Giuseppe Protano

Antimony accumulation in Achillea ageratum, Plantago lanceolata and Silene vulgaris growing in an old Sb-mining area

Preliminary data of a biogeochemical survey concerning antimony transfer from soil to plants in an abandoned Sb-mining area are presented. Achillea ageratum, Plantago lanceolata and Silene vulgaris can strongly accumulate antimony when its extractable fraction in the soil is high (139-793 mg/kg). A. ageratum accumulates in basal leaves (1367 mg/kg) and inflorescences (1105 mg/kg), P. lanceolata in roots (1150 mg/kg) and S. vulgaris in shoots (1164 mg/kg). In these plant species, the efficiency of antimony accumulation decreases when the antimony availability in the soil is high. In A. ageratum and S. vulgaris, the death of the epigeal target part at the end of the growing season contributes to a reduction of the antimony load in the plant. A study to test the use of these species as bioindicators of antimony availability in soil is suggested by our results.

Arsenic in soil and vegetation of contaminated areas in southern Tuscany (Italy)

Abstract Arsenic contents of soils and higher plants were surveyed in two former Sb-mining areas and in an old quarry once used for ochre extraction. Total As in the soils ranged from 5.3 to 2035.3 mg kg −1 , soluble and extractable As from 0.01 to 8.5 and from 0.04 to 35.8 mg kg −1 , respectively. The As concentrations in the different fractions of soil were correlated significantly or very significantly. Sixty-four plant species were analyzed. The highest As contents were found in roots and leaves of Mentha aquatica (540 and 216 mg kg −1 , respectively) and in roots of Phragmites australis (688 mg kg −1 ). In general, the As contents of plants were low, especially in crops and in the most common wild species. In the analyzed species, roots usually showed the highest content followed by leaves and shoots. Arsenic levels in soils and plants were positively correlated, while the ability of the plants to accumulate the element (expressed by their Biological Accumulation Coefficients and Concentration Factors) was independent of the soil As content. Comparison with the literature data, relationships between the As contents in plants and soils, and biogeochemical and environmental aspects of these results are discussed.

Environmental geochemical maps of Italy from the FOREGS database

The Geochemical Atlas of Italy addresses the need for geochemical mapping of the country, based on FOREGS procedures. Data from samples of Italian topsoil, subsoil, stream water, stream sediment and floodplain sediment have been extracted from the FOREGS database and supplemented with data from eight new sample sites. In total 360 geochemical maps have been produced and spatial correlations have been found between the underlying geology and element abundances in the sampled media. The aim of the Geochemical Atlas of Italy is to document background/baseline chemical element variation at the national scale. It is found to be a suitable tool to support government decision-makers to assess trigger and action limits at the local scale, when considered in the light of the complex spatial variability of Italian geology. Maps presented here demonstrate that low density geochemical mapping is a viable tool to obtain an impression of natural element variation at the country scale and to identify areas where more detailed sampling is advisable.

Does salt water intrusion constitute a mercury contamination risk for coastal fresh water aquifers

Four different sampling surveys were carried out in 1998 to evaluate the possible causes of severe mercury contamination involving many wells spread over a vast territory along the coast of southern Tuscany (Italy). Several samples of groundwater and coastal sea water were collected to determine the Hg, Cl, Ar, He and N contents. Anthropogenic or deep-seated sources of the Hg involved in the contamination event can be excluded. The observed coupling of Hg pollution with progressive salt water intrusion along the coastal aquifer indicates a close causal relation between these two phenomena.

Chemical and biological methods to evaluate the availability of heavy metals in soils of the Siena urban area (Italy)

A biogeochemistry field study was conducted in the Siena urban area (Italy) with the main objective of establishing the relationship between available amounts of heavy metals in soil assessed by a chemical method (soil fractionation) and bioavailability assessed by a biological method (bioaccumulation in earthworm tissues). The total content of traffic-related (Cd, Cu, Pb, Sb, Zn) and geogenic (Co, Cr, Ni, U) heavy metals in uncontaminated and contaminated soils and their concentrations in soil fractions and earthworms were used for this purpose. The bioavailability of heavy metals assessed by earthworms did not always match the availability defined by soil fractionation. Earthworms were a good indicator to assess the bioavailability of Pb and Sb in soil, while due to physiological mechanisms of regulation and excretion, Cd, Cu and Zn tissue levels in these invertebrates gave misleading estimates of their bioavailable pool. No relationship was identified between chemical and biological availability for the geogenic heavy metals, characterized by a narrow range of total contents in soil. The study highlighted that chemical and biological methods should be combined to provide more complete information about heavy element bioavailability in soils.

Heavy element accumulation in Evernia prunastri lichen transplants around a municipal solid waste landfill in central Italy

This paper presents the results of a biomonitoring study to evaluate the environmental impact of airborne emissions from a municipal solid waste landfill in central Italy. Concentrations of 11 heavy elements, as well as photosynthetic efficiency and cell membrane integrity were measured in Evernia prunastri lichens transplanted for 4months in 17 monitoring sites around the waste landfill. Heavy element contents were also determined in surface soils. Analytical data indicated that emissions from the landfill affected Cd, Co, Cr, Cu, Ni, Pb, Sb and Zn concentrations in lichens transplanted within the landfill and along the fallout direction. In these sites moderate to severe accumulation of these heavy elements in lichens was coupled with an increase in cell membrane damage and decrease in photosynthetic efficiency. Nevertheless, results indicated that landfill emissions had no relevant impact on lichens, as heavy element accumulation and weak stress symptoms were detected only in lichen transplants from sites close to solid waste. The appropriate management of this landfill poses a low risk of environmental contamination by heavy elements.

Potentially toxic element contamination in soil and accumulation in maize plants in a smelter area in Kosovo

A biogeochemical field study was carried out in the industrial area of Kosovska Mitrovica in northern Kosovo, where agricultural soils were contaminated by potentially toxic elements due to smelting activity. Total and bioavailable contents of As, Cd, Co, Cu, Pb, Sb, U and Zn in soil and their concentrations in maize roots and grains were determined. Soil contamination by As, Cd, Cu, Pb, Sb and Zn was variable from slightly to highly contaminated soils and influenced both the bioavailable fraction and accumulation of these potentially toxic elements in maize tissues. The comparison between potentially toxic element concentrations in roots and grains indicated that maize is able to limit the transfer of non-essential elements to edible parts. The plant-to-soil bioconcentration indices suggested that the transfer of potentially toxic elements from soil to plant was predicted better by bioavailable concentrations than by the total contents. These indices further identified some competitions and interactions among these elements in root uptake and root-to-grain translocation.

Trace element distribution and 235U/238U ratios in Euphrates waters and in soils and tree barks of Dhi Qar province (southern Iraq).

To assess the quality of the environment in southern Iraq after the Gulf War II, a geochemical survey was carried out. The survey provided data on the chemistry of Euphrates waters, as well as the trace element contents, U and Pb isotopic composition, and PAH levels in soil and tree bark samples. The trace element concentrations and the (235)U/(238)U ratio values in the Euphrates waters were within the usual natural range, except for the high contents of Sr due to a widespread presence of gypsum in soils of this area. The trace element contents in soils agreed with the common geochemistry of soils from floodplain sediments. Some exceptions were the high contents of Co, Cr and Ni, which had a natural origin related to ophiolitic outcrops in the upper sector of the Euphrates basin. The high concentrations of S and Sr were linked to the abundance of gypsum in soils. A marked geochemical homogeneity of soil samples was suggested by the similar distribution pattern of rare earth elements, while the (235)U/(238)U ratio was also fairly homogeneous and within the natural range. The chemistry of the tree bark samples closely reflected that of the soils, with some notable exceptions. Unlike the soils, some tree bark samples had anomalous values of the (235)U/(238)U ratio due to mixing of depleted uranium (DU) with the natural uranium pool. Moreover, the distribution of some trace elements (such as REEs, Th and Zr) and the isotopic composition of Pb in barks clearly differed from those of the nearby soils. The overall results suggested that significant external inputs occurred implying that once formed the DU-enriched particles could travel over long distances. The polycyclic aromatic hydrocarbon concentrations in tree bark samples showed that phenanthrene, fluoranthene and pyrene were the most abundant components, indicating an important role of automotive traffic.

Concordance between plant species, oribatid mites and soil in a Mediterranean stone pine forest

Biological interactions between above-ground and below-ground organisms are not clearly defined among communities with regard to compositional patterns. The study investigates the concordance of species assemblages between vascular plants and oribatid mites and soil chemical properties with special attention to the role of vegetation structure, i.e. tree, shrub and herbaceous cover, for biological components. Data were collected in a Mediterranean coastal Nature Reserve using sampling design based on random selection of plots with cover of stone pine (Pinus pinea L.) exceeding 15%. Agreement of distribution patterns was verified by Spearman’s rank correlation coefficient applied to pairs of matrices of plot scores by principal component analysis (plants, mites and soil) and the Mantel test. The feasible role of vegetation cover on plant and mite assemblages was tested by redundancy analysis (RDA). Significant correlations were found for biological assemblages, indicating congruent plant–mite compositional patterns. On the other hand, the hypothesis of concordance between biological communities and soil was rejected. Moreover, RDA showed that vegetation cover was a driver of both plant and oribatid mite assemblages. In particular, herbaceous cover proved to be a good proxy for the two biological communities investigated, with different taxa linked to forest clearings and to areas with denser tree cover. Our results indicate that soil features were not of primary importance for below-ground and above-ground community assemblages in the study area. In the light of our findings and ongoing threats in coastal areas, we recommend that management measures be directed at maintenance of diversified vegetation structure, which may ensure above-ground and below-ground biodiversity with diverse biological community assemblages.

Influence of ore processing activity on Hg, As and Sb contamination and fractionation in soils in a former mining site of Monte Amiata ore district (Italy)

A geochemical study was carried out at the former Abbadia San Salvatore (ASS) mining site of the Monte Amiata ore district (Italy). Hg, As and Sb total contents and fractionation using a sequential extraction procedure were determined in soil and mining waste samples. Ore processing activities provided a different contribution to Hg contamination and concentration in soil fractions, influencing its behaviour as volatility and availability. Soils of roasting zone showed the highest Hg contamination levels mainly due to the deposition of Hg released as Hg0 by furnaces during cinnabar roasting. High Hg contents were also measured in waste from the lower part of mining dump due to the presence of cinnabar. The fractionation pattern suggested that Hg was largely as volatile species in both uncontaminated and contaminated soils and mining waste, and concentrations of these Hg species increased as contamination increased. These findings were in agreement with the fact that the ASS mining site is characterized by high Hg concentrations in the air and the presence of Hg0 liquid droplets in soil. Volatile Hg species were also prevalent in uncontaminated soils likely because the Monte Amiata region is an area characterized by anomalous fluxes of gaseous Hg from natural and anthropogenic inputs. At the ASS mining site soils were also contaminated by Sb, while As contents were comparable with its local background in soil. In all soil and waste samples Sb and As were preferentially in residual fraction.