Antonio Marcomini - Academia.edu (original) (raw)

Papers by Antonio Marcomini

Environmental Toxicology and Chemistry, 2004

The exposure of the Venice lagoon (Italy) to endocrine-disrupting compounds (EDCs) from different... more The exposure of the Venice lagoon (Italy) to endocrine-disrupting compounds (EDCs) from different sources was investigated. Spatial and time distribution of EDC concentrations were determined in four sampling sessions (December 2001-May 2002) by solid phase extraction followed by high-performance liquid chromatography separation coupled with mass spectrometry detection via electrospray interface (SPE-HPLC-ESI-MS), which allowed identification of natural (estradiol, estrone) and synthetic estrogenic compounds, both steroidal (ethinylestradiol, mestranol) and nonsteroidal (benzophenone, bisphenol-A, nonylphenol, nonylphenol monoethoxylate carboxylate). No significant differences in the EDC distribution were observed between stations located near selected sources (raw sewage from the historical center of Venice, treated municipal and industrial effluents from sewage treatment plants, and areas undergoing the inflow of rivers). While synthetic nonsteroidal analytes were recorded in the 1 to 1,040 ng/L range (average concentration: 34 ng/L), steroidal EDC (estradiol, ethinylestradiol) concentrations were lower (1-125 ng/L; average concentration: 8 ng/L). The estrogenic activity of lagoon waters was estimated in terms of estradiol equivalent concentration (EEQ) by applying the estradiol equivalency factors (EEFs). Steroidal EDCs (estradiol, ethinylestradiol) contributed Ͼ97% to the total potential estrogenicity of the waters, which accounted for 4 to 172 ng/L (average: 25 ng/L), as total EEQs. These levels are likely to pose adverse effects on the Venice lagoon aquatic organisms.

Environmental Pollution, 2001

apsule'': Kriging and principal component analysis were useful in obtaining additional informatio... more apsule'': Kriging and principal component analysis were useful in obtaining additional information from data sets.

Environmental Pollution, 2004

Risk assessment studies apply fate and transport models to predict the behaviour of chemicals in ... more Risk assessment studies apply fate and transport models to predict the behaviour of chemicals in the environment. The definition of physico-chemical properties is crucial to predict the mobility of pollutants and heavy metals in particular within the environmental compartments. The conservative approach normally adopted at a screening level in attributing a value to the K(d) value, results in an extremely variable mobility in soil. In this paper a regression model to estimate rapidly the K(d) for heavy metals is proposed and applied to Pb, allowing a considerable reduction (3-4 orders of magnitude) of the estimation uncertainty. The application of a stepwise forward multiple regression to literature data provided a pH-dependent regression equation of the soil-water distribution coefficient (K(d)) for Pb: log K(d)=1.99+0.42 pH.

Environmental Toxicology and Chemistry, 1994

The effects on mitochondrial respiratory parameters of linear alkylbenzene sulfonates (LAS), nony... more The effects on mitochondrial respiratory parameters of linear alkylbenzene sulfonates (LAS), nonylphenol polyeth-oxylates (NPEO), and some of their biotransformation products, namely sulfophenyl carboxylates (SPCs), nonylphenol (NP), and nonylphenoxy acetic acid (NP1EC), were recorded by using the in vitro response of submitochondrial particles (SMP) from beef heart. The toxicity of these compounds was estimated by determining their effects on the energy-coupled reverse electron transfer (RET), which is induced by ATP and succinate at the first site level of the respiratory chain and reduces exogenous NAD+ to NADH. The toxicity of the substances, expressed as the toxicant concentration decreasing the reduction rate of NAD+ to an extent of 50% (EC50), ranged from 0.61 mg/L for a commercial LAS mixture to 18,000 mg/L for individual SPCs; from 1.3 mg/L for NPEO, with an average of 10 ethoxy units, to 8.2 and 1.8 mg/L for NP1EC and NP, respectively. These results were related to the molecular structure of each compound class and compared with the toxicity values obtained by a variety of biological systems currently used for toxicity testing. The acute toxicity data have demonstrated that (a) the SMP bioassay is suitable for reproducing the toxicological response of whole organisms, such as fishes and invertebrates, to the tested chemicals; and (b) the hydrophobic moiety of these compounds plays a significant role in eliciting their toxic effects. From a toxicological standpoint, attention must be paid to the occurrence in natural waters of residual LAS, whereas in the case of NPEO both unaltered surfactant and all biotransformation products need to be identified and quantified.

Journal of Chromatography A, 1987

An enrichment procedure involving percolation through octadecylsilica cartridges was applied to t... more An enrichment procedure involving percolation through octadecylsilica cartridges was applied to the extraction of linear alkylbenzenesulphonates (LASS), alkylphenol polyethoxylates (APEOs) and nonylphenol (NP) from treated and untreated municipal waste waters. The analytes were quantitated by reversed-phase highperformance liquid chromatography with UV-fluorescence detection. Recoveries higher than 80% were obtained from the analysis of biologically treated waste waters. The method allows rapid, precise and reliable determination of LASS and APEOs at concentrations as low as 20 and 4 ,ug l-r, respectively.

Journal of Chromatography A, 1993

A method for the determination of 7 alpha-hydroxy-4-cholesten-3-one in human serum has been devel... more A method for the determination of 7 alpha-hydroxy-4-cholesten-3-one in human serum has been developed. The method is based upon solid-phase (C18) extraction of serum after addition of 7-beta-hydroxy-4-cholesten-3-one as internal standard. The extract is analysed by reversed-phase HPLC using acetonitrile-water as a mobile phase. The effluent is monitored at 241 nm. The overall recoveries of the method range from 96% to 105%. The coefficient of variation for the within-run precision is 3.2% (n = 20, mean = 13.0 ng/ml) and for the between-run precision 3.8% (n = 32, mean = 13.3 ng/ml). The limit of detection is 3 ng at a signal-to-noise ratio of 3:1, which corresponds to 1 ng/ml using 3 ml of serum. The median value of 7 alpha-hydroxy-4-cholesten-3-one found in blood donors (n = 27) was 8.9 ng/ml (range 2-35 ng/ml).

Water Research, 1988

A~tract--The fluxes of linear alkylbenzenesulphonates (LAS), nonylphenol (NP), nonylphenol monoet... more A~tract--The fluxes of linear alkylbenzenesulphonates (LAS), nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) through sewage and sludge treatment of 29 Swiss sewage treatment plants were investigated. Reversed-phase high-performance liquid chromatography (HPLC) was used to determine LAS. Normal-phase HPLC was employed to measure NP, NP 1EO and NP2EO which are metabolites of the nonionic surfactants of the nonylphenol polyethoxylate type (NPnEO). Quantitative determinations were performed of raw sewage, primary and secondary effluents and of sewage sludge. Under normal conditions of sewage and sludge treatment, LAS were efficiently removed from the raw wastewater (> 99% w/w) and were partly transferred to the sewage sludge (15-20% w/w). About 50% (molar base) of NPnEO in the sewage were transformed to NP and accumulated in the digested sludge. Large variations existed among different sewage treatment plants. It was estimated that 1.0 g m -2 y 1 of LAS and 0.3 g m 2 y ~ of NP are applied with sewage sludge to Swiss soils.

Comparative Biochemistry and Physiology C-toxicology & Pharmacology, 2007

Pharmaceuticals and Personal Care Products (PPCPs) are a class of emerging environmental pollutan... more Pharmaceuticals and Personal Care Products (PPCPs) are a class of emerging environmental pollutants with the potential of affecting various aquatic organisms through unexpected modes of action. Triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether) (TCS), is a common antibacterial agent that is found in significant amounts in the aquatic environment. In this work, the possible effects and modes of action of TCS were investigated in the marine bivalve Mytilus galloprovincialis Lam. In mussel immune cells, the hemocytes, in vitro short-term exposure to TCS in the low μM range reduced lysosomal membrane stability (LMS) and induced extracellular release of lysosomal hydrolytic enzymes. The effects on LMS were mediated by activation of ERK MAPKs (Extracellularly Regulated Mitogen Activated Protein Kinases) and PKC (protein kinase C) α and βII isoforms, as demonstrated by both specific kinase inhibitors and Western blotting with specific anti-phospho-antibodies. The effects of TCS were confirmed in vivo, in the hemocytes of mussels injected with different concentrations of TCS (corresponding to 0.29, 2.9 and 29 ng/g dry weight) and sampled at 24 h post-injection. The possible in vivo effects of TCS were also evaluated on the activity of different enzymes in the digestive gland, the tissue mainly involved in accumulation and metabolism of organic contaminants in mussels. Significant increases were observed in the activity of the glycolytic enzymes PFK (phosphofructokinase) and PK (pyruvate kinase), as well as of GST (GSH transferase) and GSR (GSSG reductase), whereas a decrease in catalase activity was observed. The results demonstrate that in mussels TCS can act on kinasemediated cell signalling, lysosomal membranes and redox balance in different systems/organs. Although further studies are needed in order to evaluate possible consequences of environmental exposure to TCS on mussel health, the results represent the first data on the possible modes of action of this widespread antibacterial in aquatic invertebrates.

Environmental Health Perspectives, 2005

Existing environmental risk assessment procedures are limited in their ability to evaluate the co... more Existing environmental risk assessment procedures are limited in their ability to evaluate the combined effects of chemical mixtures. We investigated the implications of this by analyzing the combined effects of a multicomponent mixture of five estrogenic chemicals using vitellogenin induction in male fathead minnows as an end point. The mixture consisted of estradiol, ethynylestradiol, nonylphenol, octylphenol, and bisphenol A. We determined concentrationresponse curves for each of the chemicals individually. The chemicals were then combined at equipotent concentrations and the mixture tested using fixed-ratio design. The effects of the mixture were compared with those predicted by the model of concentration addition using biomathematical methods, which revealed that there was no deviation between the observed and predicted effects of the mixture. These findings demonstrate that estrogenic chemicals have the capacity to act together in an additive manner and that their combined effects can be accurately predicted by concentration addition. We also explored the potential for mixture effects at low concentrations by exposing the fish to each chemical at one-fifth of its median effective concentration (EC 50 ). Individually, the chemicals did not induce a significant response, although their combined effects were consistent with the predictions of concentration addition. This demonstrates the potential for estrogenic chemicals to act additively at environmentally relevant concentrations. These findings highlight the potential for existing environmental risk assessment procedures to underestimate the hazard posed by mixtures of chemicals that act via a similar mode of action, thereby leading to erroneous conclusions of absence of risk.

Marine Environmental Research, 1999

Standing crop and production of macroalgae and seagrasses were recorded, together with the main p... more Standing crop and production of macroalgae and seagrasses were recorded, together with the main physical and chemical parameters, including nutrient concentrations of the water column and 5-cm top sediment porewater, the grazing pressure and the settled paniculate matter ( ...

Aquatic Toxicology, 2007

Endocrine disrupting compounds (EDCs) are almost ubiquitous in the aquatic environment. In the ma... more Endocrine disrupting compounds (EDCs) are almost ubiquitous in the aquatic environment. In the marine bivalve Mytilus the natural estrogen 17␤-estradiol (E 2 ) and different EDCs have been recently demonstrated to affect the function of the immune cells, the hemocytes. The effects were Tamoxifen-sensitive and were mediated by rapid modulation of kinase-mediated transduction pathways. In this work we compared the in vitro effects of individual estrogenic chemicals (E 2 , EE: 17␣-ethynyl estradiol; MES: mestranol; NP: nonylphenol; NP1EC: nonylphenol monoethoxylate carboxylate; BPA: bisphenol A; BP: benzophenone) on hemocyte parameters: lysosomal membrane stability (LMS), phagocytosis, lysozyme release. LMS was the most sensitive effect parameter, showing a decreasing trend at increasing concentrations of estrogens. EC 50 values obtained from LMS data were utilized to calculate the estradiol equivalency factor (EEF) for each compound; these EEFs allowed for an estimation of the estrogenic potential of a synthetic mixture with a composition very similar to that previously found in waters of the Venice lagoon. Concentrated mixtures significantly affected hemocyte parameters in vitro and the effects were prevented by Tamoxifen. Significant effects of the mixture were also observed in vivo, at longer exposure times and at concentrations comparable with environmental exposure levels. The results indicate that Mytilus immune parameters can be suitably utilized to evaluate the estrogenic potential of environmental samples.

Environmental Science & Technology, 2007

Recent research into the effects of mixtures of estrogenic chemicals has revealed the capacity fo... more Recent research into the effects of mixtures of estrogenic chemicals has revealed the capacity for similarly acting chemicals to act in combination, according to the principles of concentration addition. This means that, collectively, they may pose a significant environmental risk, even when each component is present at a low and individually ineffective concentration. The aim of this study was to investigate the ecological significance of mixture effects at low-effect concentrations by assessing the combined effect of estrogenic chemicals on the reproductive performance of fish. Pairs of fathead minnows were exposed to five estrogenic chemicals.

Marine Chemistry, 1987

Pavoni, B., . Concentration and flux profiles of PCBs, DDTs and PAHs in a dated sediment core fro... more Pavoni, B., . Concentration and flux profiles of PCBs, DDTs and PAHs in a dated sediment core from the lagoon of Venice. Mar. Chem., 21: 25-35.

Environmental Toxicology and Chemistry, 2000

Aerobic biodegradation of aliphatic alcohol polyethoxylates (AEs) was tested under screening test... more Aerobic biodegradation of aliphatic alcohol polyethoxylates (AEs) was tested under screening test conditions (Organization for Economic Cooperation and Development [OECD] 301E protocol) using recently developed analytic methodologies for the specific determination ...

Environment International, 2007

We report a survey on the occurrence and distribution of natural (17beta-estradiol, E2; estrone, ... more We report a survey on the occurrence and distribution of natural (17beta-estradiol, E2; estrone, E1) and synthetic (nonylphenol, NP; nonylphenol monoethoxylate carboxylate, NP1EC; bisphenol-A, BPA; benzophenone, BP; mestranol, MES; 17alpha-ethinylestradiol, EE2; diethylstilbestrol, DES) endocrine disrupting compounds (EDCs) in water, sediment and biota (Mediterranean mussel, Mytilus galloprovincialis) in the Venice lagoon, a highly urbanized coastal water ecosystem that receives both industrial and municipal wastewater effluents. The survey was preceded by the development of tailor made extraction and clean-up procedures for the simultaneous HPLC-ESI-MS determination of all examined EDCs in sediment and biota samples. Satisfactory extraction performances and method detection limits (MDLs) were obtained for almost all EDCs. Most of the selected compounds were found in water and sediment (concentration range: 2.8-211 ng/L, and 3.1-289 microg/kg, d.w., respectively), while only 17alpha-ethinylestradiol and nonylphenol were recorded in biota samples (conc. range: 7.2-240 ng/g, d.w.). 17beta-estradiol and ethinylestradiol contributed mostly to the water estradiol equivalent concentration (EEQ) (1.1-191 ng/L, average: 25 ng/L), while synthetic EDCs (17alpha-ethinylestradiol, diethylstilbestrol) were mainly responsible of the sediment EEQ (1.1-191 microg/kg, average: 71 microg/kg, d.w.). Whenever diethylstilbestrol was not recorded in the sediment, water EEQs were similar to sediment EEQs. A remarkable increase of nonylphenol was observed in sediments over the last decade.

Chemosphere, 2003

The available experimental information on the occurrence of PCDD/Fs in the Venice Lagoon, Italy, ... more The available experimental information on the occurrence of PCDD/Fs in the Venice Lagoon, Italy, was compiled and used to calculate fugacities for the environmental compartments of sediment, suspended particulate matter (SPM), water and air and then used to estimate fugacity ratios and assess the likely net direction of flux between media. The bottom sediment: SPM fugacity ratios for different PCDD/Fs indicate conditions close to equilibrium, suggestive of the close coupling of SPM with re-suspended sediment. Sediment/water and the sediment/air fugacity ratios suggest that net flux directions vary depending on the congener and the location within the lagoon. Net sediment-water-air movement (i.e. re-mobilisation/volatilisation) is suggested for the lighter congeners from the industrial canals, where the highest PCDD/F concentrations in the lagoon occur. The tendency to volatilise increases with decreasing congener molecular weight. In contrast, net deposition (air-water-sediment) appears to be occurring for the heaviest (hepta-and octa-) substituted PCDD/Fs. OCDF represents a marker of the industrial district of the lagoon, decreasing in concentration and as a fraction of total PCDD/Fs with increasing distance. The fugacity-based quantitative water air sediment interaction (QWASI) mass-balance model was applied to the central part of the lagoon. The key parameters for the determination of the model output, identified by a sensitivity analysis, were: the sediment active depth, the sediment resuspension and deposition rates, and the total input of PCDD/Fs to the system. The QWASI model also indicates the tendency for the lighter PCDD/Fs to be released from surface sediment to the water column.

International Journal of Environmental Analytical Chemistry, 1989

Octadecylsilica was employed as reversed-phase HPLC packing material for the simultaneous separat... more Octadecylsilica was employed as reversed-phase HPLC packing material for the simultaneous separation and determination of linear alkylbenzenesulphonates (LAS) and nonylphenol polyethoxylates (NPEO). The role of NaClO4 dissolved in the mobile phase on the separation of LAS and NPEO was investigated: it turned out to affect only the elution volumes of LAS. Alkylphenol polyethoxylates were exhaustively extracted from liquid commercial cleaning

Marine Environmental Research, 1997

Environmental Science & Technology, 1994

On the basis of solid-phase extraction, a simple procedure for determining simultaneously two aro... more On the basis of solid-phase extraction, a simple procedure for determining simultaneously two aromatic surfactant classes, i.e., linear alkylbenzene sulfonates (LAS) and nonylphenol polyethoxylates (NPEO), as well as their biodegradation intermediates in raw and treated sewages is presented. This procedure involved passing 10 and 100 mL of an influent and effluent water sample, respectively, through a 1-g graphitized carbon black (GCB) extraction cartridge. By exploiting the presence of positively charged active centers on the GCB surface, we succeeded in fractionating the complex mixture of the analytes considered by differential elution. The first fraction contained NPEO and nonylphenol (NP). The second fraction contained the carboxylated biotransformation products of NPEO, i.e., nonylphenoxy carboxylic acids (NPEC). Finally, the last fraction contained LAS and their metabolites, Le., carboxylic sulfophenyl acids (SPC). By suitably adjusting the chromatographic conditions, any group of analytes was subfractionated and quantified by liquid chromatography with fluorometric detection. Recoveries of all compounds of interest ranged between 89 % and 99%. This procedure was empolyed for 1 year to assess monthly the concentrations of the analytes considered in raw and treated sewages of a mechanicalbiological treatment plant.

Environmental and Molecular Mutagenesis, 2008

Viability, cell cycle effects, genotoxicity, reactive oxygen species production, and mutagenicity... more Viability, cell cycle effects, genotoxicity, reactive oxygen species production, and mutagenicity of C60 fullerenes (C60) and single-walled carbon nanotubes (SWCNT) were assessed in the FE1-Muta™Mouse lung epithelial cell line. None of these particles induced cell death within 24 hr at doses between 0 and 200 μg/ml or during long-term subculture exposure (576 hr) at 100 μg/ml, as determined by two different assays. However, cell proliferation was slower with SWCNT exposure and a larger fraction of the cells were in the G1 phase. Exposure to carbon black resulted in the greatest reactive oxygen species generation followed by SWCNT and C60 in both cellular and cell-free particle suspensions. C60 and SWCNT did not increase the level of strand breaks, but significantly increased the level of FPG sensitive sites/oxidized purines (22 and 56%, respectively) determined by the comet assay. The mutant frequency in the cII gene was unaffected by 576 hr of exposure to either 100 μg/ml C60 or SWCNT when compared with control incubations, whereas we have previously reported that carbon black and diesel exhaust particles induce mutations using an identical exposure scenario. These results indicate that SWCNT and C60 are less genotoxic in vitro than carbon black and diesel exhaust particles. Environ. Mol. Mutagen., 2008. © 2008 Wiley-Liss, Inc.