Dual C and Cl compound-specific isotope analysis and metagenomic insights into the degradation of the pesticide methoxychlor.

This study investigates the use of multi-element compound-specific isotope analysis (ME-CSIA) to monitor degradation processes of methoxychlor, a persistent organochlorine insecticide. Laboratory experiments examined the kinetics, release of transformation products, and carbon and chlorine isotope effects during methoxychlor degradation through alkaline hydrolysis, oxidation with alkaline-activated persulfate, and biotic reductive dechlorination. Results showed that hydrolysis and oxidation did not cause significant carbon and chlorine isotope fractionation, indicating that C-H rather than C-Cl bond cleavage was the rate-determining step. Conversely, biotic reductive dechlorination by a field-derived microcosm under strictly anoxic conditions displayed significant carbon (εC = -0.9 ± 0.3 ‰) and chlorine (εCl = -1.9 ± 1.0 ‰) isotope fractionation. Its corresponding calculated dual isotope slope (ΛC/Cl = 0.4 ± 0.1) and apparent kinetic isotope effects (AKIEC = 1.014 ± 0.005 and AKIECl = 1.006 ± 0.003) indicate a C-Cl bond cleavage as the rate-determining step, highlighting the difference with respect to the other studied degradation mechanisms. Changes in the microbial community diversity revealed that families such as Dojkabacteria, Anaerolineaceae, Dysgonomonadaceae, Bacteroidetes vadinHA17, Pseudomonadaceae, and Spirochaetaceae, may be potential agents of methoxychlor reductive dechlorination under anoxic conditions. This study advances the understanding of degradation mechanisms of methoxychlor and improves the ability to track its transformation in contaminated environments, including for the first time an isotopic perspective.

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.

Novel extraction methods and compound-specific isotope analysis of methoxychlor in environmental water and aquifer slurry samples.

Multi-element compound-specific stable isotope analysis (ME-CSIA) allows monitoring the environmental behavior and transformation of most common and persistent contaminants. Recent advancements in analytical techniques have extended the applicability of ME-CSIA to organic micropollutants, including pesticides. Nevertheless, the application of this methodology remains unexplored concerning harmful insecticides such as methoxychlor, a polar organochlorine pesticide usually detected in soil and groundwater. This study introduces methods for dual carbon and chlorine compound-specific stable isotope analysis (δ13C-CSIA and δ37Cl-CSIA) of both methoxychlor and its metabolite, methoxychlor olefin, with a sensitivity down to 10 and 100 mg/L, and a precision lower than 0.3 and 0.5 ‰ for carbon and chlorine CSIA, respectively. Additionally, three extraction and preconcentration techniques suitable for ME-CSIA of the target pesticides at environmentally relevant concentrations were also developed. Solid-phase extraction (SPE) and liquid-solid extraction (LSE) effectively extracted methoxychlor (107 ± 27 % and 87 ± 13 %, respectively) and its metabolite (91 ± 27 % and 106 ± 14 %, respectively) from water and aquifer slurry samples, respectively, with high accuracy (Δδ13C and Δδ37Cl ≤ ± 1 ‰). Combining CSIA with polar organic chemical integrative samplers (POCISs) for the extraction of methoxychlor and methoxychlor olefin from water samples resulted in insignificant fractionation for POCIS-CSIA (Δδ13C ≤ ± 1 ‰). A relevant sorption of methoxychlor was detected within the polyethersulfones membranes of the POCISs resulting in temporary carbon isotope fractionation depending on the sorbed mass fraction during the first deployment days. This highlights the critical role of the interactions of polar analytes with POCIS sorbents and membranes in the performance of this method. Altogether, this study proposes a proof of concept for ME-CSIA of methoxychlor and its metabolites, opening the door for future investigations of their sources and transformation processes in contaminated sites.

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.

Human exposure to elements through consumption of raw and cooked fish in an urban region of the central Brazilian Amazon biome: Health risks.

Fish is an important source of animal protein for local communities in the Amazon basin, whose food safety must be assured. However, certain potential toxicants elements, can bioaccumulate in fish species, which inhabit anthropogenically polluted waters, ultimately posing a risk to human health. In the present study, the concentrations of nine elements (Al, As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) were determined in raw and cooked samples of eight fish species consumed in Santarém (northern Brazil, Amazon biome). The potential for non- carcinogenic human health risks linked to the consumption of cooked fish were evaluated for adults and children in two different scenarios. Four carnivores, three omnivores and one detritivore, all of them regularly marketed and consumed by the Santarém population, were the target species. The safety reference values set by national and international guidelines for humans, in both raw and cooked preparations, were used. In most cases, the cooking process showed a trend to increase elements concentrations compared to raw samples, however the differences were not significant. Moreover, the risk assessment showed danger for children in relation to Hg from the consumption of fish, in both scenarios evaluated. For adults, in one of the scenarios, there was a health risk associated to Hg as a result of carnivorous fish consumption. In a context of combined exposure to all elements, children were at risk when consuming fish, especially carnivorous and omnivorous species. For adults, the mixture of elements posed a risk to health human only for carnivorous fish consumption. The results reveal an environmental scenario of Hg contamination, which requires monitoring actions to preserve the aquatic biodiversity and human health in the Brazilian Amazon biome.

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 of organic pollutants and metals/metalloids in infant formula marketed in Brazil: Risks to early-life health.

Infant formula intake is recommended to ensure comprehensive nutritional and caloric fulfillment when exclusive breastfeeding is not possible. However, similarly to breast milk, infant formulas may also contain pollutants capable of inducing endocrine-disrupting and neurotoxic effects. Thus, considering the sensitivity of their developing physiological systems and that infants have heightened susceptibility to environmental influences, this study was aimed at assessing the contents of essential elements, and inorganic and organic pollutants in infant formulas marketed in Brazil. Additionally, health risk assessments for selected contaminants were also performed. Measured contents of essential elements (Ca, Fe, Mg, Mn, Cu, Se, and Zn) were congruent with label information. Nevertheless, some toxic elements (Pb, Cd, As, Ni, and Al) were also detected. Notably, in the upper-bound scenario, Pb and Cd surpassed established threshold values when comparing the estimated daily intake (EDI) and tolerable daily intake (TDI - 3.57 and 0.36 µg/kg bw, respectively). Bisphenol P (BPP) and benzyl butyl phthalate (BBP) were frequently detected (84 % detection rate both) with elevated contents (BPP median = 4.28 ng/g and BBP median = 0.24 ng/g). Furthermore, a positive correlation (0.41) was observed between BPP and BBP, implying a potential co-occurrence within packaging materials. Methyl-paraben also correlated positively with BBP (0.57), showing a detection rate of 53 %. The cumulative PBDE contents ranged from 0.33 to 1.62 ng/g, with BDE-154 and BDE-47 the dominant congeners. When comparing EDI values with TDIs, all organic pollutants remained below the thresholds across all exposure scenarios. Moreover, non-carcinogenic risks were below the threshold (HQ > 1) when dividing the EDIs by the respective reference doses for chronic exposure. While the current findings may suggest that infant formula intake poses no immediate risk in terms of the evaluated chemicals, it remains imperative to conduct further research to safeguard the health of infants considering other chemicals, as well as their potential cumulative effects.

Effects of an organic diet intervention on the levels of organophosphorus metabolites in an adult cohort.

Pesticides are a group of organic compounds used to control weeds or insect infestations in agriculture. Diet is the major route of human exposure to these compounds, which can cause serious health problems, even when the intake occurs at low concentrations. Hence, the consumption of organic food is an appropriate strategy to minimize the exposure to pesticides. A prospective, randomized study was conducted to assess the impact of an organic dietary intervention on the levels of urinary dialkyl phosphates (DAP). A screening of 204 pesticides was also carried out in order to confirm the absence of these compounds in organic food. The analytical results showed that only 20 of the 204 pesticides (9.8 %) had concentrations above the limit of quantification in one or more samples of the organic food consumed by the participants. It is substantially lower than the levels of pesticides found in other studies analysing conventional food, confirming the diet as suitable for the organic dietary intervention. A general reduction of most DAP metabolites in urine was found, being significant (p < 0.05) the decrease of dimethyl phosphate (DMP) (0.49 µg/g creatinine in Day 1 vs. 0.062 µg/g creatinine in Day 6), dimethyl thiophosphate (DMTP) (0.49 µg/g creatinine in Day 1 vs. 0.093 µg/g creatinine in Day 6) and diethyl phosphate (DEP) (0.28 µg/g creatinine in Day 1 vs. 0.12 µg/g creatinine in Day 6). In addition, the molar score for the total dimethyl DAP (ΣMP) and total dialkyl phosphate (ΣDAP) also showed significant differences after changing a conventional diet by an organic diet, being reduced from 0.008 µmol/g to 0.002 µmol/g for ΣMP and from 0.012 µmol/g to 0.003 µmol/g for ΣDAP. To the best of our knowledge, this is the first study that evaluates both the impact of an organic diet in the exposure to DAP and the levels of 204 pesticides in the organic food provided to the participants. In summary, the consumption of organic products decreases the dietary intake of pesticides, thus reducing also the potential adverse effects on human health.

Assessment of urinary aromatic amines in Brazilian pregnant women and association with DNA damage: Influence of genetic diversity, lifestyle, and environmental and socioeconomic factors.

Aromatic amines (AAs) are polar organic chemicals with a wide environmental distribution originating from various sources, such as tobacco smoke, diesel exhaust, and dermal absorption from textile products with azo dyes. The toxicity profile of AAs is directly related to the amino group's metabolic activation and the generation of the reactive intermediate, forming DNA adducts and potential carcinogenicity. Urinary levels of 8-hydroxy-2'-deoxyguanosine (8OHdG) are an important biomarker of DNA damage. Since AAs have been shown to cross the placental barrier, being a risk factor for adverse birth outcomes, prenatal exposure is a great public health concern. The present study aimed to measure the urinary levels of 58 AAs in Brazilian pregnant women (n = 300) and investigated the impact of this exposure on DNA damage by quantifying 8OHdG levels. The influence of tobacco smoke exposure and dermal absorption of AAs by clothes on urinary levels was also assessed. The results showed a 100% detection rate for eight AAs, two of them regulated by the European Union (2,6-dimethylaniline and 2,4-diaminotolune). Hundreds of AAs may be derived from aniline, which here showed a median of 1.38 ng/mL. Aniline also correlated positively with 2,6-dimethylaniline, p-aminophenol, and other AAs, suggesting exposure to multiple sources. The present findings suggest that both tobacco smoke and dermal contact with clothes containing azo dyes are potential sources that might strongly influence urinary levels of AAs in Brazilian pregnant women. A multiple regression linear model (R2 = 0.772) suggested that some regulated AAs (i.e., 2-naphthylamine and 4-aminobiphenyl), nicotine, smoke habit, age, and Brazilian region could induce DNA damage occurrence, increasing the levels of 8OHdG. Given the limited available data on human exposure to carcinogenic AAs, as well as the lack of toxicological information on those non-regulated, further studies focused on measuring their levels in human fluids and the potential exposure sources are clearly essential.

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.

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.

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.

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.

Dermal exposure to bisphenols in pregnant women's and baby clothes: Risk characterization.

Textile manufacturing consists of a multiple-step process in which a wide range of chemicals is used, some of them remaining in the final product. Bisphenols (BPs) are non-intentionally added compounds in textiles, whose prolonged skin contact may mean a significant source of daily human exposure, especially in vulnerable groups of the population. The present study aimed to determine the levels of bisphenol A (BPA) and some BP analogs (BPB, BPF, and BPS) in 120 new clothes commercialized in Spain for pregnant women, newborns, and toddlers. In addition, exposure assessment and risk characterization were also carried out. Traces of BPA were found in all the samples, with a median concentration of 7.43 ng/g. The highest values were detected in textile samples made of polyester. Regarding natural fibers, higher concentrations of BPs were observed in garments made of conventional cotton than in those made of organic cotton, with a significant difference for BPS (1.24 vs. 0.76 ng/g, p < 0.05). Although toddlers have a larger skin-area-to-body-weight ratio, pregnant women showed higher exposure to BPs than children. Anyhow, the non-carcinogenic risks associated with BPA exposure were below the unity, even under the upper-bound scenario. However, risks could be underestimated because other exposure routes were not considered in this study. The use of BPA has been restricted in some food-related products; therefore, BPA should also be regulated in the textile industry.

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.

Legacy and emerging pollutants in Latin America: A critical review of occurrence and levels in environmental and food samples.

The increase and indiscriminate use of personal care products, food products, fertilizers, pesticides, and health products, among others, have resulted/are resulting in extensive environmental contamination. Most of these products contain traces of widespread chemicals, usually known as emerging pollutants (EPs) or pollutants of emerging concern (PEC). The Latin American (LA) region comprises 20 countries with different social and cultural aspects, with 81 % of the population living in urban areas. The LA region has some countries on the top list of users/consumers of EPs, from pesticides and fertilizers to personal care products. However, there is a gap in information related to the distribution of EPs in the environment of this region, with very few existing review texts exploring this issue. Therefore, this present paper advances this approach. An exhaustive literature review, with the selection of 176 documents, provided unique up-to-date information on the presence/distribution of 17 classes of legacy or emerging pollutants in different food and environmental matrices (soil, sediment, water, and air). The study shows that the wide distribution and recorded levels of these pollutants in the continental environment are potential risks to human health, mainly through food and drinking water ingestion. Polycyclic aromatic hydrocarbons are pollutants of deep public concern since they show carcinogenic properties. Several classes of pollutants, like endocrine disruptors, have caused harmful effects on humans and the environment. Besides that, pharmaceutical products and pesticides are compounds of high consumption worldwide, being environmental contamination a real and ongoing possibility. Finally, gaps and future research needs are deeply pointed out.

Human exposure to polybrominated diphenyl ethers (PBDEs) through the diet: An update of the scientific literature.

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame-retardants (BFRs). As for other persistent organic pollutants, dietary intake (followed by dust inhalation) is the main route of human exposure to PBDEs. In 2012, we reviewed the scientific literature on the concentrations of PBDEs in foodstuffs and their dietary exposure. The current review is aimed at updating the results of recent studies (2012-2022) focused on determining the levels of PBDEs in food samples, as well as the dietary intake of these compounds. We have revised studies conducted over the world. The current information on the concentrations of PBDEs in food and their dietary intake is now much more notable than that available in our previous review, being China the country contributing with the highest number of studies. Because of the important differences in materials and methods used in the available studies, the comparison of results is certainly complicated. However, there seems to be a general trend towards a decrease in the levels of PBDEs in foods, and consequently, in the dietary intake of these contaminants. The lack of tolerable daily intakes of PBDEs is an issue that needs to be solved for assessing human health risks of these BFRs.

Mixture of environmental pollutants in breast milk from a Spanish cohort of nursing mothers.

Breastfeeding is one of the most effective ways to ensure child health and survival, with several benefits for both the infants and their mothers. However, breast milk can contain environmental pollutants with endocrine disruption capacity, neurotoxicity and/or potential to alter microbiota. Monitoring breast milk provides information on the current chemical exposure of breastfed infants and, in addition, on the current and historical exposure of nursing mothers. In this study, the levels of a wide range of pollutants were measured in breast milk of Spanish nursing mothers. Target chemicals were dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethylene (DDE), hexachlorobenzene (HCB), oxy-chlordane, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), per- and poly-fluoroalkyl substances (PFASs) (including perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA)), chlorpyrifos, bisphenol A (BPA), tetrabromobisphenol A (TBBPA), and a number of toxic and essential elements. Traces of most chemicals were found. A correlation between the levels of some persistent organic pollutants (POPs) and maternal characteristics (age and body mass index) was observed, while smoking was associated to higher concentrations of some toxic elements. Higher levels of PCBs were detected in samples from Spanish primiparous mothers compared to non-Spanish multiparous women. Breast milk from low-income mothers showed higher content of DDT and DDE than high-income mothers. Although breastfeeding is clearly beneficial for babies, the exposure to this mixture of hazardous substances, as well as their interaction and combined effects must not be disregarded.

Early-Life Exposure to Formaldehyde through Clothing.

Clothes contain a wide range of chemicals, some of them potentially hazardous. Recently, there has been a growing interest in eco-friendly clothing, including the use of organic cotton. However, the process of eco-friendly fabric production does not exclude the use of toxic substances, such as formaldehyde, a known human carcinogen. The present investigation was aimed at determining the presence of formaldehyde in eco-friendly and conventional clothing of pregnant women, babies, and toddlers from the Catalan (Spain) market. The potential effects of washing were also investigated by comparing the reduction of formaldehyde in unwashed and washed clothing. Formaldehyde was detected in 20% of samples, with a mean level of 8.96 mg/kg. Formaldehyde levels were surprisingly higher in eco-friendly than in regular garments (10.4 vs. 8.23 mg/kg). However, these differences were only significant (p < 0.05) for bras (11.6 vs. 7.46 mg/kg) and panties (27.1 vs. 6.38 mg/kg) of pregnant women. Dermal exposure and health risks were assessed for three vulnerable population groups: pregnant women, babies, and toddlers. In general, exposure was higher in babies (up to 1.11 × 10−3 mg/kg/day) than in other groups (2.58 × 10−4 and 4.50 × 10−3 mg/kg/day in pregnant women and toddlers, respectively). However, both non-carcinogenic and carcinogenic risks were below the safety limits (<1 and <10−5, respectively) according to national regulations. Notwithstanding, although formaldehyde levels were below the legal limits (<75 mg/kg) and health risks were within acceptable ranges, clothing may contain other toxic substances in addition to formaldehyde, thus increasing the risks. Finally, since no formaldehyde was detected in washed textile samples, a safe and simple practice for the consumers is to wash clothing before the first use.