The mechanism of iron binding processes in erionite fibres

Fibrous erionite-Na from Rome (Oregon, USA) was K-exchanged and characterized from the structural point of view. In addition, the modifications experienced after contact with a Fe(II) source were investigated for evaluating if the large potassium ions, blocking off nearly all the erionite cavity openings, might prevent the Fe(II) binding process, which is currently assumed to be one of the reasons of the toxicity of erionite. The K-exchanged sample had a 95% reduction of the BET surface area indicating that it behaves as a mesoporous material. Exchanged K is segregated at K2 and at OW sites commonly occupied by H2O. The latter K cations provide a relevant contribution to the reduction of the surface area. Surprisingly, despite the collapse of its surface area the sample preserves the tendency to bind Fe(II). Therefore, yet in the case of a peculiar and potentially hostile structural environment the Fe(II) ion-exchange process has essentially the same kinetics observed in a typical erionite sample. This is a clear evidence of the very limited effect of the chemical composition of erionite on the Fe(II) binding process and reasonably it does not play a significant role in its toxicity

Modelling the Fenton reaction of amphibole asbestos

In this work a sample of UICC crocidolite and a sample of fibrous tremolite were leached up to 1 week both in a simplified Gamble’s solution at acidic pH and in a phosphate buffered medium at neutral pH, in presence of H2O2. Surface chemical modifications were monitored by XPS spectroscopy. Subsequently, the generation of HO• radicals following reaction of both pristine and leached fibres with H2O2 (Fenton reaction) was investigated by spin trapping/EPR spectroscopy, with the aim of better clarifying the relationships between possible surface alteration occurring in vivo and chemical reactivity of amphibole asbestos. Moreover, the generation of HO• radicals was monitored on thermally treated fibres after leaching in phosphate buffered medium at neutral pH and in presence of H2O2 to investigate how chemical reactivity may be modulated by Fe oxidation state. Results showed that, for both amphibole asbestos, the surface alteration following incubation in the modified Gamble’s solution does not alter HO• radical generation. Interestingly, leaching in phosphate buffered solution in presence of H2O2 induced a progressive increase in HO• release for crocidolite fibres, whereas a strong reduction was observed for asbestos tremolite. This behaviour is likely due to the quicker alteration of the crocidolite surface due to the interaction with H2O2, as indicated by XPS analysis. In particular, the oxidation induced by H2O2 promotes the dissolution of the first atomic layer of the crocidolite structure and the following occurrence on its surface of new reactive Fe centres, particularly under the form of Fe(II), of which the bulk is richer than the oxidized surface. Accordingly, the heated samples showed a reduced, but not suppressed by thermal oxidation, chemical reactivity, with no significant evolution following incubation in phosphate buffered medium at neutral pH and in presence of H2O2

Content, mineral allocation and leaching behavior of heavy metals in urban PM2.5

This work provides a novel perspective in the field of urban airborne particle investigation that is not currently found in the literature. Four sampling campaigns were performed in the urban area of Rome (Central Italy) during the winter and summer seasons (February and July 2013 and 2014, respectively). The measured concentrations of the regulated 34 elements of As, Cd, Ni and Pb were consistent with those reported by the local Environmental Agency (ARPA Lazio), but non-regulated heavy metals, including Fe, Cu, Cr and Zn, were also found in PM2.5 and analyzed in detail. As an novelty, heavy metals were associated with the host-identified mineral phases, primarily oxides and alloys, and to a lesser extent, other minerals, such as sulfates, carbonates and silicates. Leaching tests of the collected samples were conducted in a buffered solution mimicking the bodily physiological environment. Despite the highest concentration of heavy metals found during the winter sampling period, all of the elements showed a leaching trend leading to major mobility during the summer period. To explain this result, an interesting comparative analysis between the leaching test behavior and innovative mineral allocation was conducted. Both the heavy metal content and mineral allocation in PM2.5 might contribute to the bioavailability of toxic elements in the pulmonary environment. Hence, for regulatory purposes, the non-linear dependency of heavy metal bioavailability on the total metal content should be taken into account

Determination of phenolic acids using Trametes versicolor laccase

WOS: 000244059600047PubMed ID: 19071305Two biosensors based on Trametes versicolor laccase (TvL) were developed for the determination of phenolic compounds. Commercial oxygen electrode and ferrocene-modified screen-printed graphite electrodes were used for preparation of laccase biosensors. The systems were calibrated for three phenolic acids. Linearity was obtained in the concentration range 0.1-1.0 mu M caffeic acid, 0.05-0.2 mu M ferulic acid, 2.0-14.0 mu M syringic acid for laccase immobilised on a commercial oxygen electrode and 2.0-30.0 mu caffeic acid, 2.0-10.0 mu M ferulic acid, 4.0-30.0 mu M syringic acid for laccase immobilised on ferrocene-modified screen-printed electrodes. Furthermore, optimal pH, temperature and thermal stability studies were performed with the commercial oxygen electrode. Both electrodes were used for determination of a class of phenolic acids, achieving a cheap and fast tool and an easy to be used procedure for screening real samples of human plasma. (c) 2006 Elsevier B.V. All rights reserved

Dissolution of amphibole asbestos in modified Gamble's solution at pH 4.5. A combined ICP-OES, XPS and TEM investigation

This study analizes the dissolution reactions, and the corresponding surface modifications, of two amphibole asbestos incubated for 1, 24, 48, 168 and 720 h in a modified Gamble's solution at pH 4.5. The investigated samples are UICC crocidolite from Koegas Mine, Northern Cape (South Africa), and fibrous tremolite from Montgomery County, Maryland (USA). lnductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) was used to monitor the ion release into solution, X-Ray Photoelectron Spectroscopy (XPS) was performed to unveil the chemistry of the leached surface, and High Resolution Transmission Electron Microscopy (HR-TEM) was exploited for monitoring the structural modifications of the fibres. An incongruent cation mobilization was observed in both samples. Fe mobilization was detected only in UICC crocidolite, due to the occurrence of Fe-bearing accessory phases in the sample (siderite, iron carbonate, and minnesotaite, an iron-bearing phyllosilicate). Notably, tremolite lifetime is shown to be roughly ten times that of UICC crocidolite under the same experimental conditions. This result agrees with previous dissolution studies at pH 7.4 indicating a higher dissolution and surface alteration for UICC crocidolite with respect to tremolite

Zinc Oxide Nanorods-Decorated Graphene Nanoplatelets: A Promising Antimicrobial Agent against the Cariogenic Bacterium Streptococcus mutans

Nanomaterials are revolutionizing the field of medicine to improve the quality of life due to the myriad of applications stemming from their unique properties, including the antimicrobial activity against pathogens. In this study, the antimicrobial and antibiofilm properties of a novel nanomaterial composed by zinc oxide nanorods-decorated graphene nanoplatelets (ZNGs) are investigated. ZNGs were produced by hydrothermal method and characterized through field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) techniques. The antimicrobial activity of ZNGs was evaluated against Streptococcus mutans, the main bacteriological agent in the etiology of dental caries. Cell viability assay demonstrated that ZNGs exerted a strikingly high killing effect on S. mutans cells in a dose-dependent manner. Moreover, FE-SEM analysis revealed relevant mechanical damages exerted by ZNGs at the cell surface of this dental pathogen rather than reactive oxygen species (ROS) generation. In addition, inductively coupled plasma mass spectrometry (ICP-MS) measurements showed negligible zinc dissolution, demonstrating that zinc ion release in the suspension is not associated with the high cell mortality rate. Finally, our data indicated that also S. mutans biofilm formation was affected by the presence of graphene-zinc oxide (ZnO) based material, as witnessed by the safranin staining and growth curve analysis. Therefore, ZNGs can be a remarkable nanobactericide against one of the main dental pathogens. The potential applications in dental care and therapy are very promising

Surface alteration mechanism and topochemistry of iron in tremolite asbestos. A step toward understanding the potential hazard of amphibole asbestos

Non-occupational, environmental and unintentional exposure to fibrous tremolite, one of the most widespread naturally occurring asbestos, represents a potentially significant geological risk in several parts of the world. The toxicity of amphibole asbestos is commonly related to iron content and oxidation state, but information available on surface iron topochemistry and amphibole alteration mechanism is still rather poor. With the aim to shed a light on this mechanism, two tremolite samples, one from Italy (Castelluccio) and one from USA (Maryland), immersed in a buffer solution (pH7.4) with H2O2 were characterized by a multi-technique approach. X-ray photoelectron spectroscopy (XPS) and high resolution-transmission electron microscopy (HR-TEM) were used to investigate the surface chemistry of the incubated samples and to detect structural modifications of the fibres, while inductively coupled plasma optical emission spectrometry (ICP-OES) was used to determine the concentration of dissolved elements.An original four-step model for amphibole alteration pathway is proposed. The alteration process starts with an incongruent dissolution of the amphiboles that produces an amorphous, altered surface layer and that is followed by iron oxidation and formation of FeOOH species. Then the congruent dissolution of the altered layer starts and, subsequently, the residual Fe oxi-hydroxides aggregates and insoluble, Fe-rich, amorphous nanoparticles on top of the fibres are formed. The results are compared to those obtained on crocidolite, a highly toxic amphibole asbestos with a 10 to 20 times higher iron content than tremolite. The high chemical reactivity observed in the literature for tremolite appears to be related not only to its iron content and oxidation state, but also to the low nuclearity of iron on the altered surfaces, in contrast to pronounced Fe clusterization at crocidolite surfaces. This is a significant step toward a conceivable explanation of why asbestos tremolite is potentially as toxic as crocidolite

Toxicity of the readily leachable fraction of urban PM2.5 to human lung epithelial cells. Role of soluble metals

Fine airborne particulate matter (PM2.5) has been repeatedly associated with adverse health effects in humans. The PM2.5 soluble fraction, and soluble metals in particular, are thought to cause lung damage. Literature data, however, are not consistent and the role of leachable metals is still under debate. In this study, Winter and Summer urban PM2.5 aqueous extracts, obtained by using a bio-compatible solution and different contact times at 37 °C, were used to investigate cytotoxic effects of PM2.5 in cultured lung epithelial cells (A549) and the role played by the leachable metals Cu, Fe, Zn, Ni, Pb and Cd. Cell viability and migration, as well as intracellular glutathione, extracellular cysteine, cysteinylglycine and homocysteine concentrations, were evaluated in cells challenged with both PM2.5 extracts before and after ultrafiltration and artificial metal ion solutions mimicking the metal composition of the genuine extracts. The thiol oxidative potential was also evaluated by an abiotic test. Results demonstrate that PM2.5 bioactive components were released within minutes of PM2.5 interaction with the leaching solution. Among these are i) low MW (<3 kDa) solutes inducing oxidative stress and ii) high MW and/or water-insoluble compounds largely contributing to thiol oxidation and to increased homocysteine levels in the cell medium. Cu and/or Ni ions likely contributed to the effects of Summer PM2.5 extracts. Nonetheless, the strong bio-reactivity of Winter PM2.5 extracts could not be explained by the presence of the studied metals. A possible role for PM2.5 water-extractable organic components is discussed

A comprehensive approach to the investigation of atmospheric particulate PM2.5: preliminary results

Understanding the health effects induced in humans by the inhalation of air particulate matter requires first that airborne particles be characterized in detail. Aiming at elucidating some prominent mechanisms and processes involved in the atmospheric environment - human organism interaction, a comprehensive approach was adopted to thoroughly investigate PM2.5 from a mineralogical, chemical and chemical-physical point of view. In the present study, two summer and winter samplings collected from the Rome urban area were investigated by different techniques (SEM-EDS, XRD, ICP-MS, ICP-OES, TGA-DTA). Mineralogical and physical characterization gave important information on the prevalent phases (oxides, sulphates, silicates, carbonates, and abundant carbonaceous particles hosting metals) contained into the material under study. The bulk chemical composition evidenced the presence of heavy metals, in particular As, Cd, Cu, Cr, Fe, Pb, Ni, and Zn. Consequently, in order to verify the potential mobility of such heavy metals, batch kinetic leaching tests were carried out by using a physiological solution mimicking the lung environment and samples were collected from the solution at different times of treatment. Among the metals contained into the particulate, a leaching trend was observed mainly for Pb, Cd and Cu, with Cd resulting the most mobile metal, whereas no Fe release was observed. The leaching solution mimicking the human intrapulmonary fluid will be exploited for future toxicological tests in cellular models, in order to assess the potentially harmful role of the above metals in biological systems

Dissolution Reaction and Surface Modification of UICC Amosite in Mimicked Gamble’s Solution: A Step towards Filling the Gap between Asbestos Toxicity and Its Crystal Chemical Features

This study focuses on the dissolution process and surface characterization of amosite fibres following interaction with a mimicked Gamble’s solution at a pH of 4.5 and T = 37 °C, up to 720 h. To achieve this, a multi-analytical approach was adopted, and the results were compared to those previously obtained on a sample of asbestos tremolite and UICC crocidolite, which were investigated under the same experimental conditions. Combining surface chemical data obtained by XPS with cation release quantified by ICP-OES, an incongruent behaviour of the fibre dissolution was highlighted for amosite fibres, similarly to asbestos tremolite and UICC crocidolite. In particular, a preferential release of Mg and Ca from the amphibole structure was observed, in agreement with their Madelung site energies. Notably, no Fe release from amosite fibres was detected in our experimental conditions (pH of 4.5 and atmospheric pO2), despite the occurrence of Fe(II) at the M(4) site of the amphibole structure, where cations are expected to be rapidly leached out during mineral dissolution. Moreover, the oxidation of both the Fe centres initially present on the fibre surface and those promoted from the bulk, because of the erosion of the outmost layers, was observed. Since biodurability (i.e., the resistance to dissolution) is one of the most important toxicity parameters, the knowledge of the surface alteration of asbestos possibly occurring in vivo may help to understand the mechanisms at the basis of its long-term toxicity