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Estrogen levels were assessed in surface sediments from one of the most industrialized and urbanized estuarine systems in Latin America (SSES, Santos and São Vicente estuarine system). Estriol (E3) presented quantifiable levels in all sampled sites, ranging from 20.9 ng g -1 to 694.2 ng g -1 . 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) were also detected in almost all sampled sites. The highest concentration of E2 was 23.9 ng g -1 , whereas high levels of EE2 86.3 ng g -1 . The occurrence of estrogens in SSES was diffuse and partially related to a domestic sewage outfall. Estrogens were also found in areas with substantial contribution of sanitary effluents from domiciles not covered by sanitation services. Our results reinforce that studies on environmental contamination by estrogens should not be spatially limited to the vicinities of point sources. These results contribute to raise awareness on the need of a formal approach to assess ecological risks of estrogens in the SSES., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP(ESR)) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP(ESR) results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100cm(-1) and 1600cm(-1) indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A novel, simple, rapid and eco-friendly method based on dispersive liquid-liquid microextraction using a bromosolvent was developed to determine six estrogenic mycotoxins (zearalenone, zearalanone, α-zearalanol, β-zearalanol, α-zearalenol and β-zearalenol) in water samples by liquid chromatography-electrospray ionization tandem mass spectrometry in the negative mode (LC-ESI-MS/MS). The optimal conditions for this method include the use of 100 μL bromocyclohexane as an extraction solvent (using a non-dispersion solvent), 10 mL of aqueous sample (adjusted to pH 4), a vortex extraction time of 2 min, centrifugation for 10 min at 3500 rpm and no ionic strength adjustment. The calibration function was linear and was verified by applying the Mandel fitting test with a 95% confidence level. No matrix effect was observed. According to the relative standard deviations (RSDs), the precision was better than 13% for the repeatability and intermediate precision. The average recoveries of the spiked compounds ranged from 81 to 118%. The method limits of detection (LOD) and quantification (LOQ) considering a 125-fold pre-concentration step were 4-20 and 8-40 ng L(-1), respectively. Next, the method was applied to the analysis of the environmental aqueous samples, demonstrating the presence of β-zearalanol and zearalanone in the river water samples., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Recently introduced rapidly mutating Y-chromosomal short tandem repeat (RM Y-STR) loci, displaying a multiple-fold higher mutation rate relative to any other Y-STRs, including those conventionally used in forensic casework, have been demonstrated to improve the resolution of male lineage differentiation and to allow male relative separation usually impossible with standard Y-STRs. However, large and geographically-detailed frequency haplotype databases are required to estimate the statistical weight of RM Y-STR haplotype matches if observed in forensic casework. With this in mind, the Italian Working Group (GEFI) of the International Society for Forensic Genetics launched a collaborative exercise aimed at generating an Italian quality controlled forensic RM Y-STR haplotype database. Overall 1509 male individuals from 13 regional populations covering northern, central and southern areas of the Italian peninsula plus Sicily were collected, including both "rural" and "urban" samples classified according to population density in the sampling area. A subset of individuals was additionally genotyped for Y-STR loci included in the Yfiler and PowerPlex Y23 (PPY23) systems (75% and 62%, respectively), allowing the comparison of RM and conventional Y-STRs. Considering the whole set of 13 RM Y-STRs, 1501 unique haplotypes were observed among the 1509 sampled Italian men with a haplotype diversity of 0.999996, largely superior to Yfiler and PPY23 with 0.999914 and 0.999950, respectively. AMOVA indicated that 99.996% of the haplotype variation was within populations, confirming that genetic-geographic structure is almost undetected by RM Y-STRs. Haplotype sharing among regional Italian populations was not observed at all with the complete set of 13 RM Y-STRs. Haplotype sharing within Italian populations was very rare (0.27% non-unique haplotypes), and lower in urban (0.22%) than rural (0.29%) areas. Additionally, 422 father-son pairs were investigated, and 20.1% of them could be discriminated by the whole set of 13 RM Y-STRs, which was very close to the theoretically expected estimate of 19.5% given the mutation rates of the markers used. Results obtained from a high-coverage Italian haplotype dataset confirm on the regional scale the exceptional ability of RM Y-STRs to resolve male lineages previously observed globally, and attest the unsurpassed value of RM Y-STRs for male-relative differentiation purposes., (Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.)

This paper describes the validation of a method consisting of solid-phase extraction followed by gas chromatography-tandem mass spectrometry for the analysis of the ultraviolet (UV) filters benzophenone-3, ethylhexyl salicylate, ethylhexyl methoxycinnamate and octocrylene. The method validation criteria included evaluation of selectivity, analytical curve, trueness, precision, limits of detection and limits of quantification. The non-weighted linear regression model has traditionally been used for calibration, but it is not necessarily the optimal model in all cases. Because the assumption of homoscedasticity was not met for the analytical data in this work, a weighted least squares linear regression was used for the calibration method. The evaluated analytical parameters were satisfactory for the analytes and showed recoveries at four fortification levels between 62% and 107%, with relative standard deviations less than 14%. The detection limits ranged from 7.6 to 24.1 ng L(-1). The proposed method was used to determine the amount of UV filters in water samples from water treatment plants in Araraquara and Jau in São Paulo, Brazil., (Copyright © 2014 Elsevier B.V. All rights reserved.)

This report describes the development and validation of a simple, rapid, and efficient method in which solid-phase extraction followed by analysis in a gas chromatograph equipped with an electron capture detector (SPE-GC-ECD) is used for the simultaneous determination of dicofol, dieldrin, endosulfan, and permethrin in rat adipose tissue. This study targeted pesticides for which controversies exist regarding the harm that they may cause to humans, such as endocrine disruption or cancer, and that have also been found in recent years in vegetables consumed by the Brazilian population. The analytical procedure was optimised for SPE extraction and for GC-ECD conditions. The optimised method includes the extraction of the samples with n-hexane followed by an SPE procedure in which deactivated neutral alumina cartridges are used as the sorbent and a mixture of n-hexane:dichloromethane is used for elution. Recovery studies with spiked samples were used to evaluate the method's efficiency. Mean recoveries ranged from 75% to 119% with relative standard deviations (RSD)<19%. Quantification limits (LOQs) were 0.05 mg kg(-1) for dieldrin and endosulfan and 0.5 mg kg(-1) for dicofol and permethrin. The matrix effect was pronounced for all of the pesticides studied and ranged from 26% to 49%. In comparison to other related methods, this method requires less time and solvent and allows for rapid isolation of the target analytes with high selectivity. This method therefore allows for the screening of numerous samples and can also be used for routine analyses., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Non-mechanised sugarcane harvesting preceded by burning exposes workers and the people of neighbouring towns to high concentrations of pollutants. This study was aimed to evaluate the respiratory symptoms, lung function and oxidative stress markers in sugarcane workers and the residents of Mendonça, an agricultural town in Brazil, during the non-harvesting and harvesting periods and to assess the population and individual exposures to fine particulate matter (PM(2.5)). Sugarcane workers and healthy volunteers were evaluated with two respiratory symptom questionnaires, spirometry, urinary 1-hydroxypyrene levels, and the measurement of antioxidant enzymes and plasma malonaldehyde during the non-harvesting and harvesting periods. The environmental assessment was determined from PM(2.5) concentration. PM(2.5) level increased from 8 μg/m³ during the non-harvesting period to 23.5 μg/m³ in the town and 61 μg/m³ on the plantations during the harvesting period. Wheezing, coughing, sneezing, and breathlessness increased significantly in both groups during the harvesting period, but more markedly in workers. A decrease in lung function and antioxidant enzyme activity was observed in both populations during harvesting; this decrease was greater among the sugarcane workers. The urinary 1-hydroxypyrene levels only increased in the sugarcane workers during the harvesting period. The malonaldehyde levels were elevated in both groups, with a higher increase observed in the workers. This research demonstrates the exposure of sugarcane workers and the inhabitants of a neighbouring town to high PM(2.5) concentrations during the sugarcane harvest period. This exposure was higher among the sugarcane workers, as illustrated by both higher PM(2.5) concentrations in the sugarcane fields and higher urinary 1-hydroxypyrene levels in the volunteers in this group. The higher incidence of respiratory symptoms, greater decrease in lung function and more marked elevation of oxidative stress markers among the sugarcane workers during the harvest confirms the greater effect magnitude in this population and a dose-dependent relationship between pollution and the observed effects., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Biodiesel production has received considerable attention in the recent past as a nonpolluting fuel. However, this assertion has been based on its biodegradability and reduction in exhaust emissions. Assessments of water and soil biodiesel pollution are still limited. Spill simulation with biodiesel and their diesel blends in soils were carried out, aiming at analyzing their cytotoxic and genotoxic potentials. While the cytotoxicity observed may be related to diesel contaminants, the genotoxic and mutagenic effects can be ascribed to biodiesel pollutants. Thus, taking into account that our data stressed harmful effects on organisms exposed to biodiesel-polluted soils, the designation of this biofuel as an environmental-friendly fuel should be carefully reviewed to assure environmental quality., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The designation of biodiesel as a green fuel has increased its commercialization and use, making its fate in the environment a matter of concern. Fuel spills constitute a major source of aquatic pollution and, like diesel spills, biodiesel can produce adverse effects on aquatic environments, animals and humans. The present study assessed cytotoxic effects of water systems contaminated with neat biodiesel and its diesel blends by means of different procedures on human T cell leukemia (Jurkat) and human hepatocellular carcinoma (HepG2) cells [detection of changes in mitochondrial membrane potential (ΔΨ(m)) using tetramethylrhodamine ethyl ester (TMRE), apoptosis recognition by Annexin V and impedance real-time cell analyzer (xCELLigence™ system)]. The data obtained showed concordance across the different bioassays, with cytotoxic effects observed as a dose-dependent response only for waters contaminated with pure diesel (D100) and B5 blend, which is characterized by a mixture of 95% diesel and 5% biodiesel. The data can also lead us to hypothesize that diesel accounts for the harmful effects observed, and that biodiesel does not worsen the impacts caused by diesel pollution., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Brazil contains 25% of the total land planted with sugarcane in the world and is thus one of the major producers. The annual burning of sugarcane fields prior to harvesting emits huge amounts of pyrogenic particles. Biomass burning is an important primary and secondary source of aerosol particles. The presence of carbonaceous particles in the inhalable size range makes it important to study this fraction in view of the possible effects on human health and the climate. In this study, the mutagenic activity associated with inhalable airborne particulate matter (PM(10)) collected on air filters in a sugarcane-growing area near the city of Araraquara (SE Brazil) was determined. The extracts were dissolved in dimethylsulfoxide and tested for mutagenicity by the Ames plate incorporation test with Salmonella typhimurium YG1024 in the presence and absence of the S9 mixture. To assess the association between mutagenicity and PM(10), samples were collected in sugarcane harvesting and non-harvesting periods of the year. Significant mutagenicity was detected in organic solvent extracts of all samples, with differences between the two periods. The highest values of mutagenic potency (13.45 and 5.72 revertants/m(3) of air in the absence and presence of the S9 mixture, respectively) were observed during the harvest. In this period, a Teflon™-coated glass-fiber air filter trapped 67.0 μg of particulate matter per m(3) of air. In the non-harvest period, on the same type of filter, only 20.9 μg of particulate matter was found per m(3). The mutagenic potencies at this time were 1.30 and 1.04 revertants/m(3) of air, in the absence and presence of the S9 mixture, respectively. Period, concentration of PM(10) and mutagenicity were associated with each other. For routine monitoring of mutagenicity in the atmosphere, the use of YG1024 tester strain without metabolic activation (S9) is recommended., (Copyright © 2011 Elsevier Inc. All rights reserved.)

For the first time, organotin compounds were determined in surface sediment samples collected from São Francisco do Sul, Itajaí-Navegantes and Imbituba Harbors, located in Santa Catarina State, Brazil. Butyltins (BTs) were determined by gas chromatography with a pulsed flame photometric detector (GC-PFPD) after being modified using the Grignard derivatization method. The concentrations of BTs derivatives ranged from n.d. to 1136.6 ng (Sn) g(-1) of dry weight (dw) sediment for tributyltin (TBT), n.d. to 394.4 ng (Sn)g(-1) dw for dibutyltin (DBT) and n.d. to 312.2 ng (Sn) g(-1) dw for monobutyltin (MBT). The highest concentration of total BTs was found at the Itajaí-Açu River dockyard, indicating intense inputs of antifouling paints to the environment. The relative difference in the BTs levels is a particular characteristic of sediments from harbors and may be related to the shipyards and the boat traffic which still use TBT-based antifouling paints., (Copyright 2010 Elsevier B.V. All rights reserved.)

Sugarcane workers in Brazil are exposed to various genotoxic compounds, including polycyclic aromatic hydrocarbons (PAHs), derived from an incomplete combustion process of burnt sugarcane fields. The effects of the occupational exposure to sugarcane fields burning were measured in urine samples of sugarcane workers from the northwest of the State of São Paulo when exposed (harvesting) and when non-exposed (non-harvesting). The urinary levels of 1-hydroxypyrene (1-OHP) and the influence of the genetic polymorphisms CYP1A1, GSTM1, GSTT1 and GSTP1 were evaluated. Our results showed that the 1-OHP levels were significantly higher (P<0.0000) in the exposed sugarcane workers (0.318 mumol mol(-1) creatinine) than in the non-exposed workers (0.035 mumol mol(-1) creatinine). In an unvaried analysis, no influence regarding the polymorphisms was observed. However, multivariate regression analysis showed that the CYP1A1()4 polymorphism in the exposed group, and age and the GSTP1 polymorphism in the non-exposed group significantly influenced urinary 1-OHP excretion levels (P<0.10). The same group of sugarcane workers was significantly more exposed to PAHs during the harvesting period than during the non-harvesting period.