Air concentrations of trace elements in a municipality under the influence of Tarragona petrochemical complex: Human health risks.

One of the largest petrochemical complexes of southern Europe is located in Tarragona County (Catalonia, Spain). Despite environmental monitoring is routinely conducted in the area, the long-term occurrence of airborne trace elements has been poorly investigated. In the present study, the concentrations of arsenic (As), cadmium (Cd), chromium (Cr), nickel (Ni), lead (Pb) and vanadium (V) were analysed in air samples collected in El Morell, a town potentially impacted by the petrochemical. Air samples were simultaneously collected in the town of Cambrils, as a background site. Meteorological data and retro trajectories analysis were used to evaluate the impact of the petrochemical industry on the levels of trace elements in air. Subsequently, human health risks due to inhalation exposure to the trace elements were also assessed. Except for V, air concentrations were significantly higher near the oil refinery than the background levels. Human health risks were also estimated to be higher in the vicinity of the petrochemical complex. In turn, air inhalation of Pb and V was higher than their dietary intakes. The present data should be considered only as preliminary, since the sampling was taken during only three weeks, which is an insufficient period to extract reliable conclusions. Further long-term studies should be focused on assessing the influence of temporary variables, such as meteorological conditions and fugitive or sporadic emissions.

Levels and health risk assessment of twenty-one current-use pesticides in urban and riverside waters of the Brazilian Amazon Basin.

In Brazil, the favorable weather conditions and abundant land contribute to the thriving agricultural production. Brazilian crops extensively employ pesticides due to their high efficacy, cost-effectiveness, and permissive regulatory framework. However, pesticide use also endangers water resources, animal organisms, and human health. Due to the lack of data on pesticide use in the Amazonas forest-based Brazil, the present study aimed to assess the levels of twenty-one current-use pesticides (CUPs) from five different classes in river waters collected from urban and riverside areas in this region. Moreover, the non-carcinogenic risks associated with water consumption were also characterized. Thirteen CUPs were detected in concentrations above the limit of detection (LOD) in at least one of the water samples, and most pesticides were detected in riverside areas. In contrast, only 18% of the analyzed samples were considered "clean," with only one compound detected. Fenitrothion showed the highest concentration, with a mean value of 4.86 ng/mL (0.30-14.3 ng/mL). Up to 33% of the samples showed levels of fipronil above the LOD, an issue of environmental and human health concern, mainly because of the adverse effects observed in honeybees. Despite this, the human health risk assessment showed a target hazard quotient below one (HQ < 1) in adults for all substances, suggesting that pesticide exposure through water consumption should not mean risk for the riverside populations. Taking into account the large extension of Brazil, as well as its different agricultural practices throughout the country, it would be of great importance to conduct extensive research in other areas. It would help to gain knowledge in this field and to promote eco-friendly alternatives to mitigate pesticide use and, consequently, to reduce their potential adverse effects on human health and the ecosystems.

Regulatory compliance of PCDD/F emissions by a municipal solid waste incinerator. A case study in Sant Adrià de Besòs, Catalonia, Spain.

Despite incineration is an important emission source of toxic pollutants, such as heavy metals and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), it is still one of the most widely used methods for the management of municipal solid waste. The current paper summarizes the results of a 20-year follow-up study of the emissions of PCDD/Fs by a municipal solid waste incinerator (MSWI) in Sant Adrià de Besòs (Catalonia, Spain). Samples of ambient air, soils and herbage were periodically collected near the facility and the content of PCDD/Fs was analyzed. In the last (2017) survey, mean levels in soil were 3.60 ng WHO-TEQ/kg (range: 0.40-10.6), being considerably higher than the mean concentrations of PCDD/Fs in soil samples collected near other MSWIs in Catalonia. Moreover, air PCDD/F concentrations were even higher than those found in a previous (2014) survey, as they increased from 0.026 to 0.044 pg WHO-TEQ/m3. Ultimately, the PCDD/F exposure would be associated to a cancer risk (2.5 × 10-6) for the population living in the surrounding area. Globally, this information indicates that the MSWI of Sant Adrià de Besòs could have had a negative impact on the environment and potentially on public health, being an example of a possible inappropriate management for years. The application of Best Available Techniques to minimize the emission of PCDD/Fs and other chemicals is critical.

Urinary concentrations of heavy metals in pregnant women living near a petrochemical area according to the industrial activity.

BACKGROUND: The progressive industrialization has resulted in an increase in heavy metal pollution in the environment, which has a dangerous impact on human health. Prenatal exposure to heavy metals, even at very low concentrations, may be especially harmful to pregnant women and their children. Different industrial activities can contribute to heavy metal pollution in a specific area. OBJECTIVE: 1) To explore the concentrations of heavy metals in urine samples of pregnant women, and 2) to evaluate the potential effect of different industrial activities in Tarragona (Spain). METHODS: Urinary levels of four heavy metals (nickel (Ni), cadmium (Cd), mercury (Hg), and lead (Pb)) from 368 pregnant women recruited in the ECLIPSES study were analyzed. Home addresses and all the industries potentially releasing heavy metals were geo-referenced. Buffer zones were established within a 1.5, 3, and 5 km radius at the center of each industry. Subsequently, the number of participants living in and out of each buffer zone was recorded. RESULTS: Urinary levels of Ni and Cd, but not those of Hg and Pb, were obviously increased in pregnant women living near most of the industrial sites. After adjustment for potential co-variates, only Cd showed notable differences according to the industrial activity. Compared to women living outside the buffer, Cd levels were increased in those living within 1.5 and 3 km of chemical industries, within 5 km of energy industries, within 1.5, 3, and 5 km of mineral industries, and within 3 and 5 km of metal processing industries. CONCLUSION: Among the analyzed heavy metals, Cd showed an increasing trend in urinary concentrations in women living near chemical, energy, mineral, and metal processing industries. This study highlights the need to develop legislative measures to minimize Cd exposure, especially by sensitive populations. Moreover, additive or synergistic effects of co-exposure to other air pollutants should not be disregarded.

Screening of regulated aromatic amines in clothing marketed in Brazil and Spain: Assessment of human health risks.

Azo dyes used in textile products contain aromatic amines (AAs), which may be released into the environment after skin bacteria cleavage the azo bond. In Europe, 22 carcinogenic AAs are regulated. Unfortunately, no information is available in many non-European countries, including Brazil. This study aimed to determine the concentrations of 20 regulated AAs in clothes marketed in Brazil and Spain. Generally, higher levels of regulated AAs were found in samples sold in Brazil than in Spain, which is linked to the lack of regulation. Sixteen AAs showed concentrations above 5 mg/kg in samples commercialized in Brazil, while 11 exceeded that threshold in Spain. Regulated AAs with levels above 5 mg/kg were more found in synthetic clothes of pink color. Concentrations in clothing were also used to evaluate the dermal exposure to AAs in 3 vulnerable population groups. The highest exposure corresponded to 2,4-diaminoanisole for toddlers in Brazil and 4,4-oxydianiline for newborns in Spain. Non-cancer risks associated with exposure to 4,4-benzidine by Brazilian toddlers was 14.5 (above the threshold). On the other hand, 3,3-dichlorobenzidine was associated with potential cancer risks for newborns and toddlers in Brazil. Given this topic's importance, we recommend conducting continuous studies to determine the co-occurrence of carcinogenic substances.

Clothing as a potential exposure source of trace elements during early life.

In recent years, the interest in determining the chemical composition of textile products has increased among the scientific community and regulatory agencies, driven by toxicological issues and environmental concerns. Chemical elements are naturally present in clothing as natural fibers or intentionally added during manufacture. Some of them show physical-chemical properties that allow their absorption through the skin. In addition, chronic situations increase the dermal exposure capacity. Because of age-specific behavioral characteristics and underdeveloped physiological function, children may be especially sensitive to exposure to trace elements. This study aimed to analyze the levels of twenty trace elements in 120 clothing items commercialized in Spain. Textile products for pregnant women and children <36 months old were included. The potential health implication of this dermal exposure in early life was also evaluated. Aluminum, zinc, and titanium showed the highest concentrations, with median levels of 27.6, 5.6, and 4.2 mg/kg, respectively. Since chromium is employed as a metal complex dye in synthetic fibers, high levels of this element were found in black polyester. Dermal exposure to titanium, which is a ubiquitous element in clothes made of synthetic fibers, was associated with a hazard quotient (HQ) higher than the threshold value (HQ > 1), with values of 1.13 for pregnant women and 1.22 for newborns. On the other hand, HQ values of other elements and cancer risks were lower than the recommended values. Assessing early-life exposure to toxic elements can help to identify potential sources and to prevent or reduce human exposure, mainly in vulnerable groups.

Multidrug-resistant Enterobacter spp. in wastewater and surface water: Molecular characterization of ß-lactam resistance and metal tolerance genes.

Among the ESKAPE group pathogens, Enterobacter spp. is an opportunistic Gram-negative bacillus, widely dispersed in the environment, that causes infections. In the present study, samples of hospital wastewater, raw and treated urban wastewater, as well as surface receiving water, were collected to assess the occurrence of multidrug-resistant (MDR) Enterobacter spp. A molecular characterization of ß-lactam antibiotic resistance and metal tolerance genes was performed. According to identification by MALDI-TOF MS, 14 isolates were obtained: 7 E. bugandensis, 5 E. kobei, and 2 E. cloacae. The isolates showed resistance mainly to ß-lactam antibiotics, including those used to treat infections caused by MDR bacteria. Multiple antibiotic resistance index was calculated for all isolates. It allowed verify whether sampling points showed a high risk due to antibiotic resistant Enterobacter spp., as well as to determine if the isolates have been in environments with a frequent antibiotic use. Twelve isolates showed ß-lactam antibiotic resistance gene, being the blaKPC widely detected. Regarding metal tolerance, 13 isolates showed at least two genes that encode metal tolerance mechanisms. Overall, metal tolerance mechanisms to silver, copper, mercury, arsenic and tellurium were found. New data on metal tolerance mechanisms dispersion and antibiotic-resistance characterization of the E. bugandensis and E. kobei species were here provided. The occurrence of MDR Enterobacter spp. in analyzed samples draws attention to an urgent need to put control measures into practice. It also evidences waterborne spread of clinically important antibiotic-resistant bacteria recognized as critical priority pathogens.

Recent trends in pesticides in crops: A critical review of the duality of risks-benefits and the Brazilian legislation issue.

Due to the increasing population worldwide, in recent years, an exponential increase in agricultural practices has occurred in order to attend to the growing demand for food. Unfortunately, this increase is not associated with the supply of foodstuffs free of environmental pollutants. In Brazil, agriculture is one of the most important economic pillars, making the country one of the largest consumers of pesticides around the world. The intense use of pesticides, mainly glyphosate, 2,4-D, and atrazine, constitutes an essential factor in the viability of this great agricultural productivity. Sugarcane, corn, soybean, and citrus crops consume around 66% of the total pesticides worldwide, representing 76% of the planted area. Pesticide residues have been frequently detected in food and the environment, becoming a significant concern for human health. Monitoring programs for pesticide use are essential to reduce the potential negative impacts on the environment and improve the overall efficiency and sustainability of their use. However, in Brazil, the approval status of pesticide-active ingredients is very discrepant compared to other agricultural countries. Moreover, the duality of benefits and risks of pesticide application creates an economic and toxicological conflict. In this paper, we have critically reviewed the duality of risks-benefits of the use of pesticides in agriculture and the current Brazilian legislation issues. We have also compared this flawed legislation with other countries with high economic potential. Due to the negative environmental impacts on soil and water by the high levels of pesticides, remediation techniques, sustainable agriculture, and the development of new technologies can be considered some viable alternatives to reduce the levels in these compartments. Besides, this paper includes some recommendations that can be included in the coming years.

Non-regulated aromatic amines in clothing purchased in Spain and Brazil: Screening-level exposure and health impact assessment.

The staggering amount of chemicals in clothes and their harmful effects on human health and the environment have attracted the attention of regulatory agencies and the scientific community worldwide. Azo dyes are synthetic dyestuffs with widespread use in textile industries, currently classified as emerging pollutants of great health concern to consumers. These compounds may release one or more aromatic amines (AAs) after reductive cleavage of their azo bounds. Twenty-two AAs have already been regulated due to their carcinogenic effects. However, since information on their potential toxicity is not currently available, several AAs have not been still regulated by the European Union. Considering this gap, the present study aimed to assess the levels of forty non-regulated AAs in 240 clothing items from Spain and Brazil. The potential impact on the health of vulnerable population groups after dermal exposure to those garments was also evaluated. In Brazil, at least one AA was detected in the clothes, while in samples obtained in Spain, only two of them showed values below the limit of detection for AAs. In 75 clothes, at least one of the measured AAs was higher than the hazardous threshold (30 mg/kg), which can mean risks to human health since these compounds are suspected to be mutagenic. Aniline, the most common AA, showed a high detection rate (82%) in clothes, with significantly higher concentrations in items commercialized in Brazil (0.35 vs. 0.17 mg/kg; p = 0.032). Moreover, o-aminobenzenesulfonic and p-phenylenediamine, suspected mutagenic, were found at relevant concentrations in several clothes, mainly made of synthetic fibers. In this study, the hazard index associated with exposure to AAs through clothing was low (0.006-0.13) for all the population groups of both countries in the medium-bound scenario. However, its value was close to 1 for Brazilian pregnant women (0.998) when the maximum concentration value was considered under an upper-bound scenario. The risk of exposure to non-regulated AAs may be underestimated since only dermal exposure was considered for risk assessment. Moreover, the co-occurrence of other carcinogenic and non-carcinogenic substances present in skin-contact clothes should mean an additional source of potential risk.

Effects of air pollution on the potential transmission and mortality of COVID-19: A preliminary case-study in Tarragona Province (Catalonia, Spain).

The number of studies published on COVID-19 in recent months is certainly impressive. However, there are still important gaps to know a great number of characteristics of this disease. Among these, some potential ways of transmission of the SARS-CoV-2 and the different reasons for the severity of the disease in different people. Various studies have suggested that certain air pollutants could be increasing the transmission of the coronavirus, as well as the risks of COVID-19 incidence and mortality. In the present preliminary case-study conducted in Tarragona Province (Catalonia, Spain), we studied the potential association of COVID-19 with PM10, NO2 and O3, as well as the differences in the incidence and lethality of this disease. This Province is divided into two "health regions": Camp de Tarragona, with an important industrial complex, and Terres de l'Ebre, with a great agricultural component. In spite of the notable limitations of the current study, our preliminary findings indicate that the industrialized/urban areas of Tarragona Province show a higher incidence and mortality of COVID-19 than the agricultural/rural zones. These - and previous - results would highlight the importance of conducting specific investigations focused on directly assessing whether air pollutants such as particulate matter can act as carriers of the SARS-CoV-2. If confirmed, the recommendation on keeping the "social distance" (1.5-2 m) might need to be adapted to this situation.

Human biomonitoring of bisphenol A along pregnancy: An exposure reconstruction of the EXHES-Spain cohort.

This study was aimed at reconstructing the exposure to bisphenol (BPA) of 60 pregnant women from the EXHES-Spain cohort. A biomonitoring study was conducted by determining BPA levels in urine samples over the three trimesters of pregnancy. Moreover, the correlations between BPA levels and the role of different potential exposure sources, with special emphasis on the dietary intake, were also studied. Urine samples were subjected to dispersive liquid-liquid microextraction and the subsequent analysis via gas chromatography-mass spectrometry. BPA was detected in 76% of the urine samples. A significant decrease of urinary BPA levels was observed along pregnancy, as mean concentrations of creatinine-adjusted BPA were 4.64, 4.84 and 2.51 µg/g in the first, second and third trimester, respectively. This decrease was essentially associated with changes in the dietary habits of the pregnant women, including a lower intake of canned food and drinks. However, the potential role of other pregnancy-related biochemical or physiological factors should not be disregarded. Very interestingly, significant differences in urine BPA levels were found according to the fruit consumption pattern, as women who ate more citrus fruits showed lower BPA concentrations in urine. The reconstructed exposure to BPA was estimated in 0.072, 0.069 and 0.038 µg BPA/kg of body weight/day in the first, second and third trimesters, respectively. These values are far below the temporary tolerable daily intake (t-TDI) established by the EFSA.

Health risks for the population living near petrochemical industrial complexes. 1. Cancer risks: A review of the scientific literature.

Petrochemical complexes and oil refineries are well known sources of a wide range of environmental pollutants. Consequently, the potential harmful health effects of living near these facilities is a topic of concern among the population living in the neighborhood. Anyhow, the number of studies carried out on this issue is rather limited and, in some cases, results are even slightly contradictory. The present Review was aimed at assessing whether living in the vicinity of petrochemical industries and oil refineries is associated with a higher incidence of cancer and cancer mortality. In this sense, up to 23 investigations were found in PubMed and Scopus databases. According to the type of cancer, leukemia and other hematological malignancies were reported as the main types of cancer for populations living in the neighborhood of petrochemical industries. This was concluded based on studies performed in Taiwan, Spain, United Kingdom, Italy and Nigeria. In contrast, no association was found in 4 different investigations conducted in Sweden, Finland and USA with the same purpose. Other scientific studies reported a high incidence of lung and bladder cancer in Taiwan, Italy and USA, as well as an excess mortality of bone, brain, liver, pleural, larynx and pancreas cancers in individuals living near petrochemical complexes from Taiwan, Spain, Italy, United Kingdom and USA. Thus, human exposure to certain carcinogenic pollutants emitted from petrochemical industries might increase the incidence of some cancers and cancer mortality. Anyway, since the limited number of investigations conducted until now, further studies are required in order to corroborate -in a more generalized way-this conclusion.

Human exposure to trace elements, aromatic amines and formaldehyde in swimsuits: Assessment of the health risks.

Nowadays, most of the swimsuits are mainly made of artificial fibres, which have interesting properties such as water repellence and fast drying. Swimsuits contain a wide range of additives, which can mean a hazard for the environment and/or human health. In this study, the concentrations of formaldehyde (free and water soluble), 24 aromatic amines, and 28 trace elements (Ag, Al, As, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sb, Sc, Se, Sm, Sr, Sn, Tl, Ti, V and Zn) were analysed in 39 swimsuits covering a wide range of materials, colours and brands. Dermal exposure and health risks were assessed for adults (men and women) aged > 18 years old, babies between 2 and < 3 years old, children (boys and girls) between 3 and < 6 years old and 6 and < 11 years old, and teenagers (boys and girls) between 11 and < 16 years old, wearing swimsuits for 4 h or 8 h. Formaldehyde and aromatic amines were below their respective detection limits in all samples (<16 and < 1.5 mg/kg, respectively). Regarding trace elements, Ti showed the highest mean levels (1844 mg/kg), being significantly higher in polyamide (3759 mg/kg) than in polyester (24.1 mg/kg) swimsuits. These high Ti levels were confirmed by environmental scanning electron microscope in a single sample made of polyamide. Increased concentrations of Cr were also observed, but only in polyamide black fabrics, with values ranging from 624 to 932 mg/kg. Non-cancer risks (hazard quotients) derived from the exposure to trace elements were in a safe zone for all analysed trace elements. Furthermore, the carcinogenic risks were evaluated for As, Cr and Pb, exhibiting values below the 10-5 threshold, with the exception of Cr in babies and children-girls. For Ti, health risks could not be calculated due to the lack of information on toxicological data. However, because Ti was the element with the highest concentrations in swimsuits, and taking into account the potential toxicity of TiO2 nanoparticles, further research is needed to assess the migration of this element from fibres to skin.

Essential and toxic elements in human milk concentrate with human milk lyophilizate: A preclinical study.

Concentrated human milk (HM-concentrate) can be obtained from the simple and inexpensive method of donated breast milk direct lyophilization. A previous study reported that HM-concentrate contains the adequate amount of main macro- and micronutrients for use as a nutritional resource for preterm infants with very low birth weight admitted to neonatal intensive care units. However, further details need to be elucidated about HM-concentrate composition, particularly its content of essential and potentially toxic trace elements. Therefore, this study aimed to determine the concentration of essential and toxic elements in human milk considered baseline (HM-baseline) and HM-concentrate, as well as to quantify changes in concentration of these elements after the HM concentration process. The concentration of Aluminum, Arsenic, Cadmium, Chromium, Iron, Mercury, Manganese, Nickel, Lead, Selenium, Tin, and Thallium was analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). Moreover, Bayesian linear mixed effect models were applied to estimate the mean difference between HM-baseline and HM-concentrate samples. After comparison (HM-concentrate versus HM-baseline), a significant increase in concentration was observed only for Manganese (0.80 µg/L; 95% CrI [0.16; 1.43]) and Selenium (6.74 µg/L; 95% CrI [4.66; 8.86]), while Lead concentration (-6.13 µg/L; 95% CrI [-8.63; -3.61]) decreased. This study provides latest and reliable information about HM composition. After milk concentration by lyophilization, there was a significant increase only in the essential elements Manganese and Selenium. The essential micronutrient content in HM-concentrate was similar or higher than that in preterm mothers' milk, which suggests it is viable for nutritional support of preterm infants. In addition, the low concentrations of potentially toxic elements in HM-concentrate indicates that it is safe for consumption by premature newborns.

Human exposure to per- and polyfluoroalkyl substances (PFAS) through drinking water: A review of the recent scientific literature.

Per- and polyfluoroalkyl substances (PFAS) are a group of water-soluble chemical compounds with an important number of applications, which have been widely used during the last 60 years. Two of them, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are the most known and well investigated. As for many other organic substances that are of environmental concern, the diet is the main route of human exposure to PFAS. However, in certain cases drinking water may also mean a significant contribution to human exposure, and to a lesser extent, dust and air (indoor exposure). In recent years, the environmental persistence of PFAS, their biomagnification in food webs, as well as their potential accumulation and toxicity, have generated a notable interest, which has been evidenced by the considerable number of publications in this regard. Recently, we carried out a wide revision on the levels of PFAS in food and human dietary intake. In the current review, we have summarized the recent information (last 10 years) published in the scientific literature (Scopus and PubMed) on the concentrations of PFAS in drinking water and the human health risks derived from the regular water consumption, when available. A large amount of data belongs to PFOS and PFOA and corresponds to studies mainly conducted in countries of the European Union, USA and China, although no information is available for most countries over the world. According to the toxicological information about PFAS that is so far available, the current health risks for the regular consumers of municipal/tap water do not seem to be of concern according to the levels considered as acceptable for various regulatory institutions.

Risk assessment due to dermal exposure of trace elements and indigo dye in jeans: Migration to artificial sweat.

The concentration of a number of trace elements (Ag, Al, As, B, Ba, Be, Bi, Cd, Cr, Co, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, Sc, Se, Sm, Sr, Sn, Tl, Ti, V and Zn) were determined in 42 commercialized denim garments (jeans and shirts), being dermal exposure subsequently assessed. Migration experiments with artificial acid and basic sweat were also conducted to determine the release of these elements, as well as indigo dye. In a similar way than for the total content, Mg (124 and 99.4 µg/g) and Mn (27.1 and 7.20 µg/g) showed the highest concentrations in both artificial sweat, acid and basic, respectively. Indigo dye migrated at levels ranged from 3.22 to 7.76 mg/g, being higher in dark than in light blue fabrics. The levels of trace elements and indigo were analysed according to materials of fabric, colour, brand, and eco-labelling. Using total content and migrations rates, dermal exposure to trace elements for adult men, women and teenagers were calculated under the two sweat extractions. Non-carcinogenic and carcinogenic risks due to dermal exposure to the elements here analysed in cloths were assessed. Both risks were in the limits of safe to according to international regulations. However, the maximum exposure to Sb reached a hazard quotient (HQ) of 0.3 in clothes partially made of polyester. Despite some authors have established that indigo is an agonist of the aril receptor, health risks due to exposure to indigo dye were not calculated due the lack of toxicological data.

Metals in biological tissues of the population living near a hazardous waste incinerator in Catalonia, Spain: Two decades of follow-up.

During the period 1996-1998, a hazardous waste incinerator (HWI) was built in Constantí (Tarragona County, Catalonia, Spain). Because of the potential adverse effects of toxic emissions, mainly metals and dioxins and furans, waste incinerators in general have been an important cause of concern for the public opinion. For that reason, to assess its environmental impact on the surroundings, as well as the potential human health risks of the HWI, environmental and biological monitoring studies have been carried out since 1996-1998, when the baseline concentrations were established. This article summarizes all the results corresponding to metals in biological tissues of the population living near the HWI, two decades after the construction of the facility. In 1996-1998, the baseline concentrations of a number of elements (As, Be, Cd, Cr, Hg, Mn, Ni, Pb, Sn, Tl and V) were determined in samples of hair, blood and autopsy tissues (bone, brain, liver, lung and kidney) of subjects living in the area. In successive 5-year periods, new surveys were conducted to periodically measure the levels of metals in the same biological tissues. The daily dietary intake of these metals was also estimated for the population of the area. The results of this surveillance program do no suggest additional adverse health risks of metals for the population living near the HWI. However, special attention should be paid to Cr, due not only to the increases of this element observed in most analyzed biological tissues, but also in its dietary intake.

Monitoring dioxins and furans in plasma of individuals living near a hazardous waste incinerator: Temporal trend after 20 years.

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in 40 plasma samples of individuals living in zones under potential influence of the emissions of a hazardous waste incinerator (HWI) (Tarragona County, Catalonia, Spain). Samples corresponded to subjects of different gender, age and specific areas of residence. The levels of PCDD/Fs were compared to those obtained in a baseline study (1998), as well as in previous surveys (2002, 2007 and 2012). The current mean concentration of PCDD/Fs in plasma was 6.79 pg I-TEQ/g lipid, which was significantly lower than the baseline concentration (27.0 pg I-TEQ/g lipid). A significant decrease was also observed in comparison to the results obtained in 2002 and 2007 (15.7 and 9.4 pg I-TEQ/g, respectively), while the current PCDD/F levels were similar to those obtained in 2012 (6.18 pg I-TEQ/g lipid). This important reduction in plasma PCDD/F levels is in accordance with the decreasing trend in the daily dietary intake of PCDD/Fs, which diminished from 210.1 pg I-TEQ (baseline) to 8.54 pg WHO-TEQ (current). OCDD was the predominant congener in plasma, while 2,3,7,8-TeCDD and 1,2,3,4,7,8,9-HpCDF showed the lowest levels. Based on the above results, as well as other recent data on the levels of PCDD/Fs in human milk, we conclude that the presence of the HWI does not mean additional and significant risks -as regards to PCDD/F exposure-for the population living in the neighborhood of the facility.

Quantification of eight bisphenol analogues in blood and urine samples of workers in a hazardous waste incinerator.

Bisphenol A (BPA) has been widely used in the manufacture of polycarbonate plastic and epoxy resins. In recent years, producers have started replacing BPA by other chemical analogues, such as bisphenol -S (BPS) and -F (BPF), all of them under the label "BPA-free". However, despite bisphenol (BP) analogues have a very similar structure, their endocrine-disrupting properties could differ from those of BPA. Unfortunately, information regarding human exposure to BP analogues is very limited, not only as single substances, but also as chemical mixtures. The aim of this study was to determine the levels of 8 BP analogues (A, S, F, B, AF, Z, E, and AP) in biological samples from a controlled cohort of workers in a hazardous waste incinerator (HWI) located in Constantí (Catalonia, Spain). Firstly, a chemical method to analyze a mixture of those 8 analogues in total blood and urine was optimized, being samples quantified by means of gas chromatography coupled to mass spectrometry (GC-MS). Furthermore, a biomonitoring study was performed by collecting samples of total blood and urine of 29 people working in the HWI. Among the 8 BP analogues assessed, BPA presented the highest levels in both biological samples, with mean total (free + conjugated) BPA concentrations of 0.58 and 0.86 µg/L in blood and urine, respectively. Free vs. total BPA levels presented a mean percentage of 79% in blood and 19% in urine. Beyond BPA, traces of BPB were also found in a single sample of blood. Furthermore, none of the remaining BP analogues was detected in blood or urine. Despite BPA has been regulated, it is still very present in the environment, being human exposure to this chemical still an issue of concern for the public health.

Prenatal exposure to PFOS and PFOA in a pregnant women cohort of Catalonia, Spain.

This study was aimed at assessing the prenatal exposure to perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a cohort of pregnant women living in Reus (Tarragona County, Catalonia, Spain). These chemicals were biomonitored in maternal plasma during the first trimester of pregnancy, at delivery, and in cord blood. The dietary exposure of PFOS and PFOA was estimated by using questionnaires of food frequency and water intake, as well as data on food levels previously reported in the same area. In addition, the exposure through air inhalation and indoor dust ingestion was also calculated. Finally, a physiologically-based pharmacokinetic (PBPK) model was applied in order to establish the prenatal exposure of the fetus/child and to adjust exposure assessment vs. biomonitoring results. Probabilistic calculations of fetal exposure were performed by forward internal dosimetry and Monte-Carlo simulation. Mean plasma levels of PFOA were 0.45, 0.13 and 0.12 ng/mL at the first trimester, at delivery and in cord plasma, while those of PFOS were 2.93, 2.21, and 1.17 ng/mL, respectively. Traces of PFOS were found in all samples in the trimester and at delivery, and almost in all cord blood samples. Transplacental transfers of PFOS and PFOA were estimated to be around 70% and 60%, respectively. A temporal decrease trend in plasma levels of PFOS and PFOA was noticed, when comparing current values with data obtained 10 years ago in the same area. In agreement with many other studies, dietary intake was the main route of exposure to PFOS and PFOA in our cohort of pregnant women. It is an important issue to establish the exposure in critical windows periods such as fetal development to perfluoroalkylated substances, but also to other endocrine disrupting chemicals.