Luca Olivi

Magnetite biomineralization in Magnetospirillum gryphiswaldense: time-resolved magnetic and structural studies.

Magnetotactic bacteria biosynthesize magnetite nanoparticles of high structural and chemical purity that allow them to orientate in the geomagnetic field. In this work we have followed the process of biomineralization of these magnetite nanoparticles. We have performed a time-resolved study on magnetotactic bacteria Magnetospirillum gryphiswaldense strain MSR-1. From the combination of magnetic and structural studies by means of Fe K-edge X-ray absorption near edge structure (XANES) and high-resolution transmission electron microscopy we have identified and quantified two phases of Fe (ferrihydrite and magnetite) involved in the biomineralization process, confirming the role of ferrihydrite as the source of Fe ions for magnetite biomineralization in M. gryphiswaldense. We have distinguished two steps in the biomineralization process: the first, in which Fe is accumulated in the form of ferrihydrite, and the second, in which the magnetite is rapidly biomineralized from ferrihydrite. Finally, the XANES analysis suggests that the origin of the ferrihydrite could be at bacterial ferritin cores, characterized by a poorly crystalline structure and high phosphorus content.

Physico-chemical Control over the Single- or Double-Wall Structure of Aluminogermanate Imogolite-like Nanotubes

It is known that silicon can be successfully replaced by germanium atoms in the synthesis of imogolite nanotubes, leading to shorter and larger AlGe nanotubes. Beside the change in morphology, two characteristics of the AlGe nanotube synthesis were recently discovered. AlGe imogolite nanotubes can be synthesized at much higher concentrations than AlSi imogolite. AlGe imogolite exists in the form of both single-walled (SW) and double-walled (DW) nanotubes, whereas DW AlSi imogolites have never been observed. In this article, we give details on the physicochemical control over the SW or DW AlGe imogolite structure. For some conditions, an almost 100% yield of SW or DW nanotubes is demonstrated. We propose a model for the formation of SW or DW AlGe imogolite, which also explains why DW AlSi imogolites or higher wall numbers for AlGe imogolite are not likely to be formed.

Molecular Insights of Oxidation Process of Iron Nanoparticles: Spectroscopic, Magnetic, and Microscopic Evidence

Oxidation behavior of nano-Fe(0) particles in an anoxic environment was determined using different state-of-the-art analytical approaches, including high resolution transmission electron microscopy (HR-TEM) combined with energy filtered transmission electron microscopy (EFTEM), X-ray absorption spectroscopy (XAS), and magnetic measurements. Oxidation in controlled experiments was compared in standard double distilled (DD) water, DD water spiked with trichloroethene (TCE), and TCE contaminated site water. Using HR-TEM and EFTEM, we observed a surface oxide layer (∼3 nm) formed immediately after the particles were exposed to water. XAS analysis followed the dynamic change in total metallic iron concentration and iron oxide concentration for the experimental duration of 35 days. The metallic iron concentration in nano-Fe(0) particles exposed to water, was ∼40% after 35 days; in contrast, the samples containing TCE were reduced to ∼15% and even to nil in the case of TCE contaminated site water, suggesting that the contaminants enhance the oxidation of nano-Fe(0). Frequency dependence measurements confirmed the formation of superparamagnetic particles in the system. Overall, our results suggest that nano-Fe(0) oxidized via the Fe(0) - Fe(OH)2 - Fe3O4 - (γ-Fe2O3) route and the formation of superparamagnetic maghemite nanoparticles due to disruption of the surface oxide layer.

Transformation of pristine and citrate-functionalized CeO2 nanoparticles in a laboratory-scale activated sludge reactor.

Engineered nanomaterials (ENMs) are used to enhance the properties of many manufactured products and technologies. Increased use of ENMs will inevitably lead to their release into the environment. An important route of exposure is through the waste stream, where ENMs will enter wastewater treatment plants (WWTPs), undergo transformations, and be discharged with treated effluent or biosolids. To better understand the fate of a common ENM in WWTPs, experiments with laboratory-scale activated sludge reactors and pristine and citrate-functionalized CeO2 nanoparticles (NPs) were conducted. Greater than 90% of the CeO2 introduced was observed to associate with biosolids. This association was accompanied by reduction of the Ce(IV) NPs to Ce(III). After 5 weeks in the reactor, 44 ± 4% reduction was observed for the pristine NPs and 31 ± 3% for the citrate-functionalized NPs, illustrating surface functionality dependence. Thermodynamic arguments suggest that the likely Ce(III) phase generated would be Ce2S3. This study indicates that the majority of CeO2 NPs (>90% by mass) entering WWTPs will be associated with the solid phase, and a significant portion will be present as Ce(III). At maximum, 10% of the CeO2 will remain in the effluent and be discharged as a Ce(IV) phase, governed by cerianite (CeO2).

Silver carbonate nanoparticles stabilised over alumina nanoneedles exhibiting potent antibacterial properties

A simple method of preparing Ag2CO3 nanoparticles utilising high area gamma-alumina nanoneedles has been developed; these are promising antimicrobial agents against diverse bacterial strains.

Long-term aging of a CeO2 based nanocomposite used for wood protection

A multi-scale methodology was used to characterize the long-term behavior and chemical stability of a CeO2-based nanocomposite used as UV filter in wood stains. ATR-FTIR and (13)C NMR demonstrated that the citrate coated chelates with Ce(IV) through its central carboxyl- and its α-hydroxyl- groups at the surface of the unaged nanocomposite. After 42 days under artificial daylight, the citrate completely disappeared and small amount of degradation products remained attached to the surface even after 112 days. Moreover, the release/desorption of the citrate layer led to a surface reorganization of the nano-sized CeO2 core observed by XANES (Ce L3-edge). Such a surface and structural transformation of the commercialized nanocomposite could have implications in term of fate, transport, and potential impacts towards the environment.

Heteroaggregation, transformation and fate of CeO2 nanoparticles in wastewater treatment

Wastewater Treatment Plants (WWTPs) are a key pathway by which nanoparticles (NPs) enter the environment following release from NP-enabled products. This work considers the fate and exposure of CeO2 NPs in WWTPs in a two-step process of heteroaggregation with bacteria followed by the subsequent reduction of Ce(IV) to Ce(III). Measurements of NP association with solids in sludge were combined with experimental estimates of reduction rate constants for CeO2 NPs in Monte Carlo simulations to predict the concentrations and speciation of Ce in WWTP effluents and biosolids. Experiments indicated preferential accumulation of CeO2 NPs in biosolids where reductive transformation would occur. Surface functionalization was observed to impact both the distribution coefficient and the rates of transformation. The relative affinity of CeO2 NPs for bacterial suspensions in sludge appears to explain differences in the observed rates of Ce reduction for the two types of CeO2 NPs studied.

Synchrotron-based speciation of chromium in an Oxisol from New Caledonia: Importance of secondary Fe-oxyhydroxides

Abstract In New Caledonia, the weathering of ultamafic rocks under a tropical climate has led to the residual accumulation of trace elements in lateritic soils widely dominated by Fe-oxyhydroxides. The speciation of trace elements, such as Cr, Ni, and Co, in these Oxisols remains a major subject of interest regarding mining and environmental issues. We have assessed the speciation of chromium in the upper part of an Oxisol, by combining bulk and spatially resolved chemical analyses (EPMA and SEM-EDS) with synchrotron-based spectroscopic data (EXAFS and XANES). EPMA indicates that the main hosts for chromium in the bedrock sample are the silicates forsterite, enstatite, and lizardite. Hosting of chromium in these easily weatherable mineral species could lead to a significant loss of this element upon weathering. However, total analyses of major elements indicate only a slight depletion of Cr, together with an immobility of Fe and Al and drastic losses of Si and Mg, after the weathering of the bedrock. Such a low mobility of chromium is likely related to its significant incorporation in goethite and hematite formed after the weathering of Fe2+-bearing primary silicates. This efficiency of secondary Fe-oxyhydroxides at immobilizing chromium is demonstrated by quantitative analysis of EXAFS data that indicates that these mineral species host between 67 and 75 wt% of total Cr (compared to the 18 to 22 wt% of total Cr hosted by chromite). In addition, SEM observation and SEM-EDS analyses performed on the Oxisol samples also show some evidence for chemical weathering of chromite. Chromite could then represent a past and/or present source of chromium upon extended tropical weathering of the studied Oxisol, rather than a stable host. These results emphasize the importance of secondary Fe-oxyhydroxides, compared to Cr-spinels, on chromium hosting in Oxisols developed upon tropical weathering of ultramafic rocks. Although the trapping mechanism of chromium mainly corresponds to incorporation within the structural network of goethite and hematite, sorption reactions at the surface of these mineral species could also be involved in such a process. In addition, considering their potential oxidative reactivity that can generate Cr6+ or enhance the chemical weathering of chromite, the occurrence of Mn oxides could significantly modify the behavior of chromium upon weathering. These considerations indicate that further studies are needed to assess the actual potential of chromium release from Oxisols developed upon weathering of ultramafic rocks under a tropical climate.

Synthesis of Ge-imogolite: influence of the hydrolysis ratio on the structure of the nanotubes

The synthesis protocol for Ge-imogolite (aluminogermanate nanotubes) consists of 3 main steps: base hydrolysis of a solution of aluminum and germanium monomers, stabilization of the suspension and heating at 95 °C. The successful synthesis of these nanotubes was found to be sensitive to the hydrolysis step. The impact of the hydrolysis ratio (from n(OH)/n(Al) = 0.5 to 3) on the final product structure was examined using a combination of characterization tools. Thus, key hydrolysis ratios were identified: n(OH)/n(Al) = 1.5 for the formation of nanotubes with structural defects, n(OH)/n(Al) = 2 for the synthesis of a well crystallized Ge imogolite and n(OH)/n(Al) > 2.5 where nanotube formation is hindered. The capability of controlling the degree of the nanotubes crystallinity opens up interesting opportunities in regard to new potential applications.

Determination of local atomic displacements in CeO1?xFxBiS2 system

We have used Bi and Ce L3-edges extended x-ray absorption fine structure measurements to study local structure of CeO(1-x)F(x)BiS2 system as a function of F-substitution. The local structure of both BiS2 active layer and CeO1-xFx spacer layer changes systematically. The in-plane Bi-S1 distance decreases (ΔRmax ∼ 0.08 Å) and the out-of-plane Bi-S2 distance increases (ΔRmax ∼ 0.12 Å) with increasing F-content. On the other hand, the Ce-O/F distance increases (ΔRmax ∼ 0.2 Å) with a concomitant decrease of the Ce-S2 distance (ΔRmax ∼ 0.15 Å). Interestingly, the Bi-S1 distance is characterized by a large disorder that increases with F-content. The results provide useful information on the local atomic displacements in CeO(1-x)F(x)BiS2, that should be important for the understanding of the coexistence of superconductivity and low temperature ferromagnetism in this system.