystal structure of Li(2)FeSiO(4) quenched from 900 degrees C is isostructural with Li(2)CdSiO(4), described in the space group Pmnb with lattice parameters a = 6.2836(1) A, b = 10.6572(1) A, and c = 5.0386(1) A. A close comparison is made with the structure of Li(2)FeSiO(4) quenched from 700 degrees C, published recently by Nishimura et al. (J. Am. Chem. Soc. 2008, 130, 13212). The two polymorphs differ mainly on the respective orientations and alternate sequences of corner-sharing FeO(4) and SiO(4) tetrahedra.

The effects of selenium biofortification on mercury bioavailability and toxicity in the lettuce-slug food chain.

The effects of foliar Se biofortification (Se+) of the lettuce on the transfer and toxicity of Hg from soil contaminated with HgCl2 (H) and soil collected near the former Hg smelter in Idrija (I), to terrestrial food chain are explored, with Spanish slug as a primary consumer. Foliar application of Se significantly increased Se content in the lettuce, with no detected toxic effects. Mercury exerted toxic effects on plants, decreasing plant biomass, photochemical efficiency of the photosystem II (Fv/Fm) and the total chlorophyll content. Selenium biofortification (Se+ test group) had no effect on Hg bioaccumulation in plants. In slugs, different responses were observed in H and I groups; the I/Se+ subgroup was the most strongly affected by Hg toxicity, exhibiting lower biomass, feeding and growth rate and a higher hepatopancreas/ muscle Hg translocation, pointing to a higher Hg mobility in comparison to H group. Selenium increased Hg bioavailability for slugs, but with opposite physiological responses: alleviating stress in H/Se+ and inducing it in I/Se+ group, indicating different mechanisms of Hg-Se interactions in the food chain under HgCl2 and Idrija soil exposures that can be mainly attributed to different Hg speciation and ligand environment in the soil.

Environmental status of the NE Adriatic Sea, Istria, Croatia: Insights from mussel Mytilus galloprovincialis condition indices, stable isotopes and metal(loid)s.

The environmental status of the marine environment in the NE Adriatic Sea was assessed, using as a bioindicator species the Mediterranean mussel Mytilus galloprovincialis Lamarck, 1819. Samples were collected seasonally from mariculture sites and from major Istrian ports between the years 2010 and 2013. The condition indices of mussels ranged from 13.3 to 20.9% at mariculture sites and from 14.3 to 23.3% at port locations. The seasonally δ13CDIC values of seawater varied between -10.9 to 0.7‰. Pollution by sewage sludge (based on δ15N values) was confirmed only in two ports. Tissue concentrations of Mn, Co, Ni, Cu, Zn, Se, Cd, and Pb were significantly higher in the tissue of the mussels collected from the ports (polluted sites). Arsenobetaine was the major As compound present in the samples and there was no significant difference in the levels of total As in mussel tissues from mariculture and port sites.

Successful Synthesis of Gold Nanoparticles through Ultrasonic Spray Pyrolysis from a Gold(III) Nitrate Precursor and Their Interaction with a High Electron Beam.

Herein, we report for the first time the successful preparation of a gold(III) nitrate [Au(NO3)3] water-based precursor for use in a bottom-up ultrasonic spray pyrolysis (USP) process. Due to its limited solubility in water, the precursor was prepared under reflux conditions with nitric acid (HNO3) as the solvent and ammonium hydroxide (NH4OH) as a neutralizer. This precursor enabled the USP synthesis of gold nanoparticles (AuNPs) and the in situ formation of low concentrations of NO2- and NO3- ions, which were caught directly in deionized water in a collection system. These ions were proven to act as stabilizers for the AuNPs. Investigations showed that the AuNPs were monodispersed and spherically shaped with a size distribution over three groups: the first contained 5.3 % AuNPs with diameters (2 r) <15 nm, the second contained 82.5 % AuNPs with 2 r between 15 and 200 nm, and the third contained 12.2 % AuNPs with 2 r>200 nm. UV/Vis spectroscopy revealed the maximum absorbance band of the AuNPs at λ=528 nm. Additionally, scanning transmission electron microscopy (STEM) observations of the smallest AuNPs (2 r<5 nm) revealed atomically resolved coalescence phenomena induced by interaction with the electron beam. Four stages of the particle-growth process were distinguished: 1) movement and rotation of the AuNPs; 2) necking mechanism; 3) orientated attachment at matching facets; 4) reshaping of the AuNPs by surface diffusion. This provided important insight into the formation/synthesis process of the AuNPs.

Robust polarization and strain behavior of Sm-modified BiFeO3 piezoelectric ceramics.

The route to phase-pure BiFeO3 (BFO) ceramics with excellent ferroelectric and electromechanical properties is severely impeded by difficulties associated with the perovskite phase stability during synthesis. This has meant that dopants and solid solutions with BFO have been investigated as a means of not only improving the functional properties, but also of improving the perovskite phase formation of BFO-based ceramics. The present work focuses on Sm-modified BFO ceramics of composition Bi0.88Sm0.12FeO3. The polarization and strain behaviors were investigated as a function of the phase composition, microstructure, and chemical composition. Addition of Sm reduces the susceptibility of the BFO perovskite to phase degradation by Si impurities. Si was observed to react into Sm-rich grains dispersed within the microstructure, with no large increases in the amount of bismuth-parasitic phases, namely Bi25FeO39 and Bi2Fe4O9. These as-prepared ceramics exhibited robust polarization behavior showing maximum remnant polarizations of ~40 to 50 µC/cm(2). The electric-fieldinduced strain showed an appreciable stability in terms of the driving field frequency with maximum peak-to-peak strains of ~0.3% and a coercive field of ~130 kV/cm.

Relevance for food sciences of quantitative spatially resolved element profile investigations in wheat (Triticum aestivum) grain.

Bulk element concentrations of whole grain and element spatial distributions at the tissue level were investigated in wheat (Triticum aestivum) grain grown in Zn-enriched soil. Inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry were used for bulk analysis, whereas micro-proton-induced X-ray emission was used to resolve the two-dimensional localization of the elements. Soil Zn application did not significantly affect the grain yield, but did significantly increase the grain Ca, Fe and Zn concentrations, and decrease the grain Na, P and Mo concentrations; bulk Mg, S, K, Mn, Cu, Cd and Pb concentrations remained unchanged. These changes observed in bulk element concentrations are the reflection of tissue-specific variations within the grain, revealing that Zn application to soil can lead to considerable alterations in the element distributions within the grain, which might ultimately influence the quality of the milling fractions. Spatially resolved investigations into the partitioning of the element concentrations identified the tissues with the highest element concentrations, which is of utmost importance for accurate prediction of element losses during the grain milling and polishing processes.

Immunomodulatory properties of nanoparticles obtained by ultrasonic spray pirolysis from gold scrap.

We prepared 5 different fractions of nanoparticles from the gold scrap, by using a new technology, Ultrasonic Spray Pirolysis (USP). The aim of this study was to characterize the microstructure and cytotoxicity of the nanoparticles along with their immunomodulatory properties, using Concanavaline A (ConA)-treated rat splenocytes as a model of activated immune cells. Fractions 1 and 2, composed of pure gold nanoparticles, although non-cytotoxic, reduced cellular proliferation. Fraction 2, containing particles smaller in size and lesser agglomerated than fraction 1, up- and down-regulated the production of IL-2 and IL-10, respectively, by activated splenocytes. Fraction 3, containing nanoparticles composed of Au and up to 3 at.% Cu, was non-cytotoxic, but reduced IL-2 production and cell proliferation. Fractions 4 and 5, contaminated with alloying elements from the gold scrap, were cytotoxic. The extent of cytotoxicity and subsequent reduction of cytokine production, as well as the mode of cell death, depended on their composition. In conclusion, we showed that USP enables the synthesis of gold nanoparticles, which could be suitable for various biological applications, and that ConA-treated splenocytes represent a reliable model for fast and accurate evaluation of the immunotoxicological profiles of these particles. However, it is necessary to improve this technology and investigate further some of the immunomodulatory mechanisms using more specific immunological tests.

A solid-liquid extraction approach to elucidate the chemical availability of metals in soil and sediment assuming Langmuir isotherm behaviour.

In an earlier paper (Anal. Chim. Acta 514 (2004) 137) we claimed that the maximal extractability of a metal from soil or sediment for a user-defined extractant, i.e. the chemical availability in that particular extractant, may be biased as a result of inadequate volume to mass (V/m) ratios. Correcting for that artifact using an implementation of the simple linear isotherm model gave good results although we cautioned the general applicability. In this paper we will theoretically derive the limitations of that approach based on the more general assumption that sorption processes are described by a Langmuir isotherm. NIST reference material 8704 was extracted with 1moll(-1) NaOAc (adjusted to pH 5) to experimentally verify the applicability of the Langmuir isotherm approach and illustrate the deviations obtained for some metals using the linear isotherm approach. Of the seven metals measured (Cr, Co, Ni, Cu, Zn, Cd, and Ba) only for Cr and Cu severe discrepancies between both approaches were found, which could be traced back to non-linear isotherm behaviour. Moreover, the Langmuir isotherm approach showed that the above mentioned extractability artifact is even more serious than earlier assumed applying the linear isotherm approach.