Salvatore Barreca

Environmental Organic Photochemistry: Advances and Perspectives

This review is a survey of recent advances in environment related aspects of organic photochemistry. Besides presenting gen- eral concepts, the manuscript is mainly focused on the photoreactivity of natural organic matter, and on the photochemistry of anthropo- genic substances under natural light irradiation.

Polychlorinated Biphenyls in Sediments from Sicilian Coastal Area (Scoglitti) using Automated Soxhlet, GC-MS, and Principal Component Analysis

A methodology for the PAHs and PCBs congener determination in sediment samples has been revised. We determined the distributions of PAHs and PCBs in the superficial sediments of the Scoglitti (Italy) coastal area to provide data for comparison with other marine systems and to hypothesize the sources. Extraction yield, for PCB, was never less than 60% in most cases, while for PAHs, utilizing perdeuterated surrogate standard (benz[a]anthracene-d12 and anthracene-d10) was never less than 72%. The total concentration of the 16 PAHs investigated, expressed as the sum of concentrations, ∑PAHs, varied from 1–5087 μg/kg of dry matrix, while the ∑ PCBs ranged from detection limit to 36 μg/kg of dry matrix. Linear relationships were found between PAHs concentration and organic matter percentages (R2 = 0.60) and water content and organic matter percentages (R2 = 0.87). Isomeric ratios were used for discriminating between pyrolitic and petroleum origin. The principal component analysis (PCA) has been conduced to discriminate the different sampling sites in internal or external harbor area.

Photochemical sample treatment for extracts clean up in PCB analysis from sediments

Sample purification can be considered the most polluting step of the whole analytical process for PCBs determination in sediment samples. The use of photochemical sample treatment represents an alternative methodology for extracts clean up allowing for a reduction of the used amount of organic solvents. The first application of a photochemical sample treatment for the selective removal or reduction of organic substances interfering with PCBs analyses in sediments is reported. The methods efficiency and robustness were compared with currently used chromatographic purification. Quality parameters such as recovery, linearity and reproducibility were studied. The entire procedure was validated by four replicate analysis of certified reference sediment. The quantification limits (LOQ) obtained by us ranged from 1 to 3.1 ng g(-1). The RSD for each congener was below 15% and recoveries were in the range 40-130%. Results based on the analysis of real and certified samples showed similar or improved detection thresholds and pointed out the advantages of the photochemical methodology in terms of costs and environmental friendly conditions.

Determination of Selected Phthalates by Gas Chromatography–Mass Spectrometry in Personal Perfumes

A simple and fast method is proposed to analyze commercial personal perfumes. Our method includes measurement of phthalates, known to be major sources of endocrine disruptor chemicals (EDC), which originate from the less volatile fraction of perfumes. The quantification of phthalates were carried out directly with no sample preparation required on 30 samples of commercial products using gas chromatography and mass spectrometry (GC-MS) as a detector. The total concentrations of 15 investigated compounds ranged from 17 to 9650 mg/L with an average of 2643 mg/L. The highest total concentration was found in cologne. Diethyl phthalate (DEP), diisobutyl phthalate (DiBP), di(2-ethylhexyl) phthalate (DEHP), and di-n-butyl phthalate (DBP) were detected in appreciable concentrations. Further, it was found that the composition of counterfeit samples varied widely from that of authentic products. The composition of old products was different from that of recent perfumes, which contain less harmful chemicals, attributed to the ban on some phthalates in Europe due their toxicity. It should be noted that older and contaminated products are not equivalent to authentic products when considering quality, safety, and probably effectiveness. Older and nonapproved perfumes contain chemicals that are not allowed for commercial use and may contain toxic impurities.

Composition, Distribution, and Sources of Polycyclic Aromatic Hydrocarbons in Sediments of the Gulf of Milazzo (Mediterranean Sea, Italy)

This article describes the characterization of Polycyclic Aromatic Hydrocarbons (PAHs) in sediments of Milazzo Gulf (Italy) located in front of an oil refinery and a power plant. The investigated area is characterized by urban and industrial activities. The sixteen PAHs identified by the USEPA, as requiring priority monitoring, and other non USEPA listed PAHs, namely perylene and some methyl derivatives, were investigated The total PAHs concentrations, expressed as ∑ 19 PAH ranges from 5.6–7402 μg/Kg d.w., with a mean value of 492 μg/Kg d.w. The concentrations of PAHs found in 64 out of 67 samples were lower than the effect range low (ERL = 2460 μg/Kg) concentration, while the remaining samples were in the range between ERL and effect range middle (ERM) concentrations. The mean values of all samples of the same stations were lower than the ERL. These findings indicated that the sediments from the entire sampling area should have no potential biological impact.

Profiles and Sources of PAHs in Sediments from an Open-Pit Mining Area in the Peruvian Andes

The Peruvian Andes are one of the most productive areas for mining and therefore also one of the most exposed to these sources of pollution. This article reports the characterization of Polycyclic Aromatic Hydrocarbons (PAHs) in sediments of Cerro de Pasco area (Peru) located close to a large open-pit mine and, in recent years, several reports have provided evidence of environmental contamination and related health problems. Investigations were carried out into the fifteen PAHs identified by the US-Environment Protection Agency (US-EPA) as requiring priority monitoring, other non US-EPA listed PAHs and perylene were also investigated in order to obtain further information on their origins. By considering the results of all the analysis, the total PAHs concentration varies from 13–1009 μg/Kg with a mean value of 224 μg/Kg. The concentrations of PAHs found in all 12 stations were lower than the effect range low (ERL). PAHs, in the most of the samples, have origin from high temperature processes. Taking into consideration that perylene concentrations were low, a small quantity of polycyclic hydrocarbons may be originated from biological activity.

Volatile Profiles of Emissions from Different Activities Analyzed Using Canister Samplers and Gas Chromatography-Mass Spectrometry (GC/MS) Analysis: A Case Study

The objective of present study was to identify volatile organic compounds (VOCs) emitted from several sources (fuels, traffic, landfills, coffee roasting, a street-food laboratory, building work, indoor use of incense and candles, a dental laboratory, etc.) located in Palermo (Italy) by using canister autosamplers and gas chromatography-mass spectrometry (GC-MS) technique. In this study, 181 VOCs were monitored. In the atmosphere of Palermo city, propane, butane, isopentane, methyl pentane, hexane, benzene, toluene, meta- and para-xylene, 1,2,4 trimethyl benzene, 1,3,5 trimethyl benzene, ethylbenzene, 4 ethyl toluene and heptane were identified and quantified in all sampling sites.

Discrimination of almonds (Prunus dulcis) geographical origin by minerals and fatty acids profiling

Abstract Twenty-one almond samples from three different geographical origins (Sicily, Spain and California) were investigated by determining minerals and fatty acids compositions. Data were used to discriminate by chemometry almond origin by linear discriminant analysis. With respect to previous PCA profiling studies, this work provides a simpler analytical protocol for the identification of almonds geographical origin. Classification by using mineral contents data only was correct in 77% of the samples, while, by using fatty acid profiles, the percentages of samples correctly classified reached 82%. The coupling of mineral contents and fatty acid profiles lead to an increased efficiency of the classification with 87% of samples correctly classified.

Speciation of vanadium in urban, industrial and volcanic soils by a modified Tessier method

Vanadium (V) concentrations in industrial, urban and volcanic soils were sequentially extracted using a modified Tessiers method. The voltammetric technique was used to determine V concentrations in solutions obtained from the various extraction steps. At the reference stations, the V concentrations (sum of four individual fractions) in soils ranged from 0.72 to 0.24 g kg(-1) dry weight (d.w.) with a mean value of 0.18 g kg(-1) d.w. V concentrations in soils of the Palermo urban area ranged from 0.34 to 2.1 g kg(-1) d.w., in the Milazzo (industrial) area between 0.26 and 5.4 g kg(-1) d.w. and in the volcanic area near Mt. Etna from 0.91 to 2.9 g kg(-1) d.w. When the V concentrations around Mt. Etna were compared with those obtained at the reference stations, it was confirmed that Mt. Etna is a continuous source of V. In all the samples analyzed, the majority of V (from 94 to 100%) was detected in the fourth fraction.

An analytical method for monitoring micro-traces of landfill leachate in groundwater using fluorescence excitation–emission matrix spectroscopy

In this study, we use three-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy for the identification of contamination of natural water bodies by landfill leachate. In particular, EEM was applied to provide information about the presence and quantities of leachate in ground waters. A good linear relationship was found between the fluorescence intensity emission of groundwater spiked with landfill leachate and the volumes of the latter, suggesting that there was no intrinsic fluorescence in the concentration range of 0–1000 μL L−1. The obtained values of the LOD (10 μL L−1; TOC = 34 μg L−1) and LOQ (34 μL L−1; TOC = 114 μg L−1) allow us to detect the presence and the amount of the landfill leachate in a sample of groundwater even when it is diluted about 100 000 times.