Determinants of exposure to polychlorinated biphenyls in the Italian population in the last decades.

Polychlorinated biphenyls (PCBs) are industrial products extensively used in the past. Because of their widespread presence and toxic effects, the international community adopted control measures to reduce their release into the environment. Currently, PCB concentrations are decreasing, but humans are still exposed. In this paper, we reported the results of a study concerning PCB concentrations in human serum samples collected in Italy over two decades. The aim of the study was to investigate the trend of major determinants of PCB human exposure, several decades after the end of their production. PCB concentrations ranged over three orders of magnitude (from 0.4 to 958 ng/g lipid), with a median value of 85 ng/g lipid. We identified age, sampling year, body mass index, sex, and living near hot spots or being occupationally exposed as relevant factors in determining body burden. Our results can give indications to refine regulatory policies on PCBs in Italy, with particular attention to the disposal of residue PCB-containing products. To improve control measures can further decrease the exposure of citizens to PCBs, limit health implications, and improve citizens' perception about chemical risk management.

Time trends of PCDDs, PCDFs, DL-PCBs, and NDL-PCBs in Italian women from biomonitoring studies.

A number of biomonitoring investigations were carried out in Italy between 2000 and 2018 by the Unit of Human Exposure to Environmental Chemicals of the Italian National Institute of Health (Rome). The investigations were characterized by different features (case-control or cross-sectional studies, participants from impacted or no impacted areas, etc), but despite the differences, it was possible to study the time trends of Σ7(PCDDs), Σ10(PCDFs), Σ12(DL-PCBs), and Σ6(NDL-PCBs) (analytical and TEQ cumulative concentrations, as appropriate). All the chemicals considered showed clear rates of a time-dependent concentration decrease, data having previously been adjusted for the sampled Region and subject age. Σ7(PCDDs) exhibited the fastest decrease with an average rate of -4.44 pg/g-fat year-1 (2009-2018), whereas Σ6(NDL-PCBs) was characterized by the slowest decrease with a rate of -0.771 ng/g-fat year-1 (2000-2018). A clear distinction between the decreasing rates of Σ7(PCDDs) and Σ10(PCDFs) was observed, as the latter decreased at half the rate of the Σ7(PCDDs). The slower rate of the Σ10(PCDFs) decline may be due to an ongoing source of PCDFs in the environment beyond those traditionally considered for this group of contaminants such as the production of PCDFs due to PCBs thermal conversion from matrices contaminated with PCBs. Production of PCDFs due to thermal conversion of matrices contaminated with PCBs could be an ongoing source which may be of concern because recent data have highlighted the diffusion of PCBs in the European environment. The decreasing rates of PCDDs + PCDFs, DL-PCBs, and PCDDs + PCDFs + DL-PCBs - original analytical data converted to "dioxin equivalents" - were respectively estimated as (pgTEQ/g-fat year-1) -2.08, -2.06, and -2.10, values exhibiting good compatibility between one another.

Biomonitoring of the adult population in the area of turin waste incinerator: Baseline levels of polycyclic aromatic hydrocarbon metabolites.

Exposure to polycyclic aromatic hydrocarbons (PAHs) was assessed in a cohort of 394 subjects, 198 residing in three small municipalities near a new waste-to-energy (WTE) incinerator located in the Turin area, and 196 residing in neighbouring control areas in the town (of Turin). The assessment of exposure to PAHs was part of a human biomonitoring study aimed at assessing potential incremental exposure to pollutants related to incineration activities through the analysis of such pollutants before the plant start-up, and after one and three years of operation. The exposure assessment described in this study was carried out before the start-up of the WTE incinerator. Ten monohydroxy-PAHs (OH-PAHs) were analyzed in urine samples, consisting in the principal metabolites of naphthalene (NAP), fluorene (FLU), phenanthrene (PHE), and pyrene (PYR). Concentrations of the sum of OH-PAHs (Σ10OH-PAHs) were in the range of 525-85200 ng/g creatinine, with P50 equal to 6770 ng/g creatinine. Metabolites of naphthalene were found at the highest concentrations (P50 values of 892 and 4300 ng/g creatinine for 1- and 2-OH-NAP, respectively) followed by the three OH-FLUs (P50 values of individual compounds in the range of 58.2-491 ng/g creatinine), the four OH-PHEs (P50 values in the range of 30.5-145 ng/g creatinine), and 1-OH-PYR (P50 value of 82.8 ng/g creatinine). Concentrations of 1-OH-NAP, 9-OH-FLU, 1-, 2-, 3, 4-OH-PHE, and 1-OH-PYR were significantly lower in subjects living near the WTE plant compared to those living in the town of Turin, with differences between the two groups in the range 14-31%. Smoking habits markedly influence the urinary concentrations OH-PAHs. Median concentrations of the single metabolites in smokers were from 1.4 fold (for 4-OH-PHE) to 14 fold higher (for 3-OH-FLU) than those observed in non-smokers. The heating system used also resulted to be a major contributor to PAH exposure. Concentrations of OH-PAHs were generally comparable with those observed in other industrialized countries. The profile pattern was consistent with those reported in the literature. Concentrations of OH-PAHs assessed in this study may be considered indicative of the background exposure to PAHs for adult population living in an urban and industrialized area.

Authentication of an Italian PDO hazelnut ("Nocciola Romana") by NIR spectroscopy.

Common hazelnuts are widely present in human diet all over the world, and their beneficial effects on the health have been extensively investigated and demonstrated. Different in-depth researches have highlighted that the harvesting area can define small variations in the chemical composition of the fruits, affecting their quality. As a consequence, it has become relevant to develop methodologies which would allow authenticating and tracing hazelnuts. In the light of this, the present work aims to develop a non-destructive method for the authentication of a specific high-quality Italian hazelnut, "Nocciola Romana," registered with a protected designation of origin (PDO). Thus, different samples of this fruit have been analyzed by near-infrared (NIR) spectroscopy and then classification models have been built, in order to distinguish between the PDO fruits and the hazelnuts not coming from the designated region. In particular, two different classification approaches have been tested, a discriminant one, partial least squares-discriminant analysis, and a class-modeling one, soft independent modeling of class analogies. Both methods led to very high prediction capability in external validation on a test set (classification accuracy in one case, and sensitivity and specificity in the other, all higher than 92%), suggesting that the proposed methodologies are suitable for a rapid and non-destructive authentication of the product.

Simultaneous quantification of caffeine and chlorogenic acid in coffee green beans and varietal classification of the samples by HPLC-DAD coupled with chemometrics.

A chromatographic procedure (HPLC-DAD) using a relatively rapid gradient has been combined with a chemometric curve deconvolution method, multivariate curve resolution-alternating least squares (MCR-ALS), in order to quantify caffeine and chlorogenic acid in green coffee beans. Despite that the HPLC analysis (at these specific operating conditions) presents some coeluting peaks, MCR-ALS allowed their resolution and, consequently, the creation of a calibration curve to be used for the quantification of the analytes of interest; this procedure led to a high accuracy in the quantification of caffeine and chlorogenic acid present in the samples. In a second part of this study, the possibility of classifying the green coffee beans on the basis of their cultivar (Arabica or Robusta), by partial least squares discriminant analysis (PLS-DA) and soft independent modeling of class analogies (SIMCA), has been explored. SIMCA resulted in 100% of sensitivity and specificity for the Arabica class, while for the Robusta, it reached 66.7% of sensitivity and 100% of specificity, or 100% of sensitivity and 100% of specificity, depending on the extraction procedure followed prior to the chromatographic analysis; PLS-DA achieved 100% of correct classification independently of the procedure used for the extraction.

Concentrations of polychlorinated dibenzodioxins, polychlorodibenzofurans, and polychlorobiphenyls in women of reproductive age in Italy: A human biomonitoring study.

BACKGROUND: Polychlorinated dibenzodioxins (PCDDs), polychlorodibenzofurans (PCDFs), and polychlorobiphenyls (PCBs) are persistent organic pollutants that represent a major concern for women of reproductive age because of the neurodevelopmental effects associated to perinatal exposure. OBJECTIVES: This study was aimed at characterizing exposure of women of reproductive age to PCDDs, PCDFs, and PCBs as a function of residence in different Italian Regions, in areas at presumable different environmental contamination and human exposure to these pollutants. METHODS: Study participants were enrolled in 2011-2012 in 6 Italian Regions representative of Northern, Central and Southern Italy; in each region, areas at presumed different exposure (rural, urban and industrial) were selected for enrolment. Each participant provided a serum sample for the analysis of PCDDs, PCDFs and PCBs. RESULTS: Median concentrations of PCDDs+PCDFs, DL-PCBs, NDL6-PCBs and NDL9-PCBs in serum samples were respectively 6.0 and 3.5 pgWHO-TE05/g fat, and 75 and 93ng/g fat. Age was the variable that most affected median serum concentrations. Age adjusted concentrations were found significantly different between geographical zones: women from Northern Italy showed the highest values, followed by Central and Southern Italy. PCDDs+PCDFs concentrations were significantly higher in the group of women residing in industrial areas compared to the group residing in rural areas. A clear diminishing temporal trend was observed compared to levels reported in previous studies. CONCLUSIONS: This study produced the largest dataset on serum concentrations of PCDDs, PCDFs and PCBs in women of childbearing age in Italy. RESULTS: confirmed that environmental and lifestyle factors may influence exposure to these contaminants and thereby the body burden. The observed marked temporal decline in body burden during three decades is in agreement with the general trend observed worldwide.

Metals in Mediterranean aquatic species.

Metals such as arsenic (As), cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb), vanadium (V), have been determined in species of Mediterranean marine organisms collected from areas supposed to be at background contamination levels. The Inductively Coupled Plasma Mass Spectrometry (ICP-MS) approach was adopted for the determination of all the metals. Arsenic, Cd and Pb determined in the 42 samples, do not exceed the pertinent maximum level except a sample of hake. In wild fish, the concentration range for Cr, Ni, V and Cu was, respectively: 0.07-0.09, 87.6-124, 0.022-0.075 and 0.79-1.74 µg/g fresh weight (fw). The farmed fish samples show concentration levels below the wild fish ones, except for Cr which range at the same levels. Cadmium and Pb show a high sample number under the quantification limit. The elements do not bio-magnify among the species considered and appear to show low variations in relation to organisms' position in the food chain and at sampling sites.

Persistent toxic substances in Mediterranean aquatic species.

Fish and fishery products may represent one of the main sources of dietary exposure to persistent toxic substances (PTSs) such as polychlorinated dibenzodioxins, dibenzofurans, and biphenyls; polybromodiphenyl ethers; organochlorine pesticides; perfluorooctanoic acid and perfluorooctane sulfonate; and inorganic mercury and methyl mercury. In this study, PTS contamination of Mediterranean fish and crustaceans caught in Italian coastal waters was investigated in order to increase the representativeness of the occurrence database for wild species. The objectives were to verify the suitability of regulatory limits for PTSs, identify background concentrations values, if any, and examine the possible sources of variability when assessing the chemical body burdens of aquatic species. Twelve wild species of commercial interest and two farmed fish species were chosen. Excluding methyl mercury, chemical concentrations found in wild species fell generally towards the low ends of the concentration ranges found in Europe according to EFSA database and were quite lower than the tolerable maximum levels established in the European Union; farmed fish always showed contamination levels quite lower than those detected in wild species. The data obtained for wild species seemed to confirm the absence of local sources of contamination in the chosen sampling areas; however, species contamination could exceed regulatory levels even in the absence of specific local sources of contamination as a result of the position in the food web and natural variability in species' lifestyle. A species-specific approach to the management of contamination in aquatic organisms is therefore suggested as an alternative to a general approach based only on contaminant body burden. A chemical-specific analysis performed according to organism position in the food chain strengthened the need to develop this approach.

Persistent organic pollutants (POPs) in fish collected from the urban tract of the river Tiber in Rome (Italy).

European eel and chub samples were analyzed to determine the levels of non-dioxin-like polychlorobiphenyls (NDL-PCBs), polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs), dioxin-like PCBs (DL-PCBs), and brominated polybromodiphenyl ethers (PBDEs) in order to evaluate the extent of contamination of the river Tiber along the urban tract through the city of Rome (Italy). All samples presented detectable levels of the chemicals analyzed, and exhibited species-specific differences in terms of congener composition and total concentrations. On average the European eel presented the highest values. In this species the dioxin-like compound sums (WHO-TEQs) exceeded the pertinent maximum levels (MLs). Non-ortho PCBs constituted approximately 80% of WHO-TEQ toxicological potential whereas NDL-PCB and PBDE concentrations appeared to match values determined in other polluted aquatic ecosystems where non-point contamination sources were present. The contamination patterns determined in fish tissues seemed to reflect the impact of generic contamination source(s).

Artificial-turf playing fields: contents of metals, PAHs, PCBs, PCDDs and PCDFs, inhalation exposure to PAHs and related preliminary risk assessment.

The artificial-turf granulates made from recycled rubber waste are of health concern due the possible exposure of users to dangerous substances present in the rubber, and especially to PAHs. In this work, we determined the contents of PAHs, metals, non-dioxin-like PCBs (NDL-PCBs), PCDDs and PCDFs in granulates, and PAH concentrations in air during the use of the field. The purposes were to identify some potential chemical risks and to roughly assess the risk associated with inhalation exposure to PAHs. Rubber granulates were collected from 13 Italian fields and analysed for 25 metals and nine PAHs. One further granulate was analysed for NDL-PCBs, PCDDs, PCDFs and 13 PAHs. Air samples were collected on filter at two fields, using respectively a high volume static sampler close to the athletes and personal samplers worn by the athletes, and at background locations outside the fields. In the absence of specific quality standards, we evaluated the measured contents with respect to the Italian standards for soils to be reclaimed as green areas. Zn concentrations (1 to 19 g/kg) and BaP concentrations (0.02 to 11 mg/kg) in granulates largely exceeded the pertinent standards, up to two orders of magnitude. No association between the origin of the recycled rubber and the contents of PAHs and metals was observed. The sums of NDL-PCBs and WHO-TE PCDDs+PCDFs were, respectively, 0.18 and 0.67×10(-5) mg/kg. The increased BaP concentrations in air, due to the use of the field, varied approximately from <0.01 to 0.4 ng/m(3), the latter referring to worst-case conditions as to the release of particle-bound PAHs. Based on the 0.4 ng/m(3) concentration, an excess lifetime cancer risk of 1×10(-6) was calculated for an intense 30-year activity.

Modeling of DR CALUX bioassay response to screen PCDDs, PCDFs, and dioxin-like PCBs in farm milk from dairy herds.

A recent issue in the EU legislation is the evaluation of the toxicologically-equivalent contribution of dioxin-like polychlorobiphenyls (DL-PCBs) in addition to that coming from polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs) as contaminants in foods for a total of 29 congeners. This fact is determining the need to revise analytical criteria both for confirmatory and screening analysis. In this work, a modeling was developed to check the reliability of the outcomes of the DR CALUX bioassay when applied to farm milk samples characterized by large differences in congener patterns. To reproduce some field conditions where DL-PCB contributions up to 90% of total WHO-TEQs (HRGC-HRMS assessment) were recorded in dairy products, goat milk samples from a common bulk were fortified at different TEQ levels with mixtures containing either PCDDs and PCDFs or non-ortho substituted DL-PCBs. Fortification ranged approximately 4.5-15 pgWHO-TEQ/g fat. Based on the results, DR CALUX relative potency value (REP) of DL-PCB 126 was estimated 0.061 against the canonical WHO-TEF of 0.1. The value of 0.061 together with the other DR CALUX REPs from the literature for the remaining 28 congeners were used to model DR CALUX response (C-TEQs) in milk samples with different congener patterns. The theoretical underestimation of DR CALUX data could be mitigated by correcting the latter with the linear correlation experimentally obtained between C-TEQs and the WHO-TEQs. Under these conditions, the use as calibrants of reference samples with different analytical patterns could help those laboratories involved in a high throughput routine to set the most appropriate decision limits to optimize screening output.

Persistent and toxic substances in the Venice lagoon biota: an approach for quantitative data analysis for risk management.

An approach based on hypothesis testing for the management of persistent inorganic and organic toxic chemicals (PTS/POPs) detected in clams and mussels from the Venice lagoon is presented. The chemicals of interest for this evaluation were the polychlorinated biphenyls (PCBs), dibenzodioxins (PCDDs), and dibenzofurans (PCDFs), hexachlorobenzene (HCB), and the heavy metals cadmium (Cd), mercury (Hg), and lead (Pb). Two statistically different populations of data for PCDDs+PCDFs (TEQs), HCB, Cd, and Pb, associated with biota samples collected respectively in the lagoon central district and in the southern and northern districts were identified. The central district is under the impact of the Porto Marghera industrial settlement and the city of Venice, whereas the southern and northern districts are subject to a general impact. Of the aforementioned chemicals, those with more discriminating power were found to be HCB and PCDDs+PCDFs.