DNA damage in A549 cells exposed to different extracts of PM(2.5) from industrial, urban and highway sites.

The aim of this research is to investigate the role played by the chemical fraction of PM(2.5) in the DNA damage induction in human lung cells (A549): in particular the effects of samples collected in urban, industrial and highway sites were compared. Organic and water-soluble extracts of PM(2.5) were analysed to quantify PAHs (by GC-MS technique) and metals (by ICP-MS technique) and tested on A549 cells to evaluate, by the Comet assay (without and with Fpg enzyme), genotoxic and oxidative damage. The chemical analysis showed a variability of PAH composition in PM organic extracts of the three different sites and pointed out the presence of 14 metals (being Fe, Cu, Zn, Sb and Ba the most abundant) in all the PM water extracts. Regarding the biological effect, all the PM(2.5) organic extracts caused a significant dose-dependent increase of the A549 DNA damage. The genotoxic effect was related to the PM(2.5) PAH content and the highest effect was observed for the highway site sample. The DNA oxidative damages were observed for the PM(2.5) water extracts of the samples collected in industrial and highway sites. The extent of the oxidative damage seems to be related to the kind and concentration of the metals present. The results of this study emphasize the importance of PM chemical composition on the biological effects and highlight the need, when evaluating the effects on health and exposure management, to always consider, beside size and concentration of PM, also their qualitative composition.

The use of clays to sequestrate organic pollutants. Leaching experiments.

Leaching experiments are performed from clay-pollutant systems in order to evaluate the capability of clays to sequestrate organic pollutants from wastewaters. Reference kaolinite KGa-1b, montmorrillonite SWy-2 and reference soil BCR-700 are the sorbent materials. 2,4,6-trichloroaniline (2,4,6-TCA) and 4-chlorophenol (4-CP) are the typical pollutants, sorbed at amounts of 10.0 mg g(-1) and 5.8 mg g(-1) on SWy-2 and 7.3 mg g(-1) and 2.2 mg g(-1) on KGa-1b, respectively. The leaching agents are ultrapure water and model solutions of acid rain and surface waters that simulate meteoric leaching. 1.0mM HNO(3), 1.0mM H(2)SO(4) solutions and a methanol/water 50/50 (v/v) mixture simulate leaching agents of industrial source. The results are compared and the preferential capability of the clays to sequestrate the more lipophilic 2,4,6-TCA is evidenced. The bond interactions are discussed and explained through preferential adsorption reactions. For montmorrillonite also a simultaneous intercalation in the phyllosilicate interlayer is proposed.

Photodegradation of E110 and E122 dyes in a commercial aperitif. A high performance liquid chromatography-diode array-tandem mass spectrometry study.

A commercial aperitif containing E110 and E122 dyes is exposed to photo-irradiation in solar box under conditions chosen to simulate sun light irradiation. After 16 days of irradiation the red-coloured aperitif assumes a very pale yellow colour. HPLC-diode array-MS/MS analysis evidences the presence in the commercial aperitif of some impurities with naphthalene-based structures. The structures for the photodegradation products are proposed.

A new hydrophilic interaction liquid chromatography tandem mass spectrometry method for the simultaneous determination of seven biogenic amines in cheese.

An HILIC-PI APCI MS/MS method is developed for the determination of seven biogenic amines (cadaverine, histamine, putrescine, spermidine, spermine, tryptamine and tyramine) in cheese. Their presence and relative amounts give useful information about freshness, level of maturing, quality of storage and cheese typicization. The major drawback in the analysis is represented by the relevant matrix effect and the general unbalanced concentrations of the different amines in cheese. The method proposed represents an improvement with respect to an HPLC-MS/MS method already developed in this laboratory. The new method permits better sensitivities it makes use of a Waters Atlantis HILIC (150.0 mm x 2.1 mm i.d., 3 microm) stationary phase and of a mobile phase of acetonitrile and ammonium formate 50.0 mM in ultrapure water brought to pH 4.00 for formic acid, flowing under gradient conditions. The chromatographic system is interfaced with a 3200QTrap LC-MS/MS system (Applied Biosystem, Foster City, CA, USA) by a Turbo V interface equipped with Heated Nebuliser (APCI) and Turbo Ion Spray (TIS) probes. LOQ values lower than 10 microg L(-1) are obtained. The method is applied in the analysis of Castelmagno cheese.

High performance liquid chromatography/tandem mass spectrometry determination of biogenic amines in typical Piedmont cheeses.

The paper presents a new HPLC method, hyphenated with mass spectrometry detection, for the separation and determination of the biogenic amines that are most commonly present in cheese, namely cadaverine, histamine, spermidine, spermine, tyramine and tryptamine. The HPLC-MS/MS method is validated by comparison of the results with those obtained through a literature HPLC-UV determination, based on a pre-column dansyl chloride derivatisation step. The intercalibration is based on the statistical t-test for multiple samples that allows to compare simultaneously the results obtained with the two methods for more analytes and to decide, at a prefixed confidence level, if the two methods are inter-changeable. The new HPLC-MS/MS method, employed in selected reaction monitoring (SRM) mode, permits to achieve for standard solutions limit of detection (LOD) values ranging from 1.7 to 22.5 microg L(-1) and LOQ (limit of quantitation) values ranging from 5.6 to 68.2 microg L(-1). In order to apply the method in the analysis of cheeses, LOD and LOQ values have also been evaluated in "ricotta" cheese, in order to take as possible into account the matrix interference. In these conditions LODs range between 5.1 and 35.0 microg L(-1) and LOQs between 14.2 and 101.2 microg L(-1). The whole methodology, comprehensive of the homogenization-extraction process and HPLC-MS/MS analysis, has been applied in the analysis of three typical Piedmont (North-West Italy) cheeses, known as Toma Piemontese, Raschera and Castelmagno.

HPLC-MSn and GC-MS methods to study sunlight and UV-lamp degradations of 1-amino-5-naphthalene sulfonate.

HPLC-DAD, HPLC-MS/MS, GC-MS and spectrophotometric methods are employed to investigate the degradation process of sodium 1-amino-5-naphthalene sulfonate (1A5NS) aqueous solutions, when exposed to sunlight and UV-lamp (254 nm) irradiations. Experimental results show that both sunlight and 254 nm UV-lamp irradiations destroy the chemical and give rise to major degradation products, characterised by the same m/z ratios. Degradation times are lower for sunlight irradiation, for which a t(1/2) value of 137.4 min has been evaluated, in comparison with the value of t(1/2) of 26.8 min, observed for UV-lamp irradiation. The degradation pathway and the structures of the degradation products are proposed.

Sorption of pesticides on kaolinite and montmorillonite as a function of hydrophilicity.

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.

HPLC-UV and HPLC-MSn multiresidue determination of amidosulfuron, azimsulfuron, nicosulfuron, rimsulfuron, thifensulfuron methyl, tribenuron methyl and azoxystrobin in surface waters.

The paper presents a new HPLC method, with UV and MS(n) detection, for the determination of seven pesticides, including the sulfonylurea herbicides amidosulfuron, azimsulfuron, nicosulfuron, rimsulfuron, thifensulfuron methyl, tribenuron methyl, and the fungicide azoxystrobin characterised by a methoxyacrilate structure. The methodology consists of a preconcentration/SPE (solid phase extraction) step and HPLC-UV (240 nm detection wavelength)-MS(n) analysis. Under the optimised conditions and after a 1000/1 preconcentration factor, the limits of detection were lower than 14.5 ng L(-1) for UV detection and lower than 8.1 ng L(-1) for MS detection. The limits of quantification were lower than 48.3 ng L(-1) in UV detection and than 26.9 ng L(-1) in MS(n) detection. The analysis of two samples, spiked with a mixture of the pesticides at threshold level concentrations, gave more than 60% recovery.

Statistical evaluation of recovery of 3,4-dichloroaniline in soil as function of particle size and analyte concentration.

A great mean value of recovery for extraction of 3,4-dichloroaniline from a soil is calculated from individual recovery values evaluated for four different fractions of the soil. Then the uncertainty associated to this great mean recovery is calculated and used to know whether to apply or not the correction in routine analysis performed for the same kind of soil and the same analyte. The most representative fractions that, as a function of particle size, can be identified in a soil are: sand (2.000-0.063mm), coarse silt (0.063-0.020mm), fine silt (0.020-0.002mm) and clay (

Oxidative degradation of food dye E133 Brilliant Blue FCF Liquid chromatography-electrospray mass spectrometry identification of the degradation pathway.

This paper is devoted to the evaluation of the degradation pathway of the E133 Brilliant Blue FCF (C.I. 42090) that is largely used in the food industry. The degradation is studied in oxidation conditions obtained by addition of potassium persulfate at different persulfate to dye molar ratios under natural sunlight irradiation. The degradation pathway of the dye passes through a species coloured in dark blue and then gives rise to uncoloured species. Due to the low volatility and the poor thermal stability of the dye, reversed-phase liquid chromatography associated to mass spectrometry and tandom mass spectrometry was employed to follow the kinetics of degradation and identify some intermediates. The identification of organic species still present in the decoloured dye and the value of COD obtained in these conditions show evidence that complete decolorization does not correspond to complete mineralisation. No direct information of toxicity is available for the uncoloured degradation products but the further formation of aromatic amines can not be excluded.