An integrated approach for chemical water quality assessment of an urban river stretch through Effect-Based Methods and emerging pollutants analysis with a focus on genotoxicity.

The impact of emerging chemical pollutants, on both status and functionality of aquatic ecosystems is worldwide recognized as a relevant issue of concern that should be assessed and managed by researchers, policymakers, and all relevant stakeholders. In Europe, the Reach Regulation has registered more than 100.000 chemical substances daily released in the environment. Furthermore, the effects related to the mixture of substances present in aquatic ecosystems may not be predictable on the basis of chemical analyses alone. This evidence, coupled with the dramatic effects of climate changes on water resources through water scarcity and flooding, makes urgent the application of innovative, fast and reliable monitoring methods. In this context, Effect-Based Methods (EBMs) have been applied in the urban stretch of the Tiber River (Central Italy) with the aim of understanding if detrimental pressures affect aquatic environmental health. In particular, different eco-genotoxicological assays have been used in order to detect genotoxic activity of chemicals present in the river, concurrently characterized by chemical analysis. Teratogenicity and embryo-toxicity have been studied in order to cover additional endpoints. The EBMs have highlighted the presence of diffuse chemical pollution and ecotoxicological effects in the three sampling stations, genotoxicological effects have been also detected through the use of different tests and organisms. The chemical analyses confirmed that in the aquatic ecosystems there is a diffuse presence, even at low concentrations, of emerging contaminants such as pharmaceuticals, not routinely monitored pesticides, personal care products, PFAS. The results of this study can help to identify an appropriate battery of EBMs for future studies and the application of more appropriate measures in order to monitor, mitigate or eliminate chemical contamination and remediate its adverse/detrimental effects on the ecosystem health.

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.

Human biomonitoring of PCDDs, PCDFs, and PCBs in women living in a Northern Italy industrial area.

In Brescia , a highly industrialized city in the Lombardy Region (Northern Italy) classified as a SIN (Contaminated Site of National Interest), a human biomonitoring study was carried out on breast milk of two groups of women residing in areas with presumably different levels of exposure to polychlorodibenzo-p-dioxins, polychlorodibenzofurans, and polychlorobiphenyls. This study was aimed at evaluating the possible difference between women living in Brescia and women living far from it but in the same Region. Between 2016 and 2018, 82 women were enrolled (41 "exposed" subjects and 41 "not exposed"), breast milk samples were collected, and a specific questionnaire was administered to the donors. Data obtained were processed by robust regression and Principal Component Factor Analysis. The differences in concentration between the two groups were significant for all the classes of analytes (except for PCDDs). The concentration increase rates from the not exposed to the exposed group resulted highly significant: some PCB congeners showed increase rates more than 1000 ng/g lb per one-unit change of the independent variable. Among the variables significantly associated with the observed concentrations, age showed the greatest influence, while BMI showed a counteracting effect. Consumption of vegetable oil and fruit resulted to possibly influence the chemicals body burden. For the not exposed group, the levels appear to be in line with the decreasing trend (2001-2018) observed for these contaminants in Italy.

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.

[Exploratory biomonitoring study among workers of livestock farms of the Taranto Province]. / Studio esplorativo di biomonitoraggio tra gli allevatori delle masserie della Provincia di Taranto.

OBJECTIVE: to conduct a survey on blood levels of metals and organochlorine compounds (dioxins and PCBs) among workers of livestock farms, and to identify the factors able to explain the magnitude and variability of the measured concentrations. DESIGN: exploratory human biomonitoring study. SETTING AND PARTICIPANTS: a sample of 45 workers from farms (masserie) located in the Province of Taranto was included in the study. The farms, located between 6 and 43 km from the industrial area, are family owned and animals (mainly sheep and goats) are locally reared outdoors. The study subjects have similar eating habits, including food consumption resulting from their production. RESULTS: manganese concentrations and, to a lesser extent, arsenic, cadmium and lead are in the medium-high range of levels observed in the Italian general population. This study does not identify factors able to explain the variability in the blood levels of metals. The amount of dioxins and PCBs, on the other hand, is strongly associated both with subjects age and the distance of farm from the industrial site. CONCLUSION: the results of this survey are suggestive of research hypotheses that need to be confirmed by biomonitoring studies of adequate design and size, in particular the hypothesis that the blood level of dioxins and PCBs decreases with increasing distance from the industrial site. We recommend ad hoc studies to better characterize the exposure of farmers (also associated with agricultural activities), and of the inhabitants of Taranto, to environmental persistent pollutants, also in terms of food matrices locally produced and consumed.

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.

An unusual aggressive presentation of late onset sepsis due to Staphylococcus aureus MRSA producing Panton-Valentine Leukocidin in preterm neonate.

We report an unusual and rare case of infection from methicillin resistant Staphylococcus aureus (MRSA) producing Panton-Valentine leukocidin in a preterm neonate in NICU. On day of life 8, a preterm baby boy suddenly developed arthritis, giant cutaneous abscesses and an osteomyelitic focus with pour clinical condition. This very aggressive presentation of infection from MRSA push us to test Panton-Valentine leukocidin resulted positive and to test contacts to discover the bearer of the germ. MRSA producing Panton-Valentine leukocidin is an unusual case of infection in preterm neonate that has not been reported elsewhere. A very aggressive sepsis in neonates from Staphilococcus aureus should evoke the need to test Panton-Valentine leukocidin to rapidly establish an appropriate treatment. We underline also the importance to test contacts to establish promptly a decontaminant therapy.

Maternal exposures to endocrine disrupting chemicals and hypospadias in offspring.

BACKGROUND: Prenatal exposures to endocrine-disrupting chemicals (EDCs) are suspected risk factors in the etiology of hypospadias. The aim of this case-control study was to test the hypothesis of an association between maternal environmental exposures to EDCs and hypospadias in the offspring. METHODS: Detailed questionnaire data on occupational and dietary exposures to EDCs in the perinatal period were collected from 80 mothers with hypospadiac infants and from 80 mothers with healthy controls within 24 months of childbirth. Maternal exposure to selected EDCs was also ascertained by measuring the concentration of dichlorodiphenyldichloroethylene, hexachlorobenzene, and several polychlorinated biphenyl congeners in the serum of primiparous mothers of 37 cases and 21 controls. RESULTS: The risk to bear an hypospadiac infant was associated with perinatal maternal occupational exposures to EDCs evaluated by a job-exposure matrix: jobs with exposure to one class of EDCs (odds ratios [OR](crude), 2.83; 95% confidence intervals [CI], 1.32-6.07; OR(adjusted), 2.44; 95% CI, 1.06-5.61) and jobs with exposure to more than one group of EDCs (OR(crude), 4.27; 95% CI, 1.43-12.78; OR(adjusted), 4.11; 95%CI, 1.34-12.59). Increase in risk was also found among mothers consuming a diet rich in fish or shellfish (OR(crude), 3.41; 95% CI, 1.42-8.23; OR(adjusted), 2.73; 95%CI, 1.09-6.82). Serum hexachlorobenzene concentration above the median of all subjects was significantly associated with the risk of hypospadias (OR(adjusted), 5.50; 95% CI, 1.24-24.31). CONCLUSIONS: This study, although based on a limited number of cases, for the first time provides evidence of an association between maternal exposure to EDCs, in particular elevated plasma hexachlorobenzene concentration, and the development of hypospadias in the offspring.

A Simple and Rapid Method for Quantitative HPLC MS/MS Determination of Selected Perfluorocarboxylic Acids and Perfluorosulfonates in Human Serum.

Per- and polyfluorinated alkyl substances (PFASs) are ubiquitous environmental contaminants, present in the environment and in the human body. They have raised global concern because of their diffusion in the environment, particularly in water, causing cases of human overexposure due to consumption of contaminated drinking water. Human biomonitoring is the most effective way to characterize human exposure to PFASs, and it is important that as many labs as possible could easily perform this kind of analysis. Analytical methods for quantitation of PFAS mixtures in human serum have been developed, but most of them required materials that are not always easily available in all the laboratories. This paper describes a very simple and accessible HPLC MS/MS method of analysis and quantification of 13 perfluorocarboxylic acids and perfluorosulfonate compounds (belonging to the class of per- and polyfluorinated alkyl substances (PFASs)) in human serum. Method development data provide detailed descriptions of the optimization process in terms of sample preparation, laboratory analysis of human serum samples, determination of analytes by HPLC MS/MS, and describing the pump gradient time, working conditions, and acquisition.

Serum concentrations of perfluorinated alkyl substances in farmers living in areas affected by water contamination in the Veneto Region (Northern Italy).

Human exposure to per- and polyfluorinated alkyl substances (PFASs) is a major public health concern because in the last decades several cases of overexposure of people to PFASs, in particular through contaminated water, occurred worldwide. In 2013-2017 a PFAS drinking water contamination was discovered and investigated in northern Italy (Veneto region) and high PFAS serum levels were detected in exposed people. 629 subjects were enrolled: 257 residing in municipalities in the areas under impact, 250 residing in municipalities in areas at presumed background exposure and 122 farmers living in contaminated rural areas producing and consuming own livestock and vegetables and frequently using well water. The highest PFAS serum concentrations (median PFOA concentrations 40 ng/g) were found in the subgroup of farmers. The main factors influencing PFAS serum levels of farmers were residence area and the related extent of drinking water contamination, gender, years of residence in the municipalities, well water consumption and consumption of own produced food. PFOA serum concentrations in farmers residing in the areas of the Veneto region impacted by PFAS contamination are among the highest found worldwide.

Biomonitoring of perfluorinated compounds in adults exposed to contaminated drinking water in the Veneto Region, Italy.

In 2013 a contamination of drinking water by perfluoroalkylated substances (PFASs) was discovered in areas of the Veneto Region (northern Italy). In this study the exposure to PFASs of people living in the aforesaid areas was characterized: contaminant serum concentrations were measured and compared with those of a control population group living in neighboring areas at background exposure (based on available drinking water data). The enrolled population was also genotyped for the OATP1A2*3 allelic variant, possibly affecting PFAS excretion and hence the internal dose. The difference in PFAS concentrations between exposed and not exposed subjects was significantly larger for nine of the 12 substances analyzed, and confirmed that water contamination had resulted in an appreciable high exposure of the residing population over time. Within the group of exposed subjects, subgroups at different exposure levels were identified. The contamination of drinking water of the residence area was found to be the main factor influencing PFAS serum levels; in addition to water contamination, other relevant influencing factors were sex, the years of residence and raising own livestock. No relationship with the genetic trait for the studied renal transporter was evidenced. These results provide a baseline characterization of PFAS exposure of the monitored population groups for further studies, planned to be carried out in the near future.

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.

Current exposure of Italian women of reproductive age to PFOS and PFOA: A human biomonitoring study.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) concentrations were determined in serum samples collected in 2011-2012 from 549 nulliparous Italian women of reproductive age who resided in six different Italian Regions. Assessment of exposure to perfluorinated compounds was part of a large human biomonitoring study (Project Life Plus "Womenbiopop") that aimed at examining the exposure of women of reproductive age to priority organic pollutants. The median concentrations of PFOS and PFOA were 2.43, and 1.55 ng g(-1), respectively. Significant differences in the concentrations of both compounds were observed among the six Regions. Women from central Italy had the highest levels of both compounds, followed by women from northern Italy, and southern Italy. No differences in the PFOS concentrations were found between women from urban/industrial areas and women from rural areas, whereas the levels of PFOA were significantly higher in women residing in urban/industrial areas than in women residing in rural areas. Taken together, the observed concentrations confirm that the overall exposure of the Italian population is among the lowest observed in industrialized countries. A downward temporal trend in exposure was observed for both compounds when comparing the results from the present study with those assessed in a study conducted in 2008.

Occupational exposure to PCDDs, PCDFs, and PCBs of metallurgical workers in some industrial plants of the Brescia area, northern Italy.

BACKGROUND: The study was carried out in order to respond to public concern on the occupational exposure of metallurgical workers to highly toxic PCDDs, PCDFs, and PCBs in the area of the city of Brescia, northern Italy. OBJECTIVES: The study investigated the effects on the haematic burden of occupational exposures to the aforesaid contaminants in different work environments, attempting to establish causal relationships and providing indications for occupational health preventive measures. METHODS: Chemical concentrations were measured in blood serum of "professionally exposed" (PE) and "not professionally exposed" (NPE) subjects. NPE subjects included industrial administrative employees, Brescia inhabitants, and remote rural people. RESULTS: The central tendency indexes of contaminant cumulative concentrations were higher in PE than in NPE samples (for the mean values: PCDDs+PCDFs, 22.9 vs. 19.5 pgWHO-TEQ(1997)/g lb; DL-PCBs, 26.0 vs. 23.6 pgWHO-TEQ(1997)/g lb; PCDDs+PCDFs+DL-PCBs (TEQ(TOT)), 48.9 vs. 43.1 pgWHO-TEQ(1997)/g lb; Σ(6)[NDL-PCBs], 427 vs. 401 ng g(-1)lb); however, no statistical differences were detected at P=0.05. A significant difference for PCDDs+PCDFs and TEQ(TOT) was observed as the NPE data were progressively reduced to those of the remote rural people. The existence of a differential occupational exposure due to different environments was detected by applying the factor analysis to congener-specific data (analytical profiles). CONCLUSIONS: Findings indicate that metallurgical workers may be exposed to PCDD, PCDF, and PCB more than the general population, in particular due to non-negligible contributions to exposure from workplace ambient air. Findings also suggest that an improvement of preventive measures may be required to avoid chemical overexposure in certain metallurgical workplaces. To identify exposure groups, the DL- and NDL-PCB analytical profiles seemed to be more sensitive to environmental exposure sources/pathways than those of PCDDs and PCDFs.

Placental transfer of persistent organic pollutants: a preliminary study on mother-newborn pairs.

The aim of this study was to characterize the placental transfer of some environmental pollutants, and to explore the possibility of quantitatively predicting in utero exposure to these contaminants from concentrations assessed in maternal blood. Levels of toxic substances such as pesticides (p,p'-DDE, ß-HCH, and HCB), polychlorinated biphenyls (PCBs), perfluorooctane sulfonate (PFOS), and perfluorooctanoic acid (PFOA) were determined in serum samples of 38 pregnant women living in Rome and in samples of cord blood from their respective newborns. The study was carried out in the years 2008-2009. PCB mean concentrations in maternal serum and cord serum ranged from 0.058 to 0.30, and from 0.018 to 0.064 ng/g · fw respectively. Arithmetic means of PFOS and PFOA concentrations in mothers and newborns were 3.2 and 1.4 ng/g · fw, and 2.9 and 1.6 ng/g · fw. A strong correlation was observed between concentrations in the maternal and the foetal compartment for PFOS (Spearman r = 0.74, p < 0.001), PFOA (Spearman r = 0.70, p < 0.001), PCB 153 (Spearman r = 0.60, p < 0.001), HCB (Spearman r = 0.68, p < 0.001), PCB 180 (Spearman r = 0.55, p = 0.0012), and p,p'-DDE (Spearman r = 0.53, p = 0.0099). A weak correlation (p < 0.1) was observed for PCBs 118 and 138.

Perfluorooctanesulfonate and perfluorooctanoic acid exposures of the Italian general population.

The serum concentrations of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) were determined in 230 subjects of the Italian general population. Participants were enrolled in 2008 in two Italian towns (Brescia, Northern Italy, and Rome, Central Italy) and belonged to the three age ranges: 20-35 years, 36-50 years, and 51-65 years. PFOS and PFOA were quantified by HPLC interfaced to a mass spectrometer operating in the electrospray negative mode. Data were acquired using multiple reaction monitoring (MRM). The isotope dilution technique was applied throughout. The median serum concentrations of all participants were 6.31 ng g(-1) and 3.59 ng g(-1) for PFOS and PFOA, respectively, and the pertinent 90th percentiles were 12.38 and 6.92. Men had higher concentrations of PFOS and PFOA than women, regardless of age. The differences were statistically significant in the 20-35 and 36-50 years groups, but not in the 51-65 group. An increase of PFOS and PFOA serum concentrations with age was observed. The Median test showed a statistically significant difference (p<<0.01) between the three age groups for both PFOS and PFOA when applied to the entire dataset (males and females). When the test was applied to the groups of males and females separately, a significant difference was observed for females (p<<0.005) but not for males (p>0.1). The observed strong correlation between PFOS and PFOA concentrations suggests same or similar exposure routes.

Serum concentrations of beta-hexachlorocyclohexane in groups of the Italian general population: a human biomonitoring study.

Because of its persistence and toxicological profile, beta-hexachlorocyclohexane (beta-HCH) has been proposed for inclusion in the Stockholm Convention on persistent organic pollutants (POPs). Although the use of technical HCH, which is the primary source of beta-HCH in the environment, has been banned in the EU in 1978 and progressively at a global level, beta-HCH is still detectable in the general environment worldwide. Human exposure mostly occurs via food and may be of concern in areas where illegal use and/or improper disposal of stockpiles occurred and locally grown food is consumed. Exposure of the Italian general population to beta-HCH has been poorly characterised. Lack of human biomonitoring data severely hinders the ability to interpret potential increases in exposure related to situations of environmental risk. We carried out a human biomonitoring study aimed to provide baseline information on background exposure of the Italian general population to this pollutant. For this purpose, we analysed 116 serum samples from groups of subjects of both sex from the general population residing in three Italian towns at different latitudes. Serum concentrations of beta-HCH resulted to be comprised between 1.64 and 300 ng/g fat, with a median value of 18.0 ng/g fat and a 90th percentile of 65.9 ng/g fat. The serum concentrations detected are in line with those detected in most Western European countries.