Marco Trifuoggi

Rare earth elements in human and animal health: State of art and research priorities.

BACKGROUND A number of applications have been developed using rare earth elements (REE), implying several human exposures and raising unsolved questions as to REE-associated health effects. METHODS A MedLine survey was retrieved from early reports (1980s) up to June 2015, focused on human and animal exposures to REE. Literature from animal models was selected focusing on REE-associated health effects. RESULTS Some REE occupational exposures, in jobs such as glass polishers, photoengravers and movie projectionists showed a few case reports on health effects affecting the respiratory system. No case-control or cohort studies of occupational REE exposures were retrieved. Environmental exposures have been biomonitored in populations residing in REE mining areas, showing REE accumulation. The case for a iatrogenic REE exposure was raised by the use of gadolinium-based contrast agents for nuclear magnetic resonance. Animal toxicity studies have shown REE toxicity, affecting a number of endpoints in liver, lungs and blood. On the other hand, the use of REE as feed additives in livestock is referred as a safe and promising device in zootechnical activities, possibly suggesting a hormetic effect both known for REE and for other xenobiotics. Thus, investigations on long-term exposures and observations are warranted. CONCLUSION The state of art provides a limited definition of the health effects in occupationally or environmentally REE-exposed human populations. Research priorities should be addressed to case-control or cohort studies of REE-exposed humans and to life-long animal experiments.

Comparative toxicities of selected rare earth elements: Sea urchin embryogenesis and fertilization damage with redox and cytogenetic effects.

BACKGROUND Broad-ranging adverse effects are known for rare earth elements (REE), yet only a few studies tested the toxicity of several REE, prompting studies focusing on multi-parameter REE toxicity. METHODS Trichloride salts of Y, La, Ce, Nd, Sm, Eu and Gd were tested in Paracentrotus lividus sea urchin embryos and sperm for: (1) developmental defects in either REE-exposed larvae or in the offspring of REE-exposed sperm; (2) fertilization success; (3) mitotic anomalies in REE-exposed embryos and in the offspring of REE-exposed sperm, and (4) reactive oxygen species (ROS) formation, and malondialdehyde (MDA) and nitric oxide (NO) levels. RESULTS REEs affected P. lividus larvae with concentration-related increase in developmental defects, 10(-6) to 10(-4)M, ranking as: Gd(III)>Y(III)>La(III)>Nd(III)≅Eu(III)>Ce(III)≅Sm(III). Nominal concentrations of REE salts were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Significant increases in MDA levels, ROS formation, and NO levels were found in REE-exposed embryos. Sperm exposure to REEs (10(-5) to 10(-4)M) resulted in concentration-related decrease in fertilization success along with increase in offspring damage. Decreased mitotic activity and increased aberration rates were detected in REE-exposed embryos and in the offspring of REE-exposed sperm. CONCLUSION REE-associated toxicity affecting embryogenesis, fertilization, cytogenetic and redox endpoints showed different activities of tested REEs. Damage to early life stages, along with redox and cytogenetic anomalies should be the focus of future REE toxicity studies.

A dynamic intraparticle model for fluid–solid adsorption kinetics

Abstract The fluid–solid adsorption batch kinetics is surely one of the most popular topic in the chemical engineering science. The water purification from pollutant components, such as metals and organic compounds, can be considered one of the main application of this field. Even if the topic is of a great scientific and industrial interest, the modeling of the mentioned systems is by now far to be reliable. As a matter of fact, most of the models reported in the literature are based on semi empirical approaches that describe the adsorption experimental data on the basis of equilibria and the kinetic terms. In this paper, a new modeling approach is proposed for adsorption kinetics investigation performed in batch reactors with a fluid–solid system. In particular, the mass balances have been developed by taking into account for both the external and internal mass transfer diffusion limitations, solving the dynamic partial differential equations (PDEs) system along the radius of the sorbent particles, considering both the fluid and solid phases that constitute the sorbent particle. From a numerical point of view, the solution of this type of problem is very challenging because it involves the simultaneous solution of many PDEs, ODEs and AEs. Here, physical parameters have to be evaluated either from existing correlations or by direct measurements. This fact makes the model predictable. In order to test the model, some Cu(II) and Pb(II) adsorption tests, taken from literature, using different kind of silica have been interpreted. The presented model can be considered of great interest, as it is the starting point for designing continuous adsorption columns for water purification.

A reinvestigation of β-TiCl3—I. Preparation and structural characterization

Abstract The preparation and the crystal structure of the β (brown) form of TiCl3 have been re-examined. Accurate X-ray diffraction measurements on crystallographically pure samples, free from A1, allowed refinement of the structure originally proposed by the Natta school in 1958, and in particular to fix the x coordinate of the chlorine atoms in the unit cell. The X-ray characterization of products with composition (β-TiCl 3 + 1 3 AlCl 3 ) gave no indication of the existence (suggested in the literature) of solid solutions β-TiCl3 · (AlCl3)0.33 analogous to those known for the violet modifications.

A reinvestigation of β-TiCl3—II. Catalytic activity in propene polymerization

Abstract The catalytic behaviour in propene polymerization of “preformed” samples of β (brown) TiCl3 was reinvestigated and compared with that of in situ TiCl4/AlR3 mixtures. Catalyst systems based on β-TiCl3 produced highly regioregular polypropene samples with microstructures close to those of polymers obtained in the presence of violet TiCl3 [apart from a lower fraction of “highly isotactic” macromolecules (insoluble in boiling heptane)]. On the other hand, catalyst systems originating from the interaction of TiCl4 and an Al-trialkyl in the polymerization medium were found to contain, in addition to a heterogeneous β-TiCl3 phase, homogeneous Ti species contributing substantially to the polymerization activity and responsible for the formation of a polymer fraction which is rather stereo- and regio-irregular and has low molecular weight.

Efficient Binding of Heavy Metals by Black Sesame Pigment: Toward Innovative Dietary Strategies To Prevent Bioaccumulation

Black sesame pigment (BSP) was shown to bind lead, cadmium, and mercury at pH 7.0 and to a lower extent at pH 2.0. BSP at 0.05 mg/mL removed the metals at 15 μM to a significant extent (>65% for cadmium and >90% for mercury and lead), with no changes following simulated digestion. The maximum binding capacities at pH 7.0 were 626.0 mg/g (lead), 42.2 mg/g (cadmium), and 69.3 mg/g (mercury). In the presence of essential metals, such as iron, calcium, and zinc, BSP retained high selectivity toward heavy metals. Model pigments from caffeic acid, ferulic acid, and coniferyl alcohol showed lower or comparable binding ability, suggesting that the marked properties of BSP may result from cooperativity of different sites likely carboxy groups and o-diphenol and guaiacyl functionalities. Direct evidence for the presence of such units was obtained by structural analysis of BSP by solid-state Fourier transform infrared spectroscopy and (13)C nuclear magnetic resonance spectroscopy.

A multidisciplinary approach for the characterization of the coastal marine ecosystems of Monte Di Procida (Campania, Italy)

A multidisciplinary survey was carried out on the quality of water and sediments of a coastal protected marine area, embedded between the inputs from Bagnoli steel plant to the south and a sewage plant, Volturno River and Regi Lagni channel to the north. The study integrated chemical-sedimentological data with biological and ecotoxicological analyses to assess anthropogenic pressures and natural variability. Data reveal marked differences in anthropogenic pollution between southeastern and northwestern zone, with the north affected by both inorganic and organic flows and the south influenced by levels of As, Pb and Zn in the sediments above law limits, deriving from inputs of the Bagnoli brownfield site. Meiobenthic data revealed at south higher relative abundance of sensitive species to pollution and environmental stress to the south, i.e. Lobatula lobatula and Rosalina bradyi, whereas to the north relative abundance of stress tolerant Quinqueloculina lata, Quinqueloculina pygmaea and Cribroelphidium cuvilleri were determined.

Sea Urchin Bioassays inToxicity Testing: I. Inorganics,Organics, Complex Mixturesand Natural Products

Sea Urchin Bioassays in Toxicity Testing: I. Inorganics, Organics, Complex Mixtures and Natural Products Based on established knowledge in physiology and embryology, sea urchins have proven to be excellent bioassay models since the early 1970’s when evaluating the impacts to early life stages and cellular functions after exposure to a number of xenobiotics. This review attempts to build a comprehensive survey of reports on sea urchin gametes and embryos used in toxicity testing of different classes of xenobiotics including inorganics, organics, different complex mixtures, and natural products. Our results provide support for common endpoints used when evaluating adverse effects on sea urchin early life stages, including frequency of developmental defects and/or cytogenetic abnormalities, changes in sperm fertilization success and offspring damage, and other endpoints related to redox alterations, DNA damage and other molecular biomarkers. Current studies using sea urchin bioassays continue to provide support for this tool in toxicology including, amongst others, studies of ocean acidification, action mechanisms of candidate new drugs, and novel xenobiotic releases to the environment.

Comparative transcriptional analysis reveals differential gene expression between Sand Daffodil tissues

Sand Daffodil (Pancratium maritimum) is a world-wide endangered Amayllidaceae species and represents an important anti-cancer medicinal resource due to alkaloids production. Despite its increasing pharmaceutical importance, there are not molecular resources that can be utilized toward improving genetic traits. In our research, the suppression subtractive hybridization (SSH) method conducted to generate large-scale expressed sequence tags (EST), was designed to identify gene candidates related to the morphological and physiological differences between the two tissues, leaves and bulbs, since lycorine, the main anti-cancer compound, is there synthesized. We focused on identification of transcripts in different tissues from Sand Daffodil using PCR-based suppression SSH to identify genes involved in global pathway control. Sequencing of 2,000 differentially screened clones from the SSH libraries resulted in 136 unigenes. Functional annotation and gene ontology analysis of up-regulated EST libraries showed several known biosynthetic genes and novel transcripts that may be involved in signaling, cellular transport, or metabolism. Real time RT-PCR analysis of a set of 8 candidate genes further confirmed the differential gene expression.

Characterization and source apportionment of polycyclic aromatic hydrocarbons (pahs) in the sediments of gulf of Pozzuoli (Campania, Italy)

Most of the literature reports on the impact of the former Bagnoli brownfield on the pollution of Bagnoli Bay, embedded in the Gulf of Pozzuoli (GoP). Thus, we studied concentrations, types and sources of sixteen PAHs (EPA) in sediments at 22 sites along 5 transects covering the entire area of GoP. Outstanding levels of PAHs were found, varying from 7.1μgg-1 to 2.5 E+3μgg-1. Sediments collected at sites far away from Bagnoli were found to be polluted to a similar extent than those facing the brownfield site, with values>100μgg-1. Total PAHs levels in the sediments of GoP were higher by thirty-eleven thousand fold than those reported by other studies from various marine sites in the world. Transit axes of fine and very fine sands and diagnostic indexes revealed a common pyrolytic PAHs pollution spreading from the Bagnoli plant to all GoP.