New geochemical data for defining origin and distribution of mercury in groundwater of a coastal area in southern Tuscany (Italy).

A geochemical study was conducted in a coastal plain in the Orbetello Lagoon area in southern Tuscany (Italy), acquiring new data on groundwater, lagoon water, and stream sediment for insights into the origin, distribution, and behaviour of mercury in a Hg-enriched carbonate aquifer. The main hydrochemical features of the groundwater are ruled by the mixing of Ca-SO4 and Ca-Cl continental fresh waters of the carbonate aquifer and Na-Cl saline waters of the Tyrrhenian Sea and Lagoon of Orbetello. Groundwater had highly variable Hg concentrations (< 0.1-11 µg/L) that were not correlated with the percentage of saline water, depth in the aquifer, or distance from the lagoon. This excluded the possibility that saline water could be the direct source of Hg in groundwater and responsible for release of the element through interaction with the carbonate lithologies of the aquifer. The origin of Hg in groundwater could be ascribed to the Quaternary continental sediments overlying the carbonate aquifer because i) high Hg concentrations were found in the continental sediments of the coastal plain and in the contiguous lagoon sediments; ii) waters from the upper part of aquifer had the highest Hg concentrations; iii) Hg levels in groundwater increased with increasing thickness of the continental deposits. The high Hg content in the continental and lagoon sediments is geogenic due to regional and local Hg anomalies and to sedimentary and pedogenetic processes. It can be assumed that i) water circulating in these sediments dissolves the solid Hg-bearing constituents and mobilises this element mainly as chloride complexes; ii) Hg-enriched water moves from the upper part of the carbonate aquifer due to the cone of depression generated by intense pumping of groundwater by fish farms in the study area.

Biochar Amendment Reduces the Availability of Pb in the Soil and Its Uptake in Lettuce.

The aim of this study was to investigate the ability of biochar amendment to reduce the availability of Pb in the soil and its uptake in lettuce (Lactuca sativa L. var. adela). Seedlings of lettuce were cultivated in Pb-contaminated soils, both with and without 5% biochar (w/w), as well as in a simplified soilless system (hydroponics) at the ecologically relevant Pb concentration of 100 µM, both with and without 1% biochar. Soils amended with biochar resulted in a ca. 50% reduction of the extractable (bioavailable) fraction of Pb, limiting the accumulation of this toxic element in the leaves of lettuce by ca. 50%. A similar behavior was observed for lettuce plants grown hydroponically, even with a much higher reduction of Pb uptake (ca. 80%). Increased cation exchange capacity and pH were likely the main factors limiting the bioavailability of Pb in the soil. Complexation with functional groups and precipitation/co-precipitation both on the biochar surface and in soil aggregates were likely the main mechanisms immobilizing this element.

Trace Element Uptake and Accumulation in the Medicinal Herb Hypericum perforatum L. Across Different Geolithological Settings.

The worldwide growing interest in traditional medicines, including herbal medicines and herbal dietary supplements, has recently been accompanied by concerns on quality and safety of this type of health care. The content of nutritional and potentially toxic elements in medicinal plants is of paramount interest as it may vary remarkably according to different environmental and ecophysiological factors. In this study, the concentrations of essential and non-essential trace elements-Co, Cr, Cu, Ni, Sr, and Zn-were determined in the roots and aerial parts of the worldwide distributed and economically important medicinal herb Hypericum perforatum L. (St. John's wort) and in its growing substrate. Most of the analyzed trace elements varied considerably in the plant parts according to edaphic conditions and soil geochemistry. However, uptake and retention in H. perforatum compartments of Co, Cr, and Ni, which markedly differentiated the investigated soils, were controlled by excluding mechanisms of the plant. Despite this, the Ni concentrations in the aerial parts, commonly used in herbal preparations, of H. perforatum plants from serpentine soils were not insignificant in relation to eventual human consumption. Good practice to assure the herbal product quality of H. perforatum collected from the wild cannot ignore the thorough understanding of the geolithological and geochemical features of the harvesting areas.

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.

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.

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.

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.

Effects of landfill leachate treatment on hepatopancreas of Armadillidium vulgare (Crustacea, Isopoda).

The major environmental impact of landfills is emission of pollutants via the leachate and gas pathways. The hepatopancreas of the terrestrial isopod Armadillidium vulgare (Isopoda, Crustacea, Latreille 1804) plays an important role in the bioaccumulation of contaminants, such as heavy metals. To evaluate the effects of landfill leachate treatment, 2 different approaches were applied: 1) the detection of accumulation of trace elements (As, Cd, Cr, Cu, Sb, Zn, Pb, Ni, V) in hepatopancreatic cells, and 2) the evaluation of biological effect of contaminants on fresh hepatopancreatic cells by flow-cytometric analyses. The presence of 2 different cell types (herein referred to as "small" [S] cells and "big" [B] cells, in agreement with the literature based on morphological examinations) was detected for the first time by flow cytometry, which also highlighted their different response to stress stimuli. In particular, B cells appeared more sensitive to landfill leachate treatment, being more damaged in the short term, while S cells seemed more adaptive. Furthermore, S cells could represent a pool from which they are able to differentiate into B cells. These findings were also confirmed by principal component analyses, underlining that S SYBR Green I bright cells correlate with specific chemicals (Ca, Cu, Co), confirming their resistance to stress stimuli, and suggesting that the decrease of specific cell types may prime other elements to replace them in a homeostasis-preservation framework.