A new hybrid system of QSAR models for predicting bioconcentration factors (BCF)

The aim was to develop a reliable and practical quantitative structure-activity relationship (QSAR) model validated by strict conditions for predicting bioconcentration factors (BCF). We built up several QSAR models starting from a large data set of 473 heterogeneous chemicals, based on multiple linear regression (MLR), radial basis function neural network (RBFNN) and support vector machine (SVM) methods. To improve the results, we also applied a hybrid model, which gave better prediction than single models. All models were statistically analysed using strict criteria, including an external test set. The outliers were also examined to understand better in which cases large errors were to be expected and to improve the predictive models. The models offer more robust tools for regulatory purposes, on the basis of the statistical results and the quality check on the input data.     

Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in emissions from an urban incineratop. 1. Average and peak values

Gas chromatography-low resolution mass spectrometry was used to quantitate PCDD and PCDF emitted from an urban incinerator. The amounts were determinated in 17 samples collected over 9 months. Wide variability in the different sample concentrations, ranging from 2.3 mg/h to 348 mg/h for PCDD and from 3.9 mg/h to 324 mg/h for the PCDF, was observed.     

Screening of endocrine-disrupting phenols, herbicides, steroid estrogens, and estrogenicity in drinking water from the waterworks of 35 Italian cities and from PET-bottled mineral water

We investigated contamination by endocrine-disrupting chemicals in drinking water from 35 major Italian cities and five popular Italian brands of bottled mineral water. The quality of Italian drinking water was assessed by combing chemical analysis with bioassay to quantify specific estrogenic contaminants and to characterize the actual biological effect of the mixture of chemicals present in drinking water including the contribution of not targeted compounds. The selected contaminants were natural and synthetic steroid estrogens, alkylphenols and bisphenol A, linuron, triazine herbicides, and their metabolites. A specific analytical method was developed based on solid phase extraction of 1 L of water and concentration to 100 μL for quantification by electrospray ionization liquid chromatography tandem mass spectrometry, achieving quantification limits of 0.05–0.36 ng/L for herbicides and 0.64–7.70 ng/L for steroids and phenols. No steroid estrogens were detected in any of the samples, while bisphenol A and nonylphenols were detected in the ranges of 0.82–102.00 and 10.30–84.00 ng/L respectively. Herbicides and their degradation products, when present, were found from slightly above the quantification limits up to 49.91 ng/L, mainly from cities in northern Italy. Chemical analyses were complemented by the performance of a bioassay for the determination of the estrogenic activity in the extracts based on the transactivation of estrogen receptor α-transfected reporter HeLa-ERE-Luciferase-Neomycin cell line. Activity was generally low with maximum estrogenicity of 13.6 pg/L estradiol equivalents.     

A protocol to select high quality datasets of ecotoxicity values for pesticides

The key to any QSAR model is the underlying dataset. In order to construct a reliable dataset to develop a QSAR model for pesticide toxicity, we have derived a protocol to critically evaluate the quality of the underlying data. In developing an appropriate protocol that would enable data to be selected in constructing a QSAR, we concentrated on one toxicity end point, the 96 h LC50 from the acute rainbow trout study. This end point is key in pesticide regulation carried out under 91/414/EEC. The dataset used for this exercise was from the US EPA-OPP database.     

Endocrine modulation, inhibition of ovarian development and hepatic alterations in rainbow trout exposed to polluted river water

Under laboratory conditions, female rainbow trout were exposed to graded concentrations of water from the River Lambro, a polluted tributary of the River Po, and to the effluent of a large wastewater treatment plant which flows into the River Lambro. In field exposures, trout were held in cages in the River Po upstream and downstream from the confluence of the River Lambro. After 10-day (laboratory) and 30-day (laboratory and field) exposures, trout were examined for several chemical, biochemical and histological endpoints. The results indicated that exposure to complex mixtures of chemicals, including estrogen receptor agonists, aryl-hydrocarbon receptor agonists, and probably antiandrogens, had occurred. Exposure altered the plasma levels of 17β-estradiol and testosterone, and some treatments also enhanced the activity of hepatic ethoxyresorufin O-deethylase. Gonadal histology showed varying levels of degenerative processes characterised by oocyte atresia, haemorrhages, melano-macrophage centres (MMCs), and oogonia proliferation. Liver histology showed less severe effects.     

Sterols in sediment samples from Venice Lagoon, Italy

Sterols of different origin were analysed in sediment samples collected in the Venice Lagoon. The purpose of the study was to investigate the degree of sewage contamination within the Lagoon using fecal sterols (coprostanol, epicoprostanol and coprostanone) and to analyse the pattern of the sterols to plot the origin of the organic matter.

Sedimentary coprostanol at Canal Grande within the city of Venice was more than one order of magnitude higher than other stations in the Lagoon and two orders higher than in a sediment sample collected in the open sea. The cholesterol/coprostanol ratio, like the percentage of coprostanol in total sterols at this sample site was very similar to values in sewage sludge. The different pattern of sterols at station 2 which had the largest amount of total sterol indicates a difference in the origin of the organic material. Nevertheless the sterols used as tracer of terrestrial vascular plants did not show any particular trend at this station, receiving fresh water inputs. (3-Sitosterol and cholestanol reached the highest levels at the station within the Chioggia basin.     

First report on chemometric modeling of hydrolysis half-lives of organic chemicals

Environmental Science and Pollution Research - Hydrolysis is one of the most important processes of transformation of organic chemicals in water. The rates of reactions, final chemical entities of...     

Volatile organic compounds produced during the aerobic biological processing of municipal solid waste in a pilot plant

The volatile organic carbon (VOC) and odours emitted during the aerobic biological processing of municipal solid waste (MSW) was studied in a pilot-scale reactor. VOCs were detected by different techniques on solid waste samples and the outlet air stream, before and after a biofilter. Organic compounds (alpha-pinene, beta-myrcene, D-limonene) were also measured in condensate water and leachate from the process. Results showed uniformity in the composition of the air in the solid waste samples, air sampled during the process and condensed water, indicating a matrix-derived origin of these compounds. Leachates, however, contained substances with a quite different molecular structure from the compounds identified in the gaseous fraction. Most of the substances in the gaseous effluent had a hydrocarbon-like structure, mainly terpenoids. The odour produced and detected through olfactometry agreed with GC-MS analyses. This was true above all for terpenes.     

PCDD/Fs in ambient air in north-east Italy: The role of a MSWI inside an industrial area

The stack gases of a municipal solid waste incinerator (MSWI), and ambient air were sampled in four locations around the plant for the analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). The sampling area was close to an industrial area near Trieste, in north-east Italy. The purpose of the study was to estimate the impact of the MSWI emissions and to distinguish the contribution of these emissions from other potential emission sources in the industrial area.PCDD/F atmospheric concentrations were similar to those generally detected in urban–rural areas with one location about 2–3 times more contaminated than the others. Since the most contaminated location was inside the industrial area but upwind of the MSWI, principal component analysis (PCA) was used to establish whether other sources were the cause. This analysis clearly showed that a local steel plant’s emission was the main source of PCDDs/Fs in ambient air. This study highlights the usefulness of multivariate data analysis such as PCA to identify, among different potential emission sources, the one really responsible for the contamination.