Daniela Medas

Natural Biomineralization in the Contaminated Sediment-Water System at the Ingurtosu Abandoned Mine

The Ingurtosu Pb–Zn mine (S-W Sardinia) was exploited for about a century until 1968. Huge amounts of tailings were abandoned, resulting in long-term heavy metal dispersion processes in both soils and waters. Zn and Pb concentration in tailings and soils attains values up to thousands of mg per kilogram. The maximum Zn concentration in water attains several hundreds of mg per liter, whereas Cd and Pb concentrations are in the order of thousands of μg per liter. Heavy metal concentration in waters of Rio Naracauli, the main stream of the area, is abated by seasonal biomineralization processes. Precipitation of hydrozincite [Zn5(CO3)2(OH)6] and of a Zn-rich amorphous phase results in a decrease of Zn concentration down to a few mg per liter. Other metals such as Pb, Cd, Cu, and Ni are coprecipitated with the Zn phases. This chapter reports the state of our knowledge on the Naracauli biomineralization process.

Zn biomineralization processes and microbial biofilm in a metal-rich stream (Naracauli, Sardinia).

Several decades after the closure of the Ingurtosu mine (SW Sardinia), a variety of seasonal Zn biomineralizations occurs. In this work, waters, microbial consortia, and seasonal precipitates from the Naracauli stream were sampled to investigate chemical composition of stream waters and biominerals, and microbial strain identity. Molecular and morphological analysis revealed that activity of dominant cyanobacterium Leptolyngbya frigida results in precipitation of Zn silicate. The activity of the cyanobacterium was associated to other bacteria and many kind of diatoms, such as Halamphora subsalina and Encyonopsis microcephala, which are trapped in the process of biomineral growth. In this work, the precipitation process is shown to be the result of many different parameters such as hydrologic regime, microbial community adaptation, and biological mediation. It results in a decrease of dissolved Zn in the stream water, and is a potential tool for Zn pollution abatement.

Microscopic processes ruling the bioavailability of Zn to roots of euphorbia pithyusa L. Pioneer plant

Euphorbia pithyusa L. was used in a plant growth-promoting assisted field trial experiment. To unravel the microscopic processes at the interface, thin slices of E. pithyusa roots were investigated by micro-X-ray fluorescence mapping. Roots and rhizosphere materials were examined by X-ray absorption spectroscopy at the Zn K-edge, X-ray diffraction, and scanning electron microscopy. Results indicate some features common to all the investigated samples. (i) In the rhizosphere of E. pithyusa, Zn was found to exist in different phases. (ii) Si and Al are mainly concentrated in a rim at the epidermis of the roots. (iii) Zn is mostly stored in root epidermis and does not appear to be coordinated to organic molecules but mainly occurs in mineral phases such as Zn silicates. We interpreted that roots of E. pithyusa significantly promote mineral evolution in the rhizosphere. Concomitantly, the plant uses Si and Al extracted by soil minerals to build a biomineralization rim, which can capture Zn. This Zn silicate biomineralization has relevant implications for phytoremediation techniques and for further biotechnology development, which can be better designed and developed after specific knowledge of molecular processes ruling mineral evolution and biomineralization processes has been gained.

Microscopic biomineralization processes and Zn bioavailability: a synchrotron-based investigation of Pistacia lentiscus L. roots

Plants growing on polluted soils need to control the bioavailability of pollutants to reduce their toxicity. This study aims to reveal processes occurring at the soil-root interface of Pistacia lentiscus L. growing on the highly Zn-contaminated tailings of Campo Pisano mine (SW Sardinia, Italy), in order to shed light on possible mechanisms allowing for plant adaptation. The study combines conventional X-ray diffraction (XRD) and scanning electron microscopy (SEM) with advanced synchrotron-based techniques, micro-X-ray fluorescence mapping (μ-XRF) and X-ray absorption spectroscopy (XAS). Data analysis elucidates a mechanism used by P. lentiscus L. as response to high Zn concentration in soil. In particular, P. lentiscus roots take up Al, Si and Zn from the rhizosphere minerals in order to build biomineralizations that are part of survival strategy of the species, leading to formation of a Si-Al biomineralization coating the root epidermis. XAS analysis rules out Zn binding to organic molecules and indicates that Zn coordinates Si atoms stored in root epidermis leading to the precipitation of an amorphous Zn-silicate. These findings represent a step forward in understanding biological mechanisms and the resulting behaviour of minor and trace elements during plant-soil interaction and will have significant implications for development of phytoremediation techniques.

Impact of Zn excess on biomineralization processes in Juncus acutus grown in mine polluted sites

Juncus acutus, an halophite plant pioneer in extremely polluted mine areas, was harvested in three different locations of Sardinia (Italy), having Zn soil concentration up to 80g/kg, and Zn water concentration ranging between 10-3g/L and 10-1g/L. Rhizosphere and plant samples were investigated combining X-ray microscopy (XM)/spectroscopy (XAFS) and infrared microspectroscopy (FTIR) to elucidate the chemical composition, (bio)mineralogy and Zn coordinative environment. The multi-technique approach allowed recognizing different biomineralization processes, and Zn complexes in the plant tissues. The Zn chemical environment in root biominerals is multi-phase and, depending on the sampling site, can comprise amorphous Zn silicate, Zn apatite, hydrozincite, and Zn sulphate. Zn cysteine and Zn histidine, complexes quoted as part of a detoxification strategy, were found mainly in plants from the site where the Zn water concentration has the highest values. This different site-specific mode of Zn biomineralization has relevant implications for phytoremediation techniques and for further biotechnology development, which can be better designed and developed after knowledge of site-specific-molecular processes ruling mineral evolution and biomineralization. Carboxylic groups and organic compounds (lignin, cellulose, hemicellulose, pectin and esters) were identified by FTIR analysis, thought the Zn speciation is not apparently linked to these carboxylic group rich biopolymers.

Binding of bis-(2-ethylhexyl) phthalate at the surface of hydrozincite nanocrystals: An example of organic molecules absorption onto nanocrystalline minerals.

As a contribution to understand the interactions between mineral surfaces and organic molecules, this study reports an accurate characterization of the bis-(2-ethylhexyl) phthalate (DEHP)-Hydrozincite (DEHP-HY), that has been conduced combining the following techniques: FTIR, NMR, XAS spectroscopies and XRD. XRD patterns indicate that the HY is made of nanocrystals whose size is not influenced by the presence of DEHP. The (1)H NMR analysis of DEHP-HY samples points out the presence of interactions of DEHP with HY. CPMAS NMR analysis suggests that the interaction is operated by ester carbonyl groups while the aliphatic chain, as expected, is not involved. MAS and CPMAS NMR measurements, performed on (13)C ester carbonyl enriched DEHP, allow to demonstrate that there are two ester carbonyl linkage sites interacting at the HY surface: an acid site with a strong link and a second one with weak chemical interactions. Zn K-edge XAS spectroscopy demonstrates that the local atomic structure around Zn in DEHP-HY sample remains essentially unchanged with respect to that of HY. Such a weak structural effect suggests that HY interaction with DEHP is limited to the nanoparticle surface.

Synchrotron Radiation and Environmental Sciences

Synchrotron-based techniques have been one of the most powerful tools for the development of molecular environmental science (MES), that is, understanding at the molecular scale the phenomena controlling environmentally relevant processes. The most commonly applied techniques include X-ray absorption spectroscopy, X-ray diffraction, X-ray imaging, and other microbeam or surface techniques.

Sediments distribution of trace metals in a coastal lagoon (Southern Sardinia, Mediterranean Sea): assessment of contamination and ecological risk

ABSTRACT Coastal lagoons are subject to several sources of contaminations. To shade light on the contamination level of the Santa Gilla lagoon (Tyrrhenian Sea) we investigated the spatial distribution of Cr, Ni, Pb, Zn and Hg in sediments and their correlation with grain size and organic matter contents. Moreover, sediment contamination levels and the ecological risk associated with metal concentration were assessed using different abiotic indicators. The lagoon is characterised by low levels of contamination, with exceptions for Pb and Hg, whose distribution reflects the position of an old chlor-alkali plant and that of an airport. These results indicate that the restoration put in place 30 years ago have not reached the expected target and that the presence of the airport deserves further attention. In the outer section of the lagoon, where clam fishery occurs, we observed low levels of contamination suggesting that such artisanal fishery could somehow help mobilising metals. We conclude that the area exposed to Hg pollution, though tentatively restored, still suffers of a potential risk of ecosystem deterioration. We pinpoint that further investigations on the mobility, bioavailability and toxicity of metals are needed to finally address the actual impairment of the Santa Gilla lagoon.

Structure of low-order hemimorphite produced in a Zn-rich environment by cyanobacterium Leptolingbya frigida

Abstract Microbes play a fundamental role in the precipitation of silicate biominerals, thereby affecting the Si geochemical cycle. The fine mechanisms ruling biomineralization are not yet fully understood, and their microscopic structures can offer deep insight into their processes of formation, reactivity and stability. In this study, a Zn silicate biomineral, extracellularly produced by cyanobacterium Leptolingbya frigida, was investigated combining nuclear magnetic resonance (NMR), Zn K-edge X-ray absorption spectroscopy (XAS) and other complementary techniques. 29Si magic angle spinning and 29Si/1H cross polarization magic angle spinning analysis, Fourier transform infrared spectroscopy (FTIR) and XAS analysis revealed a poorly crystalline phase closely resembling hemimorphite [Zn4Si2O7(OH)2·H2O]. Zn K-edge extended X-ray absorption fine structure (EXAFS) provided further structural details, revealing that the Zn-O-Si interatomic distances were 7–8% shorter than the abiotic mineral. 13C NMR spectra analysis was conducted to investigate the composition of the Zn silicate biomineral organic matrix, and results revealed that C atoms occurred in several functional groups such as carbonyl carbons, C rings, O-aliphatic chains, N-aliphatic chains, and aliphatic chains. Under slightly alkaline conditions, bacterial cell walls exhibited fundamental control on the biomineralization process by binding Zn ions and forming Zn–O–Si bonds. In this way, L. frigida cell walls served as a reactive surface for the precipitation of this Zn sorosilicate, hindering the condensation of silicon dimers. Moreover, we found a 29Si NMR band at 85 ppm that could be attributed to a (C3H6O3)2Si complex. This complex could play a role in the control of silicon polymerization, with implications for Si biomineralization processes.

Zn-biominerals: a perspective for environmental technologies to treat mine waters

Lucchi, Renata G. ... et. al.-- 87° Congresso della Societa Geologica Italiana e 90° Congresso della Societa Italiana di Mineralogia e Petrologia, The Future of the Italian Geosciences - The Italian Geosciences of the Future, 10-12 September 2014, Milan, Italy.-- 1 pageThe Montellina Spring (370 m a.s.l.) represents an example of groundwater resource in mountain region. It is a significant source of drinking water located in the right side of the Dora Baltea Valley (Northwestern Italy), SW of Quincinetto town. This spring shows a morphological location along a ridge, 400 m from the Renanchio Torrent in the lower sector of the slope. The spring was investigated using various methodologies as geological survey, supported by photo interpretation, structural reconstruction, NaCl and fluorescent tracer tests, discharge measurements. This multidisciplinary approach, necessary due to the complex geological setting, is required for the importance of the Montellina Spring. It is interesting in the hydrogeological context of Western Alps for its high discharge, relatively constant over time (average 150 l/s), and for its location outside a fluvial incision and suspended about 40 m above the Dora Baltea valley floor (Lasagna et al. 2013). According to the geological setting, the hydrogeological reconstruction of the area suggests that the large amount of groundwater in the basin is essentially favoured by a highly fractured bedrock, covered by wide and thick bodies of glacial and gravitational sediments. The emergence of the water along the slope, in the Montellina Spring, is essentially due to a change of permeability between the deep bedrock and the shallow bedrock and/or surficial sediments. The deep bedrock, showing closed fractures and/or fractures filled by glacial deposits, is slightly permeable. The shallow bedrock, strongly loosened as result of gravitational phenomena, and the local gravitational sediments are, on the contrary, highly permeable. The concentration of water at the spring is due to several reasons. a) The spring is immediately downward a detachment niche, dipping towards the spring, that essentially drains the water connected to the change of permeability in the bedrock. b) It is along an important fracture, that carries a part of the losses of the Renanchio Torrent. c) Finally, it is favored by the visible and buried morphology. Although it is located along a ridge, the spring occurs in a small depression between a moraine and a landslide body. It also can be favored by the likely concave trend of buried base of the landslide. At last, tracer tests of the Renanchio Torrent water with fluorescent tracer are performed, with a continuous monitoring in the Montellina Spring. The surveys permit to verify and quantify the spring and torrent hydrogeological relationship, suggesting that only a small fraction of stream losses feeds the spring.