Determination of pollutants, antibiotics, and drugs in surface water in Italy as required by the third EU Water Framework Directive Watch List: method development, validation, and assessment.

In this paper, we report a study concerning the quantification of new emerging pollutants in water as a request from the third European Watch List mechanism. The EU Watch List compound was investigated by an internal method that was validated in terms of detection limits, linearities, accuracy, and precision in accordance with quality assurance criteria, and it was used to monitor several rivers from 11 Italian regions. The methodology developed was satisfactorily validated from 5 to 500 ng L-1 for the emerging pollutants studied, and it was applied to different river waters sampled in Italy, revealing the presence of drugs and antibiotics. Rivers were monitored for 2 years by two different campaigns conducted in 2021 and 2022. A total of 19 emerging pollutants were investigated on 45 samples. The most detected analytes were O-desmethylvenlafaxine and venlafaxine. About azole compounds, sulfamethoxazole, fluconazole, and Miconazole were found. About antibiotics, ciprofloxacin and amoxicillin were found in three and one samples, respectively. Moreover, statistical analyses have found a significant correlation between O-desmethylvenlafaxine with venlafaxine, sulfamethoxazole with venlafaxine, and fluconazole with venlafaxine.

Determination of Perfluorooctanoic Acid (PFOA) in the Indoor Dust Matter of the Sicily (Italy) Area: Analysis and Exposure Evaluations.

Perfluorooctanoic acid (PFOA) in environmental matrices is increasingly being studied due to its environmental persistence, global occurrence, bioaccumulation, and associated human health risks. Some indoor environments can significantly impact the health of occupants due to pollutants in indoor air and household dust. To investigate the potential exposure of individuals to PFOA in specific confined environments, this study reports an analytical method and results concerning the determination of PFOA in household dust, used as a passive sampler. To the best of our knowledge, this paper represents one of the first studies concerning PFOA concentrations in indoor dust collected in the south of Italy, within the European region. A total of twenty-three dust samples were collected from two different areas of Sicily (Palermo and Milena), extracted, and analyzed by an UHPLC-QTOF-MS/MS system. Finally, PFOA exposure was estimated using a new index (Indoor PFOA Exposure Index, IPEX) that incorporates the PFOA levels in dust, exposure time, and the correlation between the PFOA in dust and blood. It was then compared across four different exposure groups, revealing that PFOA exposure for people working in chemistry laboratories was evaluated to be ten times higher than the exposure for homemakers.

Analytical Method for Quantification of Several Phthalate Acid Esters by Gas Chromatography-Mass Spectrometry in Coffee Brew Samples.

Several phthalate acid esters (PAEs), often called phthalate esters or phthalates, are substances classified as harmful due to their carcinogenic and mutagenic properties, and moreover, as dangerous for humans because they interfere with the endocrine system. In general, phthalic esters are used as plasticizers for different polymers and more other consumer products. In the present study, we describe a simple method to quantify PAEs in coffee brew using a liquid-liquid extraction without purification processes through analysing the obtained organic phase by GCMS in the single ion monitoring mode. The totals of single PAEs, in coffee brew samples analysed by us, are in the range of 159-5305 µg L-1 . Considering that, on average, a person drinks three cups (total 90 mL) of the aforementioned drink per day, this will lead to the uptake of a total 14 to 477 µg of phthalates.

Presence and biodistribution of perfluorooctanoic acid (PFOA) in Paracentrotus lividus highlight its potential application for environmental biomonitoring.

The first determination of presence and biodistribution of PFOA in ninety specimens of sea urchin Paracentrotus lividus from two differently contaminated sites along Palermo's coastline (Sicily) is reported. Analyses were performed on the sea urchins' coelomic fluids, coelomocytes, gonads or mixed organs, as well as on seawater and Posidonia oceanica leaves samples from the collection sites. PFOA concentration ranged between 1 and 13 ng/L in seawater and between 0 and 794 ng/g in P. oceanica. The analyses carried out on individuals of P. lividus from the least polluted site (A) showed PFOA median values equal to 0 in all the matrices (coelomic fluid, coelomocytes and gonads). Conversely, individuals collected from the most polluted site (B) showed median PFOA concentrations of 21 ng/g in coelomic fluid, 153 ng/g in coelomocytes, and 195 ng/g in gonads. Calculated bioconcentration factors of log10BCF > 3.7 confirmed the very bioaccumulative nature of PFOA. Significant correlations were found between the PFOA concentration of the coelomic fluid versus the total PFOA concentration of the entire sea urchin. PERMANOVA (p = 0.001) end Welch's t-test (p < 0.001) analyses showed a difference between specimens collected from the two sites highlighting the potential application of P. lividus as sentinel species for PFOA biomonitoring.

Estrogenicity of chemical mixtures revealed by a panel of bioassays.

Estrogenic compounds are widely released to surface waters and may cause adverse effects to sensitive aquatic species. Three hormones, estrone, 17ß-estradiol and 17α-ethinylestradiol, are of particular concern as they are bioactive at very low concentrations. Current analytical methods are not all sensitive enough for monitoring these substances in water and do not cover mixture effects. Bioassays could complement chemical analysis since they detect the overall effect of complex mixtures. Here, four chemical mixtures and two hormone mixtures were prepared and tested as reference materials together with two environmental water samples by eight laboratories employing nine in vitro and in vivo bioassays covering different steps involved in the estrogenic response. The reference materials included priority substances under the European Water Framework Directive, hormones and other emerging pollutants. Each substance in the mixture was present at its proposed safety limit concentration (EQS) in the European legislation. The in vitro bioassays detected the estrogenic effect of chemical mixtures even when 17ß-estradiol was not present but differences in responsiveness were observed. LiBERA was the most responsive, followed by LYES. The additive effect of the hormones was captured by ERα-CALUX, MELN, LYES and LiBERA. Particularly, all in vitro bioassays detected the estrogenic effects in environmental water samples (EEQ values in the range of 0.75-304 × EQS), although the concentrations of hormones were below the limit of quantification in analytical measurements. The present study confirms the applicability of reference materials for estrogenic effects' detection through bioassays and indicates possible methodological drawbacks of some of them that may lead to false negative/positive outcomes. The observed difference in responsiveness among bioassays - based on mixture composition - is probably due to biological differences between them, suggesting that panels of bioassays with different characteristics should be applied according to specific environmental pollution conditions.

Preliminary study on analysis and removal of wax from a Carrara marble statue.

This preliminary study has mainly focused on the wax identification by nuclear magnetic resonance (NMR) and removal. Wax is used for many purposes in the field of art as protective coatings on wooden, stone or metal objects. From the comparison of the spectra H NMR and in particular with the correspondence of the resonance peaks of the samples taken from the statue and beeswax and paraffin, we can conclude that the wax applied on the statue surface is beeswax. From our data, it can be concluded that, to remove the beeswax, from any stone support, the more effective solvent is the mixture of cyclohexane/ethyl acetate. The removal percentages ranged from 19 to 99%. Lower percentages of removal have been observed in the case of yellow marble, probably because of its high porosity. We can affirm that, this solvent mixture can be employed in real art objects using cotton swabs to remove protective wax.

Chasing phthalates in tissues of marine turtles from the Mediterranean sea.

Tissues from thirteen specimens of marine turtles, one Dermochelys coriacea and twelve Caretta caretta, found dead along the Sicilian coasts in 2016 were analyzed for the presence of phthalates. Four phthalates (DEP, DBP, BBP, and DEHP) were found at different significant concentrations in liver and gonads, while only DBP was found in muscle tissues and at a fourfold lower concentration than other phthalates in Dermochelys coriacea. No traces of DEP were detected in C. caretta tissues where DOTP was also revealed. The presence of phthalates in fat tissue in specimens of C. caretta showed a major prevalence of the most lipophilic phthalates DEHP and DOTP. The total concentration of all analyzed phthalates, showed high values in all tissues. Results suggested that for monitoring purposes from live specimens sample collection should be addressed to fat tissue with accurate manipulations.

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.

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 Tessier's 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.

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

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.

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.

Photochemical sample treatment: a greener approach to chlorobenzene determination in sediments.

Due to worker׳s exposure, solvent and stationary phases׳ consumption, sample purification is one of the most polluting steps in analytical procedures for determination of organic pollutants in real samples. The use of photochemical sample treatment represents a valid alternative methodology for extracts clean up allowing for a reduction of the used amount of organic solvents. In this paper we report the first application on the photolytic destruction of organic substances to eliminate some of the interferences in the analysis of Chlorobenzenes in sediment samples. The method׳s efficiency and robustness were compared with classic silica column purification process currently used in clean up procedures in sediment analysis. Quality parameters such as recovery, linearity and reproducibility were studied. The entire procedure was validated by three replicate analysis of spiked real sediment sample. The quantification limits (LOQ) obtained by us ranged from 1.0 to 2.3 ng g(-1), while the detection limits (LOD) were of 1.0 ng g(-1). The RSD for each congener was below 10% and recoveries were in the range 95-130%. Results based on the analysis of real samples showed similar or improved detection thresholds and pointed out the advantages of the photochemical methodology in terms of costs, use of chemical substances and operator׳s safety according to Green Analytical Chemistry principles.

The distribution of phthalate esters in indoor dust of Palermo (Italy).

In this work, phthalic acid esters (PAEs): dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate, and di-n-octyl phthalate in indoor dust (used as passive sampler) were investigated. The settled dust samples were collected from thirteen indoor environments from Palermo city. A fast and simple method using Soxhlet and GC-MS analysis has been optimized to identify and quantify the phthalates. Total phthalates concentrations in indoor dusts ranged from 269 to 4,831 mg/kg d.w. (d.w. = dry weight). The data show a linear correlation between total PAEs concentration and a single compound content, with the exclusion of the two most volatile components (DMP and DEP) that are present in appreciable amounts only in two samples. These results suggest that most of the PAEs identified in the samples of settled dust originate from the same type of material. This evidence indicates that, in a specific indoor environment, generally is not present only one compound but a mixture having over time comparable percentages of PAEs. Consequently, for routine analyses of a specific indoor environment, only a smaller number of compounds could be determined to value the contamination of that environment. We also note differences in phthalate concentrations between buildings from different construction periods; the total concentration of PAEs was higher in ancient homes compared to those constructed later. This is due to a trend to reduce or remove certain hazardous compounds from building materials and consumer goods. A linear correlation between total PAEs concentration and age of the building was observed (R = 0.71).

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 method's 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.