Paolo Massanisso

Derivatization methods for the determination of organotin compounds in environmental samples

In the analysis of organotin compounds, derivatization is required in order to achieve more volatile compounds prior to the use of techniques based on GC separation. Derivatization can be considered as one of the main critical steps in organotin analysis, since low yields of derivatization and losses of analytes can easily occur at this stage, and lead to an underestimation of their content in environmental samples. Furthermore, experimental conditions which are not perfectly under control may induce degradations, and alter the original speciation in the sample. Hydride generation, and alkylation by Grignard reagents or by NaBEt 4, are the derivatization methods usually applied for organotins. The advantages and disadvantages of these methods are reported. z2000 Elsevier Science B.V. All rights reserved.

Butyltins concentration levels and imposex occurrence in snails from the Sicilian coasts (Italy).

Two sampling campaigns have been carried out along the Sicilian coasts within the frame of a European project (Hic-TBT) financed by the LIFE programme. Snails and sediments have been sampled at 5 stations, characterised by very low (Ustica natural sea reserve), low (Ustica harbour), intermediate (Castellamare and Termini Imerese) and high shipping densities (Palermo). Biological and chemical analyses were carried out in order to evaluate the incidence of imposex occurring in snails, and the concentration levels of organotins in sediment and snail samples. Despite the low organotin concentration levels in sediment and snail samples, the results show that imposex is widespread around Sicily. In four locations almost all female snails were affected by imposex at advanced development stages, even in areas with a fairly low shipping density. Only in the natural sea reserve of Ustica Island imposex was relatively less severe. Finally a logarithmic correlation between TBT and imposex stages was observed.

Comparison of twelve selected extraction methods for the determination of butyl- and phenyltin compounds in mussel samples

Abstract Several analytical methods have been developed in the last 20 years for the determination of organotin compounds in mussel tissue. These methods encompass a huge variety of different extraction methods of poorly known efficiency. The quantitative evaluation of the extraction efficiency of these methods has been hindered by the lack of mussel reference materials and the presence of other potential sources of errors such as derivatisation and purification steps. The extraction efficiencies of 12 selected methods for the analysis of butyl- and phenyltin compounds in mussel samples have been compared. The comparison was carried out by analysing a mussel tissue reference material (CRM 477) with certified and indicative values for butyltins and phenyltins, respectively, recently made available by the European Commissions Standards, Measurements and Testing Programme. Derivatisation, clean-up and analysis were rigorously the same in all the methods considered. The high homogeneity of the samples and the identical experimental conditions allowed comparison of the extraction efficiencies.

Propolis specimens from different locations of central Italy: chemical profiling and gas chromatography-mass spectrometry (GC-MS) quantitative analysis of the allergenic esters benzyl cinnamate and benzyl salicylate.

Propolis is a beehive product popular in natural medicine thanks to its noteworthy properties. Propolis is non-toxic but is responsible for allergic reactions in sensitive individuals. In this paper, we propose a new gas chromatography-mass spectrometry (GC-MS) analytical methodology for the quantitative analysis of two allergenic esters in propolis specimens, benzyl salicylate and benzyl cinnamate, and test it on specimens from different locations of central Italy. We also present the results obtained in the chemical characterization of the same specimens. The characterization showed that the resin fractions of all of the specimens are of poplar origin.

Organotins in the sediments of the Zuari estuary, west coast of India

Industrial use of organotins such as butyltins and phenyltins has increased several folds during the last two decades. Butyltins and phenyltins are synthetic, multipurpose chemicals, which have been extensively used in marine antifouling paints. They have been known to be extremely poisonous to mollusc fishery resources (oysters, clams, etc.). Contamination of Zuari estuary sediments was assessed by quantitative determination of butyltins and phenyltins by using GC-MS using the electron ionization mode. Butyltins predominated in the whole area over phenyltins. Butyltins contributed about 70-90% of the organotins in general. The concentration of butyltins in sediments ranged from 20 to 7621 ng Sn/g. The concentration of phenyltins in sediments ranged from 0 to 46 ng Sn/g. Degradation indices for butyltins and phenyltins were calculated. The Butyltin degradation index (BDI) for the Zuari sediments ranged from 0 to 2.7 indicating a lot of fresh input of butyltins in the estuary and a lower degradation rate. The phenyltin degradation index (PhDI) ranged from 1 to 10 implying that different processes were prevalent at different stations. The observed organotin levels in the Zuari estuary indicate some highly localized areas of contamination which are severe enough to cause harmful effects on marine flora and fauna. Therefore, there is a need to regulate the use of butyltins and phenyltins as biocides in marine antifouling paints.

A new approach to testing potential leaching toxicity of fouling release coatings (FRCs)

Fouling release coatings (FRCs) are today the main environment-friendly alternative to traditional self-polishing coatings, that continuously release biocides and/or heavy metals into water. FRCs are available on the market as environmentally friendly AF paints and most of them do not contain bioactive agents, however no complete and reliable assessment of their environmental impact has yet been carried out. Only few literature data proving their AF efficacy combined with a demonstrated lack of toxicological effects are available. Ecotoxicological bioassays are commonly used to predict the potential environmental impact of traditional AF paints. Standardized methodologies to obtain leaching products from biocide-based paints are available, while few studies propose experimental methods to assess the potential effects of biocide-free FRCs leachates on non-target organisms. The aim of this work is to propose an experimental protocol to obtain leaching products from biocide-free FRCs in order to evaluate the potential release of substances having toxic effects, by means of an ecotoxicological bioassay. Two ecotoxicological end-points with different sensitivity levels were considered (multi-end-point approach). Five silicone-based commercial coatings were used: their leaching products were collected after different immersion times following the developed experimental method and then two ecotoxicological end-points were evaluated on II stage nauplii of the crustacean Amphibalanus amphitrite as model organism. Moreover, chemical analyses were performed on leachates collected after each immersion time, focusing on the presence of metals in leaching products. From the results obtained from the bioassay, even if not indicative of the real environmental impact of FRCs, a release of toxic substances was observed from tested coatings during early immersion stages, likely to affect the exposed model organism. The potential leaching toxicity of the five tested products was compared. No clear correspondence could be identified between the concentrations of metals detected in leachates and the obtained ecotoxicological data, thus suggesting that other active components might be released by FRCs responsible for the toxic effects pointed out on A. amphitrite larvae.