Bioaccessible arsenic in soil of thermal areas of Viterbo, Central Italy: implications for human health risk.

Thermal waters near the city of Viterbo (Central Italy) are known to show high As contents (up to 600 µg/l). Travertine is precipitated by these waters, forming extended plateau. In this study, we determine the As content, speciation and bioaccessibility in soil and travertine samples collected near a recreational area highly frequented by local inhabitants and tourists to investigate the risk of As exposure through accidental ingestion of soil particles. (Pseudo)total contents in the studied soils range from 17 to 528 mg/kg, being higher in soil developed on a travertine substrate (197 ± 127 mg/kg) than on volcanic rocks (37 ± 13 mg/kg). In travertines, most As is bound to the carbonatic fraction, whereas in soil the semimetal is mostly associated with the oxide and residual fractions. Accordingly, bioaccessibility (defined here by the simplified bioaccessibility extraction test, SBET; Oomen et al., 2002.) is maximum (up to 139 mg/kg) for soil developed on a travertine substrate, indicating a control of calcite dissolution on As bioaccessibility. On the other hand, risk analysis suggests a moderate carcinogenic risk associated with accidental soil ingestion, while dermal contact is negligible. By contrast, ingestion of thermal water implies a higher carcinogenic and systemic health risk.

A 200 km-long mercury contamination of the Paglia and Tiber floodplain: Monitoring results and implications for environmental management.

This paper reports the results of a joint project carried out by three regional environmental agencies of Italy to evaluate long-range mercury (Hg) transport from the abandoned Mt. Amiata Hg district in southern Tuscany (the third largest worldwide site for Hg production) to the fluvial ecosystems of the Paglia and Tiber rivers. Most of the work focused on stream sediments, surface waters and soils. A preliminary survey of Hg0 content in air was also conducted. Data obtained by public health authorities on Hg in vegetables and fish were also included. The highest Hg concentrations (up to thousands of µg/g Hg) were observed in stream sediments and soils directly impacted by Hg mine runoff. Although progressive Hg dilution was observed from north to south along the river, sediments and soils show anomalous Hg levels for over 200 km downstream of Mt. Amiata, testifying to an extreme case of long-range Hg contamination. A pervasive redistribution of Hg is observed in all sediment compartments. Presumably, the width of the impacted fluvial corridor corresponds to the entire alluvial plains of the rivers. The floodplains can be considered new sources for downstream Hg redistribution, especially during large flood events. On the other hand, results from water, air, and vegetable sampling indicate low potential for human exposure to Hg. The extent and distribution of the contamination make remediation not viable. Therefore, people and human activities must coexist with such an anomaly. On the technical side, the most urgent action to be taken is a better definition of the exact extent of the contaminated area. On the management side, it is necessary to identify which public institution(s) can best deal with such a widespread phenomenon. According to the precautionary principle, the impact of the contamination on human activities in the affected areas should be considered.

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.

Chemical stabilization of metals in mine wastes by transformed red mud and other iron compounds: laboratory tests.

A series of static and kinetic laboratory-scale tests were designed in order to evaluate the efficacy of transformed red mud (TRM) from bauxite refining residues, commercial zero-valent iron, and synthetic iron (III) hydroxides as sorbents/reagents to minimize the generation of acid drainage and the release of toxic elements from multi-contaminant-laden mine wastes. In particular, in some column experiments the percolation of meteoric water through a waste pile, alternated with periods of dryness, was simulated. Wastes were placed in columns together with sorbents/reagents in three different set-ups: as blended amendment (mixing method), as a bed at the bottom of the column (filtration method), or as a combination of the two previous methods. The filtration methods, which simulate the creation of a permeable reactive barrier downstream of a waste pile, are the most effective, while the use of sorbents/reagents as amendments leads to unsatisfactory results, because of the selective removal of only some contaminants. The efficacy of the filtration method is not significantly affected by the periods of dryness, except for a temporary rise of metal contents in the leachates due to dissolution of soluble salts formed upon evaporation in the dry periods. These results offer original information on advantages/limits in the use of TRM for the treatment of multi-contaminant-laden mine wastes, and represent the starting point for experimentation at larger scale.

Mass loads of dissolved and particulate mercury and other trace elements in the Mt. Amiata mining district, Southern Tuscany (Italy).

Total dissolved and particulate mercury (Hg), arsenic (As), and antimony (Sb) mass loads were estimated in different seasons (March and September 2011 and March 2012) in the Paglia River basin (PRB) (central Italy). The Paglia River drains the Mt. Amiata Hg district, one of the largest Hg-rich regions worldwide. Quantification of Hg, As, and Sb mass loads in this watershed allowed (1) identification of the contamination sources, (2) evaluation of the effects of Hg on the environment, and (3) determination of processes affecting Hg transport. The dominant source of Hg in the Paglia River is runoff from Hg mines in the Mt. Amiata region. The maximum Hg mass load was found to be related to runoff from the inactive Abbadia San Salvatore Mine (ASSM), and up to 30 g day(-1) of Hg, dominantly in the particulate form, was transported both in high and low flow conditions in 2011. In addition, enrichment factors (EFs) calculated for suspended particulate matter (SPM) were similar in different seasons indicating that water discharge controls the quantities of Hg transported in the PRB, and considerable Hg was transported in all seasons studied. Overall, as much as 11 kg of Hg are discharged annually in the PRB and this Hg is transported downstream to the Tiber River, and eventually to the Mediterranean Sea. Similar to Hg, maximum mass loads for As and Sb were found in March 2011, when as much as 190 g day(-1) each of As and Sb were measured from sites downstream from the ASSM. Therefore, the Paglia River represents a significant source of Hg, Sb, and As to the Mediterranean Sea.

The amorphous Zn biomineralization at Naracauli stream, Sardinia: electron microscopy and X-ray absorption spectroscopy.

An amorphous Zn biomineralization ("white mud"), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.

Neuro-Behçet: clinical features and MRI correlates.

This paper highlights the fundamental role of MRI in the diagnosis of Neuro-Behçet disease. We present 4 cases examined between 1990 and 1991. Treatment in all the cases seems to have improved the patients' prognoses.