Stefano Polesello

Common implementation strategy for the water framework directive (2000/60/EC)

This Technical Guidance Document on Biota Monitoring (the Implementation of EQSbiota) naims to facilitate the implementation of environmental quality standards (EQS) in biota nunder the Water Framework Directive by addressing in particular the sampling strategies nappropriate for monitoring programmes designed to assess compliance with biota EQS. It is nGuidance Document No. 32 in the series of guidance documents prepared to support the nCommon Implementation Strategy (CIS) for the Water Framework Directive. nIt elaborates extensively on the content of Guidance Document No. 25 on Chemical nMonitoring in Sediment and Biota under the Water Framework Directive, and is ncomplemented by Guidance Document No. 33, the Technical Guidance Document on nAnalytical Methods for Biota Monitoring. Guidance Documents 32 and 33 together address nthe requirement for guidance on biota monitoring mentioned in Article 3(8a) of Directive n2008/105/EC as amended by Directive 2013/39/EU. nThe original Directive 2008/105/EC included biota standards for mercury, nhexachlorobenzene and hexachlorobutadiene. In Directive 2013/39/EU, biota EQS were nintroduced for three other existing priority substances (fluoranthene, polyaromatic nhydrocarbons and brominated diphenylethers), and set for four new priority substances n(dicofol, perfluorooctane sulfonic acid and its derivatives, hexabromocyclododecane, and nheptachlor/heptachlor epoxide). This guidance document takes into account the fact that ntrend monitoring in sediment and/or biota is required for several other priority substances as nspecified in Article 3(6), and indicates how trend monitoring data can be used to check ncompliance with biota EQS, but does not elaborate on trend monitoring as such. nThis document constitutes guidance and Member States are therefore not legally required to nfollow the recommendations contained in it. Member States are, however, required to use nmethods compliant with the requirements of the Environmental Quality Standards Directive n2008/105/EC and the Quality Assurance/Quality Control Directive 2009/90/EC.

Chromatographic determination of vitamins in foods

Chromatographic methods for the determination of water- and fat-soluble vitamins in foods are reviewed. For each vitamin, sample preparation, detection problems and chromatographic conditions are presented and discussed. High-performance liquid chromatography (HPLC) is becoming a standard method in vitamin assay, especially for routine work. HPLC systems can be automated using in-line solid-phase extraction and column switchings, resulting in very sensitive methods, even when simple UV detection is employed.

The fate of triazine pesticides in River Po water

A group of triazine herbicides has been monitored in river Po water over a period of three years. The N-deethylated metabolite of atrazine was also found. Laboratory tests of biodcgradation of triazine performed with River Po water as cultural medium did not show any significant triazine degradation, leading to the conclusion that triazine metabolites derive from de.~-adation in soil. The chemical reactivity of triazines toward oxidants was also tested in laboratory with lead(IV) acetate, cerium(IV) ammonium nitrate and ozone. A chemical degradation pathway for triazines is suggested.

Determination of anions in rainwater by capillary electrophoresis with conductivity detection

A routine method for the determination of chloride, nitrate and sulfate anions in rainwater by capillary electrophoresis was developed. The system uses an end-column non-suppressed conductivity detector. Linear calibration plots were generated from 0.050 to 20 mg/l, which is the range generally found in wet depositions. Accuracy and precision were evaluated by analyzing certified standards of simulated rainwater and environmental samples, or by comparing CE results with those obtained by IC, the reference technique for anion analysis in wet deposition. The reproducibility of the method was satisfactory except at the lower and upper limits of the analytical range. Sensitivity lay in the range of few μg/l.

Ozone oxidation of polyethoxylated alcohols

Abstract The ozonation of a polyethoxylated alcohol (typical of one type of detergent) mixture was performed in aqueous solution under different conditions of pH, reaction time and hydrogen peroxide addition. Surfactant degradation was monitored by TOC measurements. The optimal degradation conditions were found to be at pH = 7.5 with hydrogen peroxide addition. Inspection of the reaction products was carried out by GC-MS and GC-FTIR analysis of the silylated mixtures. The main oxidation products of ethoxylated alcohols are dicarboxylic acids.

Reactivity of two models of non-ionic surfactants with ozone

The ozonation of ethylene glycol and diethylene glycol mono-n-octylether (models of non-ionic surfactants) has been performed in aqueous solution at pH 4 and pH 9.5. The experiments at acidic pH show that the methylene groups adjacent to the ethereal oxygens are transformed into carbonyl groups. At alkaline pH the aliphatic chain is cleaved. Kinetic experiments allow to suggest a reaction mechanisms.

Uptake and accumulation of sediment‐associated 4‐nonylphenol in a benthic invertebrate (Lumbriculus variegatus, freshwater oligochaete)

In the present work, the oligochaete Lumbriculus variegatus was exposed for 56 d to lake sediment spiked with 4-nonylphenol (4-NP), which is a breakdown product of alkylphenol polyethoxylates, an important class of nonionic surfactants. During the exposure period, the content of 4-NP was determined in the oligochaetes, sediment, overlying water, and pore water in order to monitor the distribution of the 4-NP in the compartments of the test system. Concentration of 4-NP in L. variegatus increased linearly over the course of the test, with an uptake rate coefficient of 1.9 x 10(-2) (+/- 0.2 x 10(-2); [g carbon/(g lipid x h)]). No steady state was reached at the end of the exposure period, suggesting that the elimination of 4-NP by the organism was negligible. Ingested sediments played an important role in the accumulation of 4-NP in L. variegatus, which may achieve very high 4-NP body concentrations. The 56-d biota sediment accumulation factor (BSAF) was 24 +/- 7 g carbon/g lipid. L. variegatus also was exposed to 4-NP-contaminated field sediment, and field oligochaetes and sediments were collected for 4-NP pollution assessment in aquatic ecosystem. The 4-NP uptake with natural sediment was in accordance with that measured with spiked sediments, suggesting that the bioavailability of sediment-associated 4-NP for L. variegatus was not affected by 4-NP sediment concentration and abiotic sediment characteristics. The BSAFs measured in field oligochaetes, ranging from 39 to 55 g carbon/g lipid, was relatively higher than the bioaccumulation factor measured in laboratory tests. The results suggest that 4-NP concentration can reach high levels in benthic oligochaetes; this can be an important way of exposure for their pelagic predators.

An Old Relict Glacier Body Preserved in Permafrost Environment: The Foscagno Rock Glacier Ice Core (Upper Valtellina, Italian Central Alps)

Abstract This paper shows the results of chemical and crystallographic analyses carried out on a core drilled within the frontal part of the Foscagno rock glacier in the Italian Alps. We use 58 vertical thin sections spaced along the massive ice core, found between depths of 2.5 and 7.65 m, to describe the ice fabric of the core. We also discuss the results of chemical analyses of more than 50 samples. The lower part of the massive ice core between 4 and 7.65 m shows a mean crystal size of 1.5 cm and a crystal shape predominantly elongated along the horizontal plane with c-axes. These characteristics are similar to those of firn ice. In contrast, the upper core between 2.5 and 4 m displays vertical elongation of large bubbles, indicating superimposed ice and the influence of melting and refreezing processes. The presence of a seasonal signal in sulfate distribution and the strong correlation between sodium and chloride in the lower part of the core confirm cold firnification without appreciable phase changes. This well-preserved glacier ice body is probably younger than 2200 ± 60 yr B.P., a minimum age for the rock glacier as indicated by the 14C age of a buried paleosoil, although the possibility that it may be older age cannot be excluded. The glacier ice body seems to be a relict of a former glacier preserved within a larger permafrost body that characterizes almost all of the rock glacier and also occurs beneath the massive ice. This finding points out that different types of ice can be preserved within a single rock glacier, reflecting a complex geological and paleoclimatic history.

An On-Line Solid Phase Extraction-Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Perfluoroalkyl Acids in Drinking and Surface Waters

An UHPLC-MS/MS multiresidue method based on an on-line solid phase extraction (SPE) procedure was developed for the simultaneous determination of 9 perfluorinated carboxylates (from 4 to 12 carbon atoms) and 3 perfluorinated sulphonates (from 4 to 8 carbon atoms). This work proposes using an on-line solid phase extraction before chromatographic separation and analysis to replace traditional methods of off-line SPE before direct injection to LC-MS/MS. Manual sample preparation was reduced to sample centrifugation and acidification, thus eliminating several procedural errors and significantly reducing time-consuming and costs. Ionization suppression between target perfluorinated analytes and their coeluting SIL-IS were detected for homologues with a number of carbon atoms less than 9, but the quantitation was not affected. Total matrix effect corrected by SIL-IS, inclusive of extraction efficacy, and of ionization efficiency, ranged between −34 and +39%. The percentage of recoveries, between 76 and 134%, calculated in different matrices (tap water and rivers impacted by different pollutions) was generally satisfactory. LODs and LOQs of this on-line SPE method, which also incorporate recovery losses, ranged from 0.2 to 5.0u2009ng/L and from 1 to 20u2009ng/L, respectively. Validated on-line SPE-LC/MS/MS method has been applied in a wide survey for the determination of perfluoroalkyl acids in Italian surface and ground waters.

Perfluoroalkyl acids in fish of Italian deep lakes: Environmental and human risk assessment

Determination of 20 PFASs in a fish species (Alosa agone) of commercial interest has been carried out in five Italian subalpine lakes to assess the risk for humans and predators for fish consumption. PFOS still presents the highest concentrations (0.9-16.6ngg-1ww) among the analysed PFASs, in spite of its normative restrictions. PFOS concentrations measured in all lakes, except in Lake Maggiore, are homogeneous with an average of 3.1±1.9ngg-1ww, which could be considered the anthropogenic background concentration of PFOS in fish of lakes located in an industrialised and urbanised region but without point sources. In Lake Maggiore, fish concentrations always exceed the EU EQSbiota (9.1ngg-1ww) based on human fish consumption. Considering the effective consumption of fish in this area, an actual risk for fish consumption by humans is not evidenced, while a moderate risk of secondary poisoning for predators is highlighted. PFOA has been detected in significant concentration only in one sample in Lake Maggiore, while long chain PFCAs have been detected without significant differences among the lakes (0.3 to 2.7ngg-1ww). The present study demonstrates that biota monitoring of fish can be used as a valuable tool to classify the quality status of water bodies regarding bioaccumulative PFAAs, even if the water concentrations are close to the reachable detection limits.