Search

The occurrence of three common antifouling biocides (Irgarol, Diuron and dichlofluanid) was investigated, both in winter and summer, in two Italian coastal areas bordering the Tyrrhenian Sea: the Gulf of Napoli (Southern Italy) and the Gulf of La Spezia (Northern Italy). Dichlofluanid was always below the limit of detection, while Irgarol and Diuron were detected in the Gulf of Napoli, at concentrations ranging from 0.8 ng/L to 134.5 ng/L, and from 1.6 ng/L to 34.8 ng/L, respectively. In the Gulf of La Spezia, the amounts were in the range

In this work we report the results of the crystal chemical, structural and surface characterization of erionite-K fibres from Rome (Oregon, USA) after interaction with Fe (III) chloride solutions at different concentrations. In addition, Fe (III) loaded samples were investigated after incubation in ascorbic acid in order to monitor the mobility of reduced Fe (II) and to highlight its possible incorporation as EF cation through ion exchange. Comparison between released and acquired charges under the form of Fe confirms, in perfect agreement with previous studies that Fe (III) is mainly fixed at the fibre surface. Nevertheless, in very diluted Fe (III) solutions (below 50 μM FeCl3) a significant fraction of Fe (III) is segregated by an ion-exchange mechanism in the erionite cavity at the Ca3 site, albeit with a significantly lower efficiency with respect to Fe (II). It is worth mentioning that, as a result of the catalytic properties of zeolites, the location of iron in well-defined crystallographic positions is the prerequisite for behaving as a very active site in the generation of reactive oxygen species. Incubation in ascorbic acid revealed that only Fe (III) residing at the fibres surface and characterized by low nuclearity is significantly reduced, whereas this reaction does not occur (or possibly occurs very marginally) in the case of the ion-exchanged metal. Considering that the total iron in lung fluids occurs at very low concentration (ca. 0.21 μM), our results strongly suggest that the physiological environment unfortunately represents the optimum condition for iron to behave as a very active site. © 2016 Elsevier Inc.

A devastating rainfall in Tuscany in November 2012 provided the opportunity to study the diffusion of As and Sb along the Tafone mining area, under extreme conditions, by comparing their concentrations in water, soil, and river sediments in drought (equilibrium) periods against those observed immediately after a flooding event and after a period of 6 weeks rebalancing of the watercourse. The data obtained at equilibrium show a significant “natural” As and Sb contamination with the highest levels along the valley in the mine surroundings. Very high Sb and As concentrations in the sediment of the Tafone Lake cause a potential continuous supply of toxic elements to the river downstream. In surface waters (river water and lake), As concentrations exceed slightly, and only occasionally, the Italian regulatory limits, while, those for Sb are always widely exceeded. In addition, the soils collected along the Tafone valley show high Sb and As total content, and were studied by a novel nine-step sequential extraction protocol, proposed for assessing the bioavailability of As and Sb in sulphide ore mining-impacted soils. Experimental data show that As and Sb mobility is strongly affected by even small variations of the pH and redox conditions, thus controlling their release into the environment. The results obtained after the flood demonstrated that extreme weather events can induce two main problems: (1) the temporary increase of As and Sb amount transported by the river water to the sea, principally as particulate and colloidal material, and (2) the sediment transport out the mining area, reaching soils eventually used for agriculture, and the potential diffusion through the food chain.

This study concerns the occurrence of arsenic in the groundwater system of the Cimino-Vico volcanic area (central Italy), different parts of which are currently widely used for local drinking water supply and for irrigation. The system shows a complex groundwater circulation, including a continuous basal aquifer, discontinuous perched aquifers, groundwater flows at high altitude, and local interactions with rising thermal fluids. Data on arsenic contents in 250 water samples from springs and wells and in 68 samples from rock outcrops were measured and combined with already existing information. Results highlight that arsenic concentrations of groundwater are influenced by type of aquifer, groundwater flow path, arsenic content of the aquifer rocks, and interaction with fluids rising from depth. Waters circulating in the Vico volcanics, one of the prominent rock units of the area, have high concentrations of arsenic, both for the basal and the perched aquifers. A large fraction of the waters associated with this rock unit have arsenic contents higher than 10 μg/L (82 percent for basal, 40 percent for perched). In contrast, waters circulating in the Cimino volcanics have lower arsenic contents: 30 percent of the basal and 10 percent of the perched aquifers have arsenic concentrations greater than 10 μg/L. Through an integrated approach, including leaching tests to investigate the arsenic behavior concerning the water-rock interaction and a geostatistical modeling of data, it has been possible to identify and tentatively quantify suitable water resources that have arsenic content not exceeding the quality standards for human consumption.

The increasing demand for environmental pollution control results in the development and use of new procedures for the determination of dangerous chemicals. Simple screening methods, which can be used directly in the field for a preliminary assessment of soil contamination, seem to be extremely advantageous. In our laboratory, we developed and optimized a rapid test for a preliminary evaluation of both the concentration and the mobility of some potentially toxic metals in soils. This screening test consists of a single extraction of the soil sample with a buffer solution, followed by the titration of the extracted solution with dithizone to determine the contents of bi-valent heavy metals (such as Pb, Cu, Zn, and Cd). This screening method was then directly applied in the field during the sampling campaign in the framework of an Italian–Serbian collaborative project, finalized in the study of metal availability in soils. The results obtained in the field with the rapid test were compared with those obtained in the laboratory following the conventional procedure commonly used to evaluate metal bioavailability (diethylenetriaminepentaacetic extraction). Moreover, selected samples were analyzed sequentially in the laboratory using the standardized BCR three-step sequential extraction procedure. The screening test gave results conceptually in good agreement with those obtained via the BCR procedure. These preliminary data show that the proposed screening test is a reliable method for the preliminary rapid evaluation of metal total concentrations and of potential metal mobility in soils, supporting sampling activities directly in the field. © 2017, Springer International Publishing AG.

The activation of natural bioremediation potentials is the challenge that research is currently addressing for overcoming bottlenecks still affecting bioremediation applications. Bioaugmentation is one possible way to activate such natural potentials, provided that the biodiversity introduced to increase catabolically relevant capacity is identified also considering the ecological context. The present work deals with bioaugmentation aimed at the remediation of a soil co-contaminated (spiked) with both diesel oil (1%, v/w), and heavy metals (Pb and Zn), using intact soil core microcosms in different experimental conditions. We supposed that both heavy metal resistance and active metabolism towards organic pollutants are essential metabolic traits to trap the energetic flux, which drives the microbial community towards biodegradation under the given experimental conditions. Consequently, the bioaugmentation was performed by introducing a tailor made microbial formula composed of 12 allochthonous strains. They belong to a stable population previously isolated from a chronic polluted site and are both hydrocarbon degraders and heavy metal resistant and, also, compatible with the autochthonous microbial community. The active role of the microbial formula in pushing the entire community towards an effective bioremediation of diesel oil close to 75%, in the presence of bioavailable metals, has been proven through hydrocarbons analysis, metabolic and molecular profiling at community level (Biolog system, DGGE).

In this paper we studied some heavy metals (Cu, Zn, Cd, Pb, As, U) probably associated to high molecular weight organic compounds present in the Antarctic snow. Snow-pit samples were collected and analysed for high molecular weight fraction and heavy metals bound to them by means of ultrafiltration treatment. High molecular weight dissolved organic matter (HMW-DOM) recovered by ultrafiltration showed a dissolved organic carbon concentration (HMW-DOC) of about 18–83% of the total dissolved organic carbon measured in Antarctic snow. The characterisation of HMW-DOM fraction evidenced an ageing of organic compounds going from surface layers to the deepest ones with a shift from aliphatic compounds and proteins/amino sugars to more high unsaturated character and less nitrogen content. The heavy metals associated to HMW-DOM fraction follows the order: Zn > Cu > Pb >> Cd ∼ As ∼ U. The percentage fraction of metals bound to HMW-DOM respect to total metal content follows the order: Cu >> Pb > Zn, Cd in agreement with humic substance binding ability (Irwing-William series). Going down to depth of trench, all metals except arsenic, showed a high concentration peak corresponding to 2.0–2.5 m layer. This result was attributed to particular structural characteristic of organic matter able to form different type of complexes (1:1, 1:2, 1:n) with metals. © 2017 Elsevier Ltd

A brief review on the occurrence of high natural concentrations of potentially toxic elements (PHEs) in soils and water is presented, analysing also various approaches and strategies applied in different Countries to address the problem of “natural” contamination. Starting from the well known case of arsenic, the situation for other elements such as beryllium, uranium and nickel, among the most interesting, is analysed. The analysis is based on already evidenced geochemical anomalies and on the possible evolution both in the estimate of their toxicological effects and the redefinition (lowering) of the limits at the moment imposed by legislation or suggested by guidelines. New data obtained in the ENEA laboratory in the last years on arsenic and beryllium are presented. The growing need of “geochemical maps” at regional, national and European level and of a continuous monitoring activity is highlighted. At the same time the importance of considering concentration and speciation of elements and how an element is bound and under what circumstances it may be bioavailable and able to damage the ecosystem, is recalled. Finally it is suggested to concentrate efforts on the development of screening methodologies that could play a key role in the characterisation of contamination and on standardising fast procedures that enable a guided real-time survey. The clear definition of a “geochemical risk” requires a complex and multidisciplinary approach, so the emerging role of Medical Geology is underlined. © 2015, Accademia Nazionale dei Lincei.

In view of the establishment of quality standards for uranium in drinking water by the European and Italian authorities, we report a comprehensive overview of the Italian situation regarding uranium concentrations in natural waters. More than 3100 data on waters all over Italy are reviewed in addition to new data for Latium Region (Central Italy) where relatively high concentrations in rocks are long been known. Our study evidences that uranium in bedrock is not the main factor ruling uranium presence in fresh and groundwater, indicating that redox conditions as well as bicarbonates and silicates control solution equilibria and accordingly the uranium content in waters. At present, and considering the provisional guideline value of 30 μg/L established by [WHO (2012) Guidelines for Drinking-Water Quality. World Health Organization, Geneva], no critical situation is envisaged in Italy, but this can be overruled if lower limits will be actually imposed. There is also a need of further studies on uranium speciation in water and of wider epidemiological studies to assess its real toxicity to overcome the uncertainties that have so far hampered the definition of reliable water quality standards. © 2015, Accademia Nazionale dei Lincei.

The anaerobic digestion of marine macroalgae biomass could meet two currently important needs, the mitigation of the eutrophication effects and the production of renewable energy. Because of the abundance of seaweed biomass its conversion can be highly desirable and convenient, mostly for countries with long coastlines or eutrophic environments. The aim of the present work is to carry out an exploratory study of biogas production from macroalgal biomass collected from the Orbetello lagoon (Tuscany, Italy) by solely exploiting the intrinsic degradation potential of the ecosystem. A fresh algae mix and sediments has been used, as both feed and inoculum of an anaerobic digestion process under psychro-mesophilic, mesophilic and thermophilic conditions, in batch reactors, without any washing and drying treatment. The presence of sediment proved to be crucial in order to achieve a good methane yield (methane yield of 380 dm 3 kg −1 VS added ) comparable with literature data obtained through different approaches. The results gave evidence that such an approach will have to be considered when planning a selective anaerobic digestion of macroalgae that could be useful in local applications for coasts and eutrophic lagoons affected by seasonal or frequent algal blooms.

We describe the eruptive activity of the Pleistocene composite Baccano maar crater in the Sabatini Volcanic Complex (Central Italy) combining stratigraphy, grain size/componentry and rare earth element and Yttrium (REY) composition of its eruptive products with the stratigraphy and geothermal data derived from deep wells drilled on the Baccano structural high. The main lithological characteristics of the basal Baccano maar pyroclastic deposit, composed of more than 60% wt of non-thermometamorphosed lithic clasts from the sedimentary basement, show that the first eruption was magmatic-hydrothermal in nature. The lithology of the sedimentary lithic clasts indicates that the fragmentation level was at a depth of −1,000 to −1,200 m, with fragment depth verified by deep well stratigraphy. The 15% wt juvenile non-vesicular glass components suggest that magma played a minor role in powering the eruption. Assuming that the high-salinity hot hydrothermal fluids (365−1,400 m) by the aggressive hydrothermal fluids enriched in acid components (HF, HCl, and H2SO4) may have contributed to increased CO2 partial pressure that helped to drive the hydrofracturing. This could have caused rapid vapour separation and pressure drop, allowing the almost simultaneous breaking of the aquifer cover and brecciation of the calcareous units down to −1,000 to −1,200 m depth. The relative abundance of calcareous lithics in the basal part of the first Baccano eruptive unit, representing about the upper 200 m of stratigraphy below the top of the Baccano structural high, reveals the descent of the piezometric surface during the eruption. Combining deep well information and maar product stratigraphy, using also REY data from maar pyroclastic fragments and the basement rocks we draw an interpretative model for the Baccano maarforming eruption, concluding that a) magmatic-hydrothermal eruptions may originate deeper than previously thought, and b) hydrothermal fluids circulating in limestone aquifers ma

Purpose Risks associated to “heavy metals” (HM) soil contamination depend not only on their total content but, mostly, on their mobility. Many extraction procedures have been developed to evaluate HM mobility in contaminated soils, but they are generally time consuming (especially the sequential extraction procedures (SEPs)) and consequently applicable on a limited number of samples. For this reason, a simple screening method, applicable even “in field”, has been proposed in order to obtain a rapid evaluation of HM mobility in polluted soils, mainly focused on the fraction associated to Fe and Mn oxide/hydroxides.

Arsenic occurrence in groundwater near the Cimino-Vico volcanoes (central Italy) was analysed considering the hydrostratigraphy and structural setting and the shallow and deep flows interacting within the Quaternary volcanics. Groundwater is the local source of drinking water. As documented in the past, arsenic in the groundwater has become a problem, and the European maximum allowable contaminant level was recently lowered to 10 μg/L. Chemical analyses of groundwater were conducted, sampled over an area of about 900 km2, from 65 wells and springs representative of the volcanic aquifer and thermal waters. Considering the type of aquifer, the nature of the aquifer formation and its substratum, the hydrochemical data highlight that the arsenic content of the groundwater is mainly connected with the hydrothermal processes in the volcanic area. Thermal waters (54–60°C) fed from deep-rising fluids show higher arsenic concentrations (176–371 μg/L). Cold waters sampled from the volcanic aquifer are characterized by a wide variability in their arsenic concentration (1.6–195 μg/L), and about 62% exceed the limit of 10 μg/L. Where the shallow volcanic aquifer is open to deep-rising thermal fluids, relatively high arsenic concentrations (20–100 μg/L) are found. This occurs close to areas of the more recent volcano-tectonic structures.

Risks posed by antifouling agents (irgarol 1051, diuron and dichlofluanid) to the aquatic environment of the Gulf of Napoli have been estimated. Seawater samples were collected monthly in selected harbours and marinas of this area during the boating season (March to November 2005) and off-season (January 2006). Concentration levels have been measured, and the resulting data used to perform a probabilistic ecological risk assessment independently on each biocide. Diuron exhibited higher concentration levels than irgarol 1051 in all the investigated locations: Dissolved concentrations of diuron ranged from

The aim of this work was to investigate the mixture toxicity of Irgarol (2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine), Diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), and copper upon the sea urchin Paracentrotus lividus and to compare the observed data with the predictions derived from approaches of Concentration Addition (CA) and Independent Action (IA). Copper spermiotoxicity was more sensitive (EC50 = 0.018 mg/L) than embryotoxicity (EC50 = 0.046 mg/L). The offspring malformations were mainly P1 type (skeletal alterations) in both cases, probably because copper competes to fix Ca2+. Irgarol and Diuron toxicity has been previously investigated. EC50 mixture embryotoxicity showed an EC50 of 1.79 mg/L, whereas spermiotoxicity mixture effects were lower than 11%. Both CA and IA modeling approaches failed to predict accurately mixture toxicity. For embryotoxicity, the IA model overestimated the mixture toxicity at effect levels of

Organophosphorous (OP) insecticides reveal acute toxicity because of their capability to affect the nervous system through the inhibition of acetyl cholinesterase function in regulating the neurotransmitter acetylcholine. The present work shows an example of an easy to be handled inhibition electrochemical biosensor, based on thick film technology for low cost production of screen printed electrodes. Anti-cholinesterase activity in specific fruits was determined measuring the inhibition of acetyl cholinesterase enzyme owing to the presence of OP pesticides. Paraoxon was taken as reference pesticide for each measurement. The main fluidic critical parameters were investigated under flow injection analysis, through the comparison of different enzymatic immobilisation methods. Analytical features were evaluated as a function of experimental parameters. The analytical detection was developed in a three step procedure and the pesticides content was measured in strawberries samples taken from the local market. T...

Non-occupational, environmental and unintentional exposure to fibrous tremolite, one of the most widespread naturally occurring asbestos, represents a potentially significant geological risk in several parts of the world. The toxicity of amphibole asbestos is commonly related to iron content and oxidation state, but information available on surface iron topochemistry and amphibole alteration mechanism is still rather poor. With the aim to shed a light on this mechanism, two tremolite samples, one from Italy (Castelluccio) and one from USA (Maryland), immersed in a buffer solution (pH7.4) with H2O2 were characterized by a multi-technique approach. X-ray photoelectron spectroscopy (XPS) and high resolution-transmission electron microscopy (HR-TEM) were used to investigate the surface chemistry of the incubated samples and to detect structural modifications of the fibres, while inductively coupled plasma optical emission spectrometry (ICP-OES) was used to determine the concentration of dissolved elements.An original four-step model for amphibole alteration pathway is proposed. The alteration process starts with an incongruent dissolution of the amphiboles that produces an amorphous, altered surface layer and that is followed by iron oxidation and formation of FeOOH species. Then the congruent dissolution of the altered layer starts and, subsequently, the residual Fe oxi-hydroxides aggregates and insoluble, Fe-rich, amorphous nanoparticles on top of the fibres are formed. The results are compared to those obtained on crocidolite, a highly toxic amphibole asbestos with a 10 to 20 times higher iron content than tremolite. The high chemical reactivity observed in the literature for tremolite appears to be related not only to its iron content and oxidation state, but also to the low nuclearity of iron on the altered surfaces, in contrast to pronounced Fe clusterization at crocidolite surfaces. This is a significant step toward a conceivable explanation of why asbestos tremolite is potentially as toxic as crocidolite. © 2015 Elsevier B.V.

Two samples of fibrous erionite from different localities of Oregon, USA were suspended in FeCl2 solutions at different concentrations, at pH ca. 5, in anaerobic conditions. Comparison between released and acquired charges under the form of Fe confirms that erionite binds Fe (II) by ion exchange with the extra framework (EF) cations, mainly Na. The Fe (II) binding process exhibited by both studied samples here investigated indicates a direct correlation between the extent of the ion-exchange process and the Fe (II) concentration of the solution used for fibres incubation. In the sample from Rome no further Fe (II) acquisition was observed for concentrations exceeding 500 μM FeCl2. XPS investigation revealed that, when comparing surface and bulk composition of the samples, no Fe enrichment of the fibre surface was observed. Moreover, the location of Fe (II) within the erionite cage has been devised by combining chemical and structural data. Results highlight that, for both samples, Fe (II) is fixed at the Ca3 site being six-fold coordinated to water molecules. The occurrence of Fe (II) within the erionite cage causes a gradual migration of the other EF cations and in addition, induces a small rearrangement of the water molecules positions. It is worth mentioning that, in Fe-loaded zeolites at rather low Fe content, the Fe sites with very low nuclearity, located in well-defined crystallographic positions, represent the active sites for the formation of reactive oxygen species. Therefore, identification of segregation of Fe (II) at Ca3, which is coupled with the high surface area of erionite, provides very important information for the understanding of the molecular mechanism/s inducing its strong carcinogenicity. © 2015 Elsevier Inc.

The effect of adding treated red mud, a by-product of alumina production, to soil polluted by an abandoned mine and characterised by high concentrations of heavy metals, relatively low reaction grade, and low organic carbon content, was investigated. Also studied was addition of both red mud and compost (produced from source-separated municipal solid waste)--the synergistic action of red mud and compost could be exploited to achieve both metal trapping and an increase in organic carbon content. Leaching batch tests were performed on four different systems: soil, soil and treated red mud, soil and compost, soil and compost plus treated red mud. Dilute sulfuric acid and EDTA solution (liquid/solid ratio 10:1) were used in the tests--sulfuric acid to "mimic" acid rain and EDTA in accordance with general methods for estimating "plant-available" metals. Sequential extraction was also applied to the same samples. The use of relatively non-specific extractant reagents in the leaching tests led to a kinetic approach (already proposed in literature), because measurements of trace elements extracted at equilibrium cannot be related to their speciation. Comparison of information obtainable by the kinetic approach to evaluation of data from leaching tests with results from sequential extraction enabled evaluation whether the "kinetic fractionation method", a relatively rapid and simple procedure, furnishes adequate information about the mobility and bioavailability of trace elements. Especially interesting results were obtained for Mn, Zn, and Ni, present in large amounts in the soil studied--their leachability was significantly reduced by addition of red mud and compost, suggesting interesting perspectives in soil-remediation activity.

Red mud is the major solid waste produced in the process of alumina extraction from bauxite (Bayer process). Environmental "compatibility" of a treated red mud was studied in order to evaluate its possible recycling in environmental compartments. The leaching test requested by the Italian law on treated solid waste to be "re-introduced in the environment" was performed on this material. Moreover, in order to better evaluate the environmental compatibility, three different types of eco-toxicological tests were applied (Microtox test, ASTM microalgae toxicity test and sea urchin embryo toxicity test). These "chemical" and eco-toxicological tests gave encouraging results. The possibility to use this material for treating contaminated waters and soils was evaluated, again with particular attention to the Italian regulatory system, through experiments on the treated red mud metal trapping ability and on the subsequent release of trapped metals, at low pH conditions. The treated red mud showed a general high metal trapping capacity and the release at low pH was generally low.

Purified acetyl cholinesterase (AChE) from electric eel or engineered yeasts (Kluyveromyces lactis) expressing cholinesterase activity from rat, were immobilised on a nylon membrane for the measurement of residual cholinesterase activity after inhibition by the organophosphorous insecticide Paraoxon (diethyl p‐nitrophenyl phosphate). Measurement was separately operated after the incubation (inhibition) step. The measurement of the residual enzyme activity was therefore performed in a standardised solution with a choline electrochemical biosensor, without any interference, avoiding the use of protecting selective membranes. Both commercial amperometric sensor and screen‐printed electrodes, produced and optimized in the laboratory, were used. The time consuming incubation step was simultaneously performed on several samples, thus lowering the analysis time per sample. Good limit of detection (LOD) (0.1 µg/L) and reproducibility were obtained for the analysis of paraoxon. A simple procedure for the ...

A method has been developed for determination of copper, lead, cadmium and zinc concentration in dry wines by stripping voltammetric with a thick-film modified graphite-containing electrode (TFMGE). This method does not require the preliminary acid digestion of the sample or other approaches for the destruction of organic substances. The optimal conditions for the determination of these elements in wines have been chosen. Supporting electrolyte was 0.5 M HCl for Cu, Pb and Cd, and 0.1 M acetate buffer (pH 5.5) and 0.35 M NaCl for Zn. The accumulation potential was −0.8 V for Cu, −1.2 V for Pb and Cd, and −1.4 V for Zn. The degree of wine dilution with the supporting electrolyte was 1:1.1 for Cu, Pb and Cd, and 1:50 for Zn. The accumulation time was 30–60 s for copper, 120 s for lead and cadmium, and 10–30 s for zinc. Results obtained under the chosen conditions with the use of TFMGE were compared with those obtained using ICP-MS for the final determination of the selected elements. Moreover, it was shown that the proposed method provided better reproducibility than methods involving wine decomposition.

Two alternative extraction methods—a routine ultrasonic bath and a microwave oven—were developed and optimized for their eventual exploitation in the three-stage sequential extraction procedure proposed by the European Standards, Measurements and Testing (S, M & T) Programme, formerly Bureau Communitaire de Reference (BCR), for the operationally defined speciation of Cd, Cr, Cu, Ni and Zn. The conventional BCR three-stage sequential extraction procedure was modified at each stage, applying ultrasonic or microwave devices in order to shorten the required 16 h of shaking in all three steps. The experimental tests and the optimization of the operating parameters were carried out on a highly homogenized estuarine sediment reference material (RM S7) prepared by the Joint Research Centre (JRC) of ISPRA. Extractable metal contents were measured by inductively coupled plasma-mass spectrometry (ICP-MS) and the results obtained in each fraction by all three methods were statistically compared for all the studied elements. The conventional and newly developed alternative extraction methods were finally compared by the analysis of BCR 601, which is certified for the three-step BCR sequential extraction procedure. According to the statistical evaluation of the results, the proposed accelerated sequential extraction methods are valid alternatives to conventional shaking, with much shorter extraction times.

Mariangela Bellusci,1 Aurelio La Barbera,1 Franco Padella,1 Mariateresa Mancuso,2 Alessandra Pasquo,2 Maria Giuseppa Grollino,2 Giorgio Leter,2 Elisa Nardi,3 Carlo Cremisini,3 Paola Giardullo,4 Francesca Pacchierotti21Technical Unit for Material Technologies, 2Technical Unit for Radiation Biology and Human Health, 3Technical Unit for Environmental Characterization, Prevention and Recovery, Agenzia Nazionale per le Nuove Tecnologie, l'Energia e lo Sviluppo Economico Sostenibile (ENEA), Casaccia Research Centre, Rome, Italy; 4Department of Radiation Physics, Marconi University, Rome, ItalyAbstract: Superparamagnetic iron oxide nanoparticles are candidate contrast agents for magnetic resonance imaging and targeted drug delivery. Biodistribution and toxicity assessment are critical for the development of nanoparticle-based drugs, because of nanoparticle-enhanced biological reactivity. Here, we investigated the uptake, in vivo biodistribution, and in vitro and in vivo potential toxicity of manganese ferrite (MnFe2O4) nanoparticles, synthesized by an original high-yield, low-cost mechanochemical process. Cultures of murine Balb/3T3 fibroblasts were exposed for 24, 48, or 72 hours to increasing ferrofluid concentrations. Nanoparticle cellular uptake was assessed by flow-cytometry scatter-light measurements and microscopy imaging after Prussian blue staining; cytotoxicity was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and colony-forming assays. After a single intravenous injection, in vivo nanoparticle biodistribution and clearance were evaluated in mice by Mn spectrophotometric determination and Prussian blue staining in the liver, kidneys, spleen, and brain at different posttreatment times up to 21 days. The same organs were analyzed for any possible histopathological change. The in vitro study demonstrated dose-dependent nanoparticle uptake and statistically significant cytotoxic effects from a concentration of 50 µg/mL for the MTT assay and 20 µg/mL for the colony-forming assay. Significant increases in Mn concentrations were detected in all analyzed organs, peaking at 6 hours after injection and then gradually declining. Clearance appeared complete at 7 days in the kidneys, spleen, and brain, whereas in the liver Mn levels remained statistically higher than in vehicle-treated mice up to 3 weeks postinjection. No evidence of irreversible histopathological damage to any of the tested organs was observed. A comparison of the lowest in vitro toxic concentration with the intravenously injected dose and the administered dose of other ferrofluid drugs currently in clinical practice suggests that there might be sufficient safety margins for further development of our formulation.Keywords: biodistribution, biosafety, ICP-MS, Prussian blue staining, MnFe2O4 nanoparticles, ferrofluid

The paper describes the fieldwork at the Italian test site of the abandoned mine of sphalerite and galena in Ingurtosu (Sardinia), with the aim to assess the applicability of a "toolbox" to establish the optimized techniques for remediation of soils contaminated by mining activities. A preliminary characterization-including (hydro)geochemistry, heavy metal concentration and their mobility in soil, bioprospecting for microbiology and botany-provided a data set for the development of a toolbox to deliver a microbially assisted phytoremediation process. Euphorbia pithyusa was selected as an endemic pioneer plant to be associated with a bacterial consortium, established with ten selected native strains, including metal-tolerant bacteria and producers of plant growth factors. The toolbox was firstly assessed in a greenhouse pot experiment. A positive effect of bacterial inoculum on E. pithyusa germination and total plant survival was observed. E. pithyusa showed to be a well-performing metallophyte species, and only inoculated soil retained a microbial activity with a high functional diversity, expanding metabolic affinity also towards root exudates. These results supported the decision to proceed with a field trial, investigating different treatments used singly or in combination: bioaugmentation with bacterial consortia, mycorrhizal fungi and a commercial mineral amendment. Microbial activity in soil, plant physiological parameters and heavy metal content in plants and in soil were monitored. Five months after the beginning, an early assessment of the toolbox under field conditions was carried out. Despite the cold season (October-March), results suggested the following: (1) the field setup as well as the experimental design proved to be effective; (2) plant survival was satisfactory; (3) soil quality was increased and bioaugmentation improved microbial activity, expanding the metabolic competences towards plant interaction (root exudates); and (4) multivariate analysis supported the data provided that the proposed toolbox can be established and the field trial can be carried forward. © 2013 Springer-Verlag Berlin Heidelberg.

The inhibition effect of heavy metals ions such as Hg(II), Cu(II), V(V), and Ni(II) on the activity of oxidase enzymes such as alcohol oxidase, glycerol 3-P oxidase, and sarcosine oxidase has been studied and used for the construction of calibration curves in flow-injection analysis. A platinum-based H2O2 probe was used to measure the enzymatic activity of the selected oxidase enzymes. The most sensitive detection system was obtained using the glycerol 3-P oxidase/Hg(II) couple. A calibration curve was obtained in the 0.05–0.4 ppm range, with a detection limit of 0.05 ppm, and a 50% of inhibition (I50) of 0.2 ppm. The enzyme alcohol oxidase was used to construct calibration curves for Cu(II) and V(V). The detection limits were 2 and 0.5 ppm, respectively, with I50 ppm for cu(II) and 2.7 ppm for V(V). Ni(II) was detected in the 1–6 ppm range, using the enzyme sarcosine oxidase; I50 was 3.8 ppm. Relative standard deviations were ≤5% for each enzyme/ion metal couple. The analytical behavior was comparable to...

Results. Middle (Cu, Cr) and low (Cd, Pb, Zn) concentrations of heavy metals in sediment samples from the deeper central part of the lagoon were observed. Cadmium resulted in mainly being associated with carbonate forms (~60%), whereas Cr and Ni occurred primarily as residual mineral phases (>50%). Zn appeared uniformly distributed among the main geochemical forms. Considerable presence of Cr, Cu and Pb was found in the oxidizable fraction (~50%), indicating organic matter and/or sulphides major sinks for these metals. Differences of heavy metal distribution among sediment samples were observed, depending on the total metal content and on sediment properties. Modifications in metal speciation induced by sediment air drying mainly consist of a transfer of the actual and potentially mobile fractions towards immobile fractions (mineral residue) by oxidation and formation of Fe and Mn oxides. Discussion. Both total content and sequential extraction results did not show an environmental critical situation: the only possible risk, associated with heavy element mobility, could occur in consequence of a drastic pH and redox equilibria variation at the water-sediment interface. Conclusions. Despite all limitations, the BCR-SEP combined with information on the chemical and mineralogical properties of the sediment solid matrix provides a valuable approach to describe the risks related to the potentially toxic HM occurring in sediments (in this paper the case of the Fusaro lagoon is examined). HM distribution among the sequentially extracted geochemical forms is affected by sediment properties, such as pH (Zn), clay (Cd), Fe easily reducible oxides (Pb) and organic matter (Cu) content. Recommendations. Political managers, usually facing limitations of time and resources, have to optimize the cognitive phases, selecting the most useful information to make 'effective and correct decisions' in the environmental field. Therefore, although conscious of the limits of the adopted quality assessment, we believe it represents a good compromise between time and resource availability (i.e. type and quality of information). Outlook. The complementary use of the simple and rapid European fractionation scheme with information on the chemical and mineralogical properties of the sediments provides more awareness about the nature of the sediment components involved and offers a more reliable way for studying HM speciation in sediments.

The efficiency of different digestion methods (six microwave decomposition methods and a wet acid digestion method) in the solubilisation of six metals (Cr, Ni, Cu, Pb, Cd, Zn), for their determination in fly ashes, was compared. Five different mineral acid mixtures and two different microwave systems were tested. The study was carried out by analyzing two highly homogenised fly ash samples (from sewage sludge and city waste incineration) provided by the Joint Research Centre of Ispra. Determinations were performed by atomic absorption spectrometry and by inductively coupled plasma atomic emission spectrometry. The analytical performance of the laboratory was evaluated using the 1633a Coal Fly Ash Standard Reference Material of National Bureau of Standards (NBS SRM 1633a). Results showed that a HNO3 microwave treatment was strong enough to solubilise metals from the considered fly ashes. Moreover, microwave methods generally provided higher release than the classical aqua regia method, whereas no significant advantage was observed using a high performance microwave unit.

Two sequential extraction procedures (a 3-step protocol proposed by the Standards, Measurements and Testing programme (SMT this CRM has been recently certified for the content of Cd, Cr, Cu, Ni, Pb and Zn in the three fractions resulting by applying the SM&T 3-step procedure. Results of this evaluation showed the high reliability of the analytical performances of the laboratory for all considered metals. Results of the comparison between 3- and 5-step procedures showed no differences for Zn and Cd whereas significant differences have been found for Pb, above all, and for Cr, Ni and Cu relatively to the oxidisable fraction.

Polychlorinated biphenyls (PCB) congeners were determined in water samples, sediments, and animal species in the frame of a survey of the River Arrone (Central Italy, near Rome) after a major contamination episode. Animal species were selected on the basis of their living and feeding habits and evaluated as candidate bioindicators of PCB pollution in this lotic ecosystem. Total PCB concentrations in water were found to be low (ng/L level), and in sediments, ranged from about 10 to 200 μg/kg dry weight, depending on the distance from the contamination source. PCB patterns in sediments showed a prevalence of higher chlorinated congeners over time. Concentrations in macroinvertebrates ( Calopteryx splendens and Anax imperator ) ranged from 60 to 400 μg/kg dry weight, showing significantly different species to species patterns. PCB concentrations were almost parallel in sediments for different sampling stations, while differences in patterns among species can be explained in terms of bioaccumulation/excretion mechanisms. Freshwater shrimps ( Palaemonetes antennarius ) were not found close to the contamination source, as a consequence of their extreme sensitivity to chemicals, and showed a peculiar pattern (almost exclusively determined by congeners 153, 138, and 180) probably originating from biodegradation mechanisms. Fish samples ( Rutilus erythrophthalmus ) showed the highest concentrations, as a combination of feeding habit, lipid content, and, probably, less effective biodegradation/excretion pathways. Congener patterns closely match those of Aroclor 1260, which originates from the contamination source. This study confirms that congener physical and chemical parameters, different degradation rates, feeding habits, and mobility of the analysed aquatic organisms, metabolism, and excretion mechanisms, are to be considered to explain the distinctive PCB patterns of different samples.

A sampling campaign for the determination of phthalate acid esters (PAEs) levels in freshwaters and sediments of rivers and lakes of the Rieti District (central Italy) was carried out in 1994. Sixty-six water samples, collected in three series, and thirteen sediment samples were analyzed by gas chromatography/mass spectroscopy (GC/MS). The analytical results on water samples showed a direct relation of PAEs levels with the input of urban or industrial treated wastewaters near the sampling point. Because of their tendency to be adsorbed on sediments, the presence of PAEs was limited to within a few kilometers of the source of contamination. Accumulation factors in sediment samples, in fact, ranged from 10 to 100.

Geochemical background concentrations of potentially harmful elements and species (PHES) may have a high spatial variability and their natural levels can be higher than those caused by anthropogenic sources of pollution. Therefore, the use of a threshold value for assessing contamination can be inadequate and local variability should be considered. In Europe, soil quality standards are widely variable. In Italy concentration levels exceeding threshold values (TVs) are allowed only if the natural concentrations for a given area are higher than those specified by law. For sediments, in Italian law TVs have not been yet established but TVs with local validity are used for contamination assessment in areas with different geochemistry. A short outline of the worldwide regulatory frameworks is presented with the intent of singling out suitable approaches and priority actions needed to tackle the weak points in law, following the indications of the scientific community and stressing the importance of assessing the real hazard using tools for the evaluation of site-specific mobility and toxicity of PHES. Cases of areas with high PHES background concentration are presented as evidence of this widespread phenomenon and of the need to find effective approaches and solutions.

Purpose: The assessment of risk related to the presence of potentially toxic elements in soils is strictly related to the knowledge of their form and mobility. These relevant properties depend on the complex interactions of the elements of concern with the soil particles that generally cannot be addressed by a single technique. This study presents an integrated approach implementing geochemical and mineralogical investigation techniques on samples from a former mining area (Tolfa Mountains district, northern Latium, Italy), where exploiting activities occurred until the recent past. In particular, the As total concentration and the As distribution in solid phases is studied with the aim to evaluate the possibility of environmental pollution and consequent risks for the health of people living in the area and possibly affected in case of significant mobilization of this toxic element. Materials and methods: Chemical (ICP-MS, ICP-OES) and mineralogical (Xray diffraction (XRD), scanning electron microscopy–energy dispersive X-ray (SEM-EDX), X-ray absorption near-edge structure (XANES)) analyses and the evaluation of the heavy metal mobility (by means of a sequential extraction procedure) were performed. Results and discussion: Chemical analyses show a high As content in the soils collected immediately downstream the marcasite mine waste deposit, that is the starting point of As pollution over the whole area. XANES analyses show that As occurs in two oxidation states (AsIII and AsV) simultaneously in the tailing samples and nearby, while it has been mainly or totally transformed into AsV at increasing distance from the mine. XRD data show that sheet silicates don’t affect As behavior, whereas sequential extractions and SEM-EDX analyses reveal the evident association of As and Fe oxyhydroxides content. Conclusions: The use of an integrated geochemical-mineralogical approach allows to single out the contaminant forms and the relative potential threat. Arsenic in the surface level of such soils could be mobilized in the case of extreme meteorological or of a not well planned human event, even though there is no evidence yet of any serious contamination of either underground or flowing waters.

In the process of remediation of mine sites, the establishment of a vegetation cover is one of the most important tasks. This study tests two different approaches to manipulate soil properties in order to facilitate plant growth. Mine waste from Ingurtosu, Sardinia, Italy rich in silt, clay, and heavy metals like Cd, Cu, and Zn was used in a series of greenhouse experiments. Bacteria with putative beneficial properties for plant growth were isolated from this substrate, propagated and consortia of ten strains were used to inoculate the substrate. Alternatively, sand and volcanic clay were added. On these treated and untreated soils, seeds of Helianthus annuus, of the native Euphorbia pithyusa, and of the grasses Agrostis capillaris, Deschampsia flexuosa and Festuca rubra were germinated, and the growth of the seedlings was monitored. The added bacteria established well under all experimental conditions and reduced the extractability of most metals. In association with H. annuus, E. pithyusa and D. flexuosa bacteria improved microbial activity and functional diversity of the original soil. Their effect on plant growth, however, was ambiguous and usually negative. The addition of sand and volcanic clay, on the other hand, had a positive effect on all plant species except E. pithyusa. Especially the grasses experienced a significant benefit. The effects of a double treatment with both bacteria and sand and volcanic clay were rather negative. It is concluded that the addition of mechanical support has great potential to boost revegetation of mining sites though it is comparatively expensive. The possibilities offered by the inoculation of bacteria, on the other hand, appear rather limited.

Beryllium is widely distributed in soils at low levels, but it can also occur naturally in higher concentrations in a variety of materials exploited for many industrial applications. Beryllium is also one of the most toxic natural elements and is known to be a human carcinogen. A concise account of the literature data on baseline concentrations of Be in soils illustrates the possibility of worldwide presence of areas with a high natural background concentration of Be (up to 300 mg/kg), the crustal abundance of which is generally estimated to be in the range 2-6 mg/kg. Nethertheless the number of available data is rather limited in comparison with those about other toxic elements such as Pb, Cd, Cr…This could have probabibly caused the choice of low values of concentration level as the reference ones for the definition of soil as contaminated: these values are not always realistic and applicable to large areas.As a case study we report and analyse a diffuse, unusually high (up to 80 mg/kg, average approximately 20 mg/kg), natural occurrence of beryllium in loose and poorly consolidated pyroclastic layers related to the Pleistocene activity of the Vico volcano. Additionally, the analysis of Be leachability has been carried out, providing evidence of a not negligible mobility in contrast with the scarce data presented in the literature that usually indicate beryllium as an element with low mobility in slighty acidic and oxidising surface environmental conditions. This research is proposed as a starting point for a possible possible reappraisal of beryllium geochemical behaviour and background levels, providing more realistic and flexible reference values for risk assessment and land management.

These are preliminary findings of recent laboratory experiments for the evaluation of short-term photosynthetic performance of Ulva laetevirens. Study of the accumulation of polychlorinated biphenyls (PCB) and the distribution of the PCB congeners as a basis for evaluating the effects on physiological processes such as photosynthesis and respiration are included in the future research programme.

Aspects related to the use of free and immobilised acetylcholinesterase (AChE) for the development of an amperometric biosensor for organophosphorus (OP) insecticides based on enzyme inhibition have been studied. Procedures based on free and immobilised AChE were previously studied from many authors but the measurement of the residual enzyme activity has been directly carried out in the same sample where incubation of AChE with OP has been performed. With AChE immobilised on a nylon net and not assembled on the sensor it is possible to perform incubation and measurement steps separately: the incubation step is performed in the sample containing the inhibitor, the measurement step is performed in a standard solution containing the specific substrate in the buffer. With this two-step procedure, a Pt electrode, only covered with a thin layer of cross-linked choline oxidase and without any membrane, has also been used in batch conditions obtaining interesting results in terms of sensitivity, precision and limit of detection.

Hg(II), methylmercury and ethylmercury have been determined with an electrochemical glucose probe. Mercury and its compounds inhibit the enzyme invertase which, in presence of its substrate, sucrose, produces glucose. When invertase is in presence of mercury its activity decreases; this causes a decrease of glucose production, which is monitored by the glucose sensor and correlated to the concentration of mercury in solution. Parameters such as pH, enzyme concentration, substrate concentration, and reaction and incubation time were optimized. Results showed that mercury, methylmercury and ethylmercury can be detected directly in aqueous solution in the range 2–10 ng/ml.

Organotin compounds are currently determined in various environmental matrices (in particular water, sediment and shellfish) to form the basis of control measures for the levels of contamination, as required in some EC Directives. Accurate measurements are a prerequisite for the enforcement of this legislation, which implies that good quality control of determinations should be ensured. One of the tools for achieving accuracy is to use certified reference materials (CRMs). With regard to tin species, however, CRMs are rather scarce and mainly concern sediment and fish matrices certified for their butyltin content. The present study deals with the preparation of a mussel candidate reference material and the verification of its homogeneity prior to the certification of the contents of butyl- and phenyl-tin compounds. 100kg of mussels (Mytilus edulis) were collected, carefully washed with fresh water in order to eliminate matrix salts and immediately frozen by immersion in liquid nitrogen. The mussels were shelled (in the frozen state) and the edible part was stored in thermally sealed polyethylene bags which were stored at −25 °C. The frozen material was ground in a Teflon-coated grinding mill, spread on sterilized flat trays and freeze-dried. The freeze-dried material was then ground for 15 days in a zirconia ball mill and sieved on a titanium sieve to separate the fibrous part. Successively, the material was mixed for 15 days under argon atmosphere in a special polyethylene-lined mixing drum and bottled in brown Pyrex-glass bottles. 21 bottles were selected during the course of the bottling procedure to verify the within- and between-bottle homogeneity of the overall batch. The within-bottle homogeneity was verified by determining the organotin (butyl- and phenyltins) content for subsamples of 500 mg in ten replicates from one bottle, whereas the between-bottle homogeneity was controlled by one organotin measurement from each of 20 bottles. The analyses were performed by GC-MS. The results showed that the homogeneity of the material makes it suitable as a candidate reference material.

Concentrations of polycyclic aromatic hydrocarbons (PAH) in atmospheric particulates have been determined in the frame of the control activities for environmental protection during the VI (1990-1991), VII (1991-1992) and VIII (1992-1993) Italian expeditions in Antarctica. Samples were collected at the four cardinal points at about 200 m from the central area of the Italian scientific base. Data show low levels of the individual PAH (95% in the range 1-50 pg m(-3)) confirming the absence, up to now, of significant contamination from the base. These results could be used as a reference for the assessment of the air pollution due to combustion sources present in the base. Any possible variation in the base's activities in the future should be analysed and evaluated with respect to these findings.

Mineralogical and geochemical studies were undertaken in the volcanic area of Biancavilla (Catania, Italy) with the aim of explaining the nature of the high As and F contents of the area’s rocks. As and F contents in soils and groundwater were also investigated. The metasomatised benmoreite lavas show fluorine and arsenic concentrations up to about 3,000 and 1,000 mg/kg, respectively. Mineralogical analyses show that fluorine occurs mostly in fluoro-edenite and apatite-(CaF) crystals, both abundantly present in the altered rocks, while As is exclusively attributed to the apatite-(CaF) crystals. Specifically, arsenic was observed only at the borders of these apatite crystals. Leaching tests and sequential extraction procedures were carried out to evaluate the potential remobilisation of As and F by the mineral phases and the eventual risks induced by their spreading. The results of the leaching tests suggest that As is almost totally associated with the ‘easily reducible’ fraction and that it is released by the preferential dissolution of the arsenic enriched rims of apatite-(CaF) crystals. In soils, As concentration is relatively low (about 15 mg/kg, on average), while F ranges from 236 to 683 mg/kg. The underground waters supplying the town of Biancavilla show As and F contents lower than the allowed limits for drinking water, (As:10 μg/L, F:1–1.5 mg/L). The limited distribution of these rocks and the relatively limited mobilisation by the minerals both contribute to maintain low As and F values, in soils and groundwaters, despite the high values in metasomatised lava samples.

Analysis of organotin compounds in environmental matrices is usually performed by chromatographic or spectroscopic techniques. Only a few papers dealing with organotin voltammetric determination have so far been published and this techniques does not seem very promising for organotin speciation. The reasons are likely to be found in the very low organotin concentration levels in the marine environment, in the complexity of environmental matrices and in the presence of several organotin compounds (butyl- and phenyltins), together with other metals, in samples; the latter leads to peak overlapping. In this paper we present a study of the influence of tropolone (2-hydroxycyclohepta-2,4,6-trienone) on the voltammetric speciation of butyltin compounds. Results suggest that tropolone, being able to form complexes of different stability with tin and its compounds, improves the applicability of voltammetry to organotin determination by enhancing sensitivity and resolution.

An analytical procedure was developed for the determination of methylmercury in human hair using capillary gas chromatography with electron capture detection (GC–ECD). Hair samples are digested in alkaline solution/toluene in an ultrasonic bath at about 50°C. After cooling and treatment with hydrochloric acid (6 mol I−1) and a saturated solution of copper sulphate, the organic phase is extracted with a cysteine solution. Methylmercury is back-extracted in toluene by adding copper sulphate and potassium bromide and analysed by GC–ECD using a DB17 capillary column. The practical detection limit of the method for methylmercury is 50 ng g−1 using 100 mg of hair sample. Column performances and injection reproducibility have been evaluated. Results on 13 samples of human hair are presented and related to the total mercury concentration. The method, consisting of the optimization of similar analytical procedures through improvements in the various steps, allows for sensitive and reliable quantitation of methylmercury in hair with good precision and accuracy.

In order to check the possible occurrence of degradation of tributyltin and triphenyltin in mussel samples during their storage, a 1-year stability study was carried out. Analyses by gas chromatography with flame photometric detection and gas chromatography-mass spectrometry were performed on freeze-dried mussel samples stored under different conditions of temperature and light. The results showed that very good stability of butyl- and phenyltins can be achieved when samples are stored at −20°C in the dark. In contrast, samples stored at room temperature showed significant variations in organotin speciation, particularly in the presence of light.

Rock, sediment and water samples from areas characterised by hydrothermal alterations in the Sabatini and Vico Volcanic Districts, near Rome and the large city of Viterbo, respectively, were collected and analysed to determine the total fluorine (F) content and to understand the F geochemical back-ground level in the volcanic districts of central Italy. Leaching and alteration processes controlling the high concentration of F in water were also investigated. Fluorine concentrations were directly determined (potentiometrically) by an F selective electrode in water samples, while the procedure for rock samples included preliminary F dissolution through alkaline fusion. F concentrations higher than 800 mg kg−1 were commonly found in the analysed rocks and sediments; the concentration depended on the lithology and on the distance from the alteration areas. A specific successive sampling campaign was con ducted in three areas where the F content in sediments was particularly high; in the same areas, measurements of CO2 flux were also performed to investigate the possible deep origin of F. To verify the relation ship among the high F contents in rocks and sediments, the leaching processes involved and the presence of F in the aquifer, we also collected water samples in the western sector of the Sabatini Volcanic District, where hydrothermal manifestations and mineral springs are common. The data were processed 40 using a GIS system in which the F distribution was combined with morphological and geological observations. The main results of our study are that (1) F concentrations are higher in volcanic and recently formed travertine (especially in hydrothermally altered sediments) than in sedimentary rocks and decrease with distance from hydrothermal alteration areas, (2) F is more easily leached from hydrother- mally altered rocks and from travertine and (3) sediments enriched with F may indicate the presence of deep regional fractures that represent direct path- ways of hydrothermal fluids from the crust to the surface.

Analytical procedures for the determination of organotin compounds in sea water, sediments and mussels have been adopted in our laboratory, intercomparison/certification exercises with other European laboratories giving satisfactory results. The characteristics of the different methodologies are discussed, the balance between practical and analytical aspects leading to the selection of the following procedures. For water samples two alternative extraction techniques are used: liquid/liquid extraction (0.3% tropolone in methylene chloride) or liquid/solid extraction (C18- or Carbopack B-loaded extraction tubes). Solid-phase extraction ensures good results and is more suitable in the field, avoiding high volumes of organic solvents and transport of fragile glassware. Extraction rubes can be easily stored, and problems with the transfer of whole samples to the laboratory, and storage and conservation problems are prevented. For sediments and mussels, sonication (0.05% tropolone in methanol) can be u...

An analytical procedure for the determination of 2-ethyl-1-hexanol (2-EH) in drinking water is presented. The method is based on volatile-compound stripping, adsorption on activated-charcoal-filled tubes, solvent elution, identification by gas chromatography/ mass spectrometry, and determination by gas chromatography with flame ionization detection. Bottled samples with undesirable organoleptic characteristics were analzyed to determine a possible correlation with the presence of 2-EH. The presence of 2-EH at 2-10 μg/L was confirmed in several samples. The presence of di-2-ethylhexyl phthalate (D2EHP) was also checked in all samples. This compound was always found at 2-30 μg/L. Hydrolysis of D2EHP was carried out for 2 weeks to evaluate its possible contribution to water contamination by 2-EH. Tests did not show measurable amounts of the alcohol. Nonetheless, the hydrolysis of phthalates in the weakly acidic conditions of the examined waters would not justify the presence of 2-EH at the observed levels, and so it is reasonable to hypothesize a direct contamination from packaging materials containing 2-EH as residue from D2EHP synthesis.