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.

Occurrence of perfluorinated alkylated substances in cereals, salt, sweets and fruit items collected in four European countries.

In the context of a European project, 12 perfluoroalkyl acids (PFAAs) were determined in 14 food items collected in four European countries representing northern, southern, eastern and western Europe. This study presents the results of PFAAs measured in fruit, cereals, sweets and salt. Out of the 12 PFAAs, 10 PFAAs were detected in 67% of the samples. Overall, PFOA was the most abundant compound and the highest concentrations were found for PFOS but all were less than 1ngg(-1). When comparing the four countries, highest levels and detection frequencies were observed in Belgium (Western Europe), followed by the Czech Republic (Eastern Europe), Italy (Southern Europe) and finally Norway (Northern Europe). Comparison of profiles and levels is difficult due to variations in constitution of the food categories in the investigated countries and countries of origin of the food items. Dietary intake assessments for PFOS and PFOA show that the daily intake of PFAAs is far below the existing tolerable levels. However, they contribute to the total dietary intake and should therefore be included in future dietary exposure assessments.

Occurrence of selected perfluorinated alkyl acids in lunch meals served at school canteens in Italy and their relevance for children's intake.

Ready-to-eat servings may be more contaminated with perfluorinated alkyl acids (PFAAs) than the corresponding unprocessed foods due to the presence of PFAAs in and transfer from food contact materials (FCM) and cookware. Therefore, the presence of selected PFAAs in meals served weekly at lunch time in six Italian school canteens was assessed. Five towns were selected representing different areas with local water and food supply. Daily lunch menus were sampled and pooled to form a composite. Analyses were carried out on the weekly composite from each canteen. UPLC-MS/MS quantification limits were in the 6.0-12 pg g⁻¹ range for the selected PFAAs (PFHxA, PFOA, PFNA, PFDA, PFUnDA, PFHxS, branched and non-branched PFOS). Non-branched PFOS was quantified in four out of six composites, with levels ranging from 14 to 25 pg g⁻¹, while PFOA and PFDA were determined in two out of six in the range 6.5-8.2 pg g⁻¹. Theoretical estimates and analytical results in the same order of magnitude indicate a negligible contribution from food processing and serving to meal contamination. When composite analytical data are transposed into dietary estimates, it is shown that Italian school-age children have intakes in the range of 0.3-1.1 and 0.5-1.4 ng kg⁻¹ bw day⁻¹ for PFOA and PFOS respectively, well below the corresponding tolerable daily intakes (TDIs).

Polychlorodibenzodioxin and -furan and dioxin-like polychlorobiphenyl distribution in tissues and dairy products of dairy buffaloes.

A pilot study was performed on three different dairy buffalo herds exposed without exposure control conditions to Polychlorodibenzodioxins and -furans (PCDDs, PCDFs) and Dioxin-like Polychlorobiphenyls (DL-PCBs). This study dealt with the relationship between the contamination levels (pg WHO2005-TE/g fat) in individual raw milk and those in edible tissues and with the contamination transfer from farm bulk milk to dairy products. On a cumulative basis, kidney (41, 67, and 21 pg WHO-TE/g fat) resulted more in equilibrium with milk (48, 42, and 20) than did muscle (25, 31, and 9), while liver showed a large bioaccumulation (221, 304, and 75), with marked differences of the congener profile. Mozzarella cheese contamination (23, 42, and 29 pg WHO-TE/g fat) was higher than that of bulk milk (20, 36, and 21), which suggested a role of casein precipitation in congener transfer. The above information could improve the effectiveness of risk management during a "dioxin" crisis.

Perfluorinated alkylated substances in vegetables collected in four European countries; occurrence and human exposure estimations.

The human diet is recognised as one possible major exposure route to the overall perfluorinated alkylated substances (PFAS) burden of the human population, resulting directly from contamination of dietary food items, as well as migration of PFAS from food packaging or cookware. Most European countries carry out national monitoring programs (food basket studies) to monitor contamination with pollutants. Usually, for PFASs, non-coordinated approaches are used in Europe, since food basket studies are mainly carried out by national authorities following national requirements and questions, making comparisons between different countries difficult. A harmonised sampling campaign collecting similar food items in a uniform procedure enabling direct comparison between different regions in Europe was designed. We selected four countries (Belgium, Czech Republic, Italy and Norway), representing the four regions of Europe: West, East, South and North. In spring 2010 and 2011, 20 different types of vegetables were sampled in Belgium, Czech Republic, Italy and Norway. Perfluorinated carboxylic acids (PFCAs) were the main group of detected PFASs, with perfluorinated octanoic acid (PFOA) as the most abundant PFCA (with exception of samples from Czech Republic), followed by perfluorinated hexanoic acid and perfluorinated nonanoic acid. Dietary intake estimates for PFOA show only low human exposure due to vegetable consumption for adults and children, mostly governed by high intake of potatoes.

Polychlorodibenzodioxin and -furan (PCDD and PCDF) and dioxin-like polychlorobiphenyl (DL-PCB) congener levels in milk of grazing sheep as indicators of the environmental quality of rural areas.

An observational study was set up to evaluate how the quality of the environment may influence the levels of of PCDDs, PCDFs, and DL-PCBs in sheep's milk. Seven farms under natural and anthropogenic pressures were considered, along with an inventory of the surrounding regular and natural sources of emissions. Analysis by HRGC-HRMS revealed the highest cumulative levels (2.1 pg of WHO(1998)-TE/g fat) in one organic and one conventional farm, each close to a relevant bushfire. Their pattern was characterized by a noticeable contribution (24%) from mono-ortho-PCB congeners to the cumulative WHO-TE. For the other farms, close to potential anthropogenic sources, the levels recorded in milk ranged from 0.7 to 1.3 pg of WHO-TE/g fat. The health and reproductive indicators were in all herds within the physiological range. Results suggest the environmental quality in extensive farming system should be eligible as a food safety factor, also for organic productions.

Bioaccumulation of dioxin-like substances and selected brominated flame retardant congeners in the fat and livers of black pigs farmed within the Nebrodi Regional Park of Sicily.

An observational study was designed to assess the bioaccumulation of polychlorodibenzodioxins (PCDD) and polychlorodibenzofurans (PCDF), dioxin-like polychlorobiphenyls (DL-PCB), and 13 selected polybromodiphenylethers (PBDE) in autochthonous pigs reared in the Nebrodi Park of Sicily (Italy). Perirenal fat and liver samples were drawn from animals representative of three different outdoor farming systems and from wild pigs and then analyzed for the chemicals mentioned previously. The highest concentrations of PCDD + PCDF and DL-PCB were detected in the fat (0.45 and 0.35 pg World Health Organization toxicity equivalents [WHO-TE] per g of fat base [FB], respectively) and livers (12.7 and 3.28 pg WHO-TE per g FB) of the wild group, whereas the free-ranging group showed the lowest levels (0.05 and 0.03 pg WHO-TE per g FB in fat and 0.78 and 0.27 pg WHO-TE per g FB in livers). The sum of PBDE congeners was highest in wild pigs (0.52 ng/g FB in fat and 5.64 ng/g FB in livers) and lowest in the farmed group (0.14 ng/g FB in fat and 0.28 ng/g FB in livers). The contamination levels in fat and livers of outdoor pigs had mean concentration values lower than those levels reported for intensively indoor-farmed animals. In wild pigs, bioaccumulation was associated with their free grazing in areas characterized by bush fires. The results of this study aid to emphasize the quality of the environment as a factor to guarantee food safety in typical processed pig meat products, specifically from outdoor and extensive Nebrodi farming systems.

Hormetic effect(s) of tetracyclines as environmental contaminant on Zea mays.

Animal wastes from intensive pig farming as fertilizers may expose crops to antimicrobials. Zea mays cultivations were carried out on a virgin field, subjected to dressing with pig slurries contaminated at 15 mg L(-1) of Oxy- and 5 mg L(-1) of Chlor-tetracycline, and at 8 mg L(-1) of Oxy and 3 mg L(-1) of Chlor, respectively. Pot cultivation was performed outdoor (Oxy in the range 62.5-1000 ng g(-1) dry soil) and plants harvested after 45 days. Tetracyclines analyses on soils and on field plants (roots, stalks, and leaves) did not determine the appreciable presence of tetracyclines. Residues were found in the 45-day pot corn only, in the range of 1-50 ng g(-1) for Oxy in roots, accounting for a 5% carry-over rate, on average. Although no detectable residues in plants from on land cultivations, both experimental batches showed the same biphasic growth form corresponding to a dose/response hormetic curve.

Temporal and spatial covariation of gender and oxidative stress in the Galápagos land iguana Conolophus subcristatus.

Abstract Physiological responses to organismal stress can have direct impacts on individual fitness. While responses to stressors mediated by glucocorticoid hormones are well studied, the regulation of the redox system via pro-oxidant and antioxidant balance as well as the natural causes of oxidative stress in nature remain poorly known, especially for reptiles. In this study, we investigate the interpopulation and intersex variation in oxidative damage and plasma antioxidant capacity in the Galápagos land iguana, Conolophus subcristatus, over a 3-yr study to evaluate what factors (e.g., season, food availability, reproductive activity) can explain levels and patterns of oxidative damage and of plasma antioxidant capacity. Our results indicate that (1) males showed lower levels of oxidative damage, higher levels of plasma antioxidant capacity, and better body condition than females and (2) significant interactions exist among patterns of oxidative damage across sexes, sampling localities, body condition, and season. These results suggest that reproductive activity and food abundance might act as determinants shaping levels and patterns of oxidative stress of land iguanas.

PCDD and PCDF depletion in milk from dairy cows according to the herd metabolic scenario.

High level of PCDD+PCDF contamination in bulk milk (9.7 pg WHO-TE g(-1) fat) from 1604 Holstein Fresian lactacting cows was observed just four weeks after the beginning of their exposure to a feed supplement contaminated at 10.4 ng WHO-TE kg(-1) dry matter. In-farm produced hay and silage showed levels not exceeding 0.2 ng WHO-TE kg(-1) dry matter. After the supplement withdrawal, it was possible to monitor the depletion phase for a following 75-day period in milk, until the levels dropped well below 3.0 pg WHO-TE g(-1) fat, the EU regulatory Maximum Residue Level for PCDD+PCDF. During this phase, the half-life was calculated as 17+/-3 days, on WHO-TEQ basis. The full availability of farm data on both cow nutrition and milk production allowed the calculation of the carry-over rate (COR) (PCDD+PCDF milk excretion vs. feed), which was 46% at the end of the exposure. This COR value is justified from the main TE contribution of Penta-CDD and -CDF congeners (63%), and the half-life is among the shortest of all those described in the literature both for experimental and naturally-exposed dairy cows. A fugacity-based model predicts a bulk milk contamination of 5 pg WHO-TE g(-1) fat, compared to the 10 pg WHO-TE g(-1) fat level observed. Such findings are discussed in light of the lactation and metabolic status of the herd for which the transition period, characterised by a negative metabolic energy balance and a consequent adipose tissue mobilization, could play a relevant role.

Oxytetracycline as environmental contaminant in arable lands.

Oxytetracycline (OXY) is a broad-range antimicrobial routinely used in pig production, at doses in the range of few g/kg of medicated feed, during the weaning period. It could persist at ppm level in pig liquid manure that routinely is used for organic fertilisation. In the present work we describe a methodology to study OXY environmental fate in arable land where crops are cultivated for animal feeding purposes. A liquid-liquid extraction followed by metal chelate affinity chromatography was applied to environmental samples of manures and soils drawn within a case-control study. Extracts were then analysed by high performance liquid chromatography with UV/DAD detection, using a reverse phase column, and expressing the results as 4-epioxytetracycline epimer. Results indicate OXY is well retained at mg kg(-1) levels in soil exposed to contaminated pig manure fertilisation. Such compartment could constitute an abiotic reservoir for the systemic and/or for the external contamination of corn.