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This work describes preparing a certified reference material for pumpkin seed flour for use in inorganic analyses of vegetable foods. The elements studied were potassium, magnesium, phosphorus, zinc, copper, iron, manganese, and calcium. The ISO Guides were employed in the homogeneity and stability tests, interlaboratory program, and assignment of uncertainty value. The material was stable for 12 months at temperatures of -10 °C, 25 °C, and 45 °C, with minor uncertainties. Chemometric techniques, such as principal component analysis (PCA) and hierarchical clustering analysis (HCA), were employed in the homogeneity and stability studies. The confidence ellipse technique allowed a simple and rapid evaluation of the data furnished by the collaborating laboratories regarding the precision of the results. The findings showed that pumpkin seed flour could be considered a raw material for preparing reference material, considering its availability and characteristics of its matrix, including the presence of trace and essential elements., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Coastal marine ecosystems, such as coral reefs, are severely threatened by climate changes, overexploitation, and marine pollution. Particularly, environmental pollution caused by petroleum-derived substances is poorly studied in coral reefs in tropical developing countries, with a total absence of data about these contaminants in some regions. In this work, we determined the levels of conventional and unconventional PAHs in the tissue and skeleton of the coral Montastraea cavernosa in a seascape scale of the Southwest Atlantic. We sampled in 12 coral reefs adjacent to the coast along approximately 200 km. We found 14 PAHs, 2 Oxy-PAHs, and 15 Nitro-PAHs in the samples, and among them, benzo[a]pyrene, chrysene, benzo[a]anthracene, benzo[k]fluoranthene, indeno[1,2,3-c,d]pyrene and dibenz[a,h]anthracene, which are mutagenic, teratogenic and carcinogenic substances. Skeletons presented predominantly lower quantities of ∑PAHs than the respective tissue, except for the skeletons from one reef severely impacted by oil spills. The ∑PAHs levels were lower in a bay near an urbanized region than in open sea reefs. Diagnostic ratios indicate mixogenic sources, with the predominance of petrogenic origin. Our study provides the first occurrence of PAHs, Nitro-PAHs, and Oxy-PAHs distribution in corals from the Southwest Atlantic Ocean, and we expect that these data will help to evaluate any future impacts and management of this ecosystem., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Coastal ecosystems, such as coral reefs, are particularly vulnerable to mercury contamination due to direct contact with terrestrial sources. Here, we evaluated, for the first time, the concentration of mercury in coral reefs in the Southwestern Atlantic using the amphi-atlantic scleractinian coral Montastraea cavernosa. Sampling was realized over an extension of 200 km along different coral reefs. Our data show mercury values ranging from 0.01 to 0.27 mg kg -1 in the tissue and 0.001-0.06 mg kg -1 in the skeleton and higher values when compared to coral worldwide. The concentration of mercury in the tissue from Todos os Santos Bay was higher than in open sea regions but also higher compared to other coral reefs of the world, while the skeleton concentration did not indicate any differences when compared to the open sea regions. The data presented is of concern as we consider the importance of coral reefs and should be used in future environmental management planning., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Ltd.)

Background and Objective: The Modified Rankin Scale (mRS) is a widely adopted scale for assessing stroke recovery. Despite limitations, the mRS has been adopted as primary outcome in most recent clinical acute stroke trials. Designed to be used by multidisciplinary clinical staff, the congruency of this scale is not consistent, which may lead to mistakes in clinical or research application. We aimed to develop and validate an interactive and automated digital tool for assessing the mRS-the iRankin., Methods: A panel of five board-certified and mRS-trained vascular neurologists developed an automated flowchart based on current mRS literature. Two international experts were consulted on content and provided feedback on the prototype platform. The platform contained five vignettes and five real video cases, representing mRS grades 0-5. For validation, we invited neurological staff from six comprehensive stroke centers to complete an online assessment. Participants were randomized into two equal groups usual practice versus iRankin. The participants were randomly allocated in pairs for the congruency analysis. Weighted kappa (kw) and proportions were used to describe agreement., Results: A total of 59 professionals completed the assessment. The kw was dramatically improved among nurses, 0.76 (95% confidence interval (CI) = 0.55-0.97) × 0.30 (0.07-0.67), and among vascular neurologists, 0.87 (0.72-1) × 0.82 (0.66-0.98). In the accuracy analysis, after the standard mRS values for the vignettes and videos were determined by a panel of experts, and considering each correct answer as equivalent to 1 point on a scale of 0-15, it revealed a higher mean of 10.6 (±2.2) in the iRankin group and 8.2 (±2.3) points in the control group (p = 0.02). In an adjusted analysis, the iRankin adoption was independently associated with the score of congruencies between reported and standard scores (beta coefficient = 2.22, 95% CI = 0.64-3.81, p = 0.007)., Conclusion: The iRankin adoption led to a substantial or near-perfect agreement in all analyzed professional categories. More trials are needed to generalize our findings. Our user-friendly and free platform is available at https://www.irankinscale.com/., Competing Interests: Declaration of conflicting interestsThe author(s) declared the following potential conflicts of interest with respect to the research, authorship, and/or publication of this article: T.J.Q. has created training materials for mRS assessment that are now hosted by a commercial provider, he also contributes to mRS adjudication for industry and academic-led studies, and he makes no personal profit from these.

This work presents the experimental assessment of a 20 mL batch reactor's efficacy in converting plastic and oil residues into biofuels. The reactor, designed for ease of use, is heated using a metallic system. The experiments explore plastic solubilization at various temperatures and residence times, employing a mixture of distilled water and ethylene glycol as the solvent. Initial findings reveal that plastic solubilization requires a temperature of 350 °C with an ethylene glycol mole fraction of 0.35, whereas 250 °C suffices with a mole fraction of 0.58. Additionally, the study includes a process simulation of a plant utilizing a double fluidized bed gasifier and an economic evaluation of the interesterification/pyrolysis plant. Simulation results support project feasibility, estimating a total investment cost of approximately $12.99 million and annual operating expenses of around $17.98 million, with a projected payback period of about 5 years., (© 2024. The Author(s).)

Plastic pellets represent a significant component of microplastic (< 5 mm) pollution. Impacts caused by plastic pellets involve physical harm and toxicity related to ingestion and non-ingestion (such as the release of chemicals in leachates). The latter is the main route of exposure for invertebrate macrobenthic populations. This study aimed to compare the toxicity of plastic pellets in distinct marine macrobenthic populations, considering the influence of sediment characteristics (organic matter and grain size) and quality (contamination by hydrophobic chemicals) on ecotoxicological effects, as well as the influence of color on the toxicity of beach-stranded plastic pellets. We performed three experiments on plastic pellet exposure using Excirolana armata from beaches with high and low pellet density. When exposed to pellets, populations that inhabit beaches without pellets demonstrate higher mortality than those inhabiting beaches with high pellet densities. The mortality of E. armata to pellets was higher when the exposure occurred in sediment with high organic matter (OM), suggesting that chemicals were transferred from pellets to OM. Yellowish beach-stranded pellets induced higher mortality of E. armata than the white tones did. We also observed lethargic (near-dead) and dead individuals being preyed upon by healthy individuals, a cannibalistic behavior that raises an ecological concern regarding the negative effects of this exposure on intraspecific interactions in marine macrobenthic populations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this work, we reported the development of a novel, simple, and green liquid-phase microextraction (LPME) procedure based on the use of a customized device for the determination of 47 multiclass pesticides in red, white, and rosè wine samples by GC-MS. The main parameters that affect the LPME were optimized using multivariate statistical techniques such as centroid-simplex mixture design and Doehlert design. The optimal conditions were: 70 μL of toluene as extractor solvent; concentration of NaCl (2.7%, m v -1 ); pH 4; and an extraction time of 30 min, under vortex-assisted agitation (at 500 rpm). After validation, it was possible to obtain LOQ values as low as 7.63 ng L -1 and extraction recoveries ranging from 81.7% to 119% for most of the target pesticides. The application of exploratory analysis, specifically Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA), provided evidence indicating contamination in the different types of wine samples, primarily by systemic fungicides., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2023. Published by Elsevier B.V.)

This work reports assessing risks to human health resulting from mercury levels in sardines (Sardinella brasiliensis), which have been highly consumed by the low-income population from Salvador, Brazil. Mercury was determined using the Direct Mercury Analysis (DMA) in fifty-one commercially acquired samples in seventeen neighborhoods. The mercury content on a wet basis ranged from 0.023 to 0.083 μg g -1 for an average value of 0.039 μg g -1 . The estimated weekly intake (EWI), target hazard quotient (THQ), and maximum safe consuming quantity (MSCQ) were used in the toxicological assessment, and all these indices denoted that this food does not pose any risks to the human health of the population that consumes it. The development of this work was very significant because most sardines sold in Salvador originate from Todos os Santos Bay, which has a history of mercury contamination., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Polycyclic aromatic sulfur heterocycles (PASHs), such as benzothiophenes (BT), dibenzothiophenes (DBT) and benzonapthothiophenes (BNT), can be emitted from vehicular traffic and deposited in fine particles matter (PM 2.5 ). The presence of these compounds in PM 2.5 is an environmental concern due to air pollution and its toxic properties. In this study, a green microscale solid-liquid extraction method was developed to determine twenty-three PASHs in PM 2.5 . A simplex-centroid mixture design was applied to optimize the extraction solvent. A full factorial design was used for preliminary evaluation of the factors that influence the extraction process (extraction time, sample size, and solvent volume) and then a Doehlert design for the significant parameters. The optimal extraction conditions based on the experimental design were: sample size, 4.15 cm 2 ; 450 μL of toluene:dichloromethane (80:20,v/v); and extraction duration, 24 min. High sensitivity (LOD < 0.66pg m -3 and LOQ < 2.21 pg m -3 ) and acceptable recovery (82.8-120 %), and precision (RSD 3.6-14.0 %) were obtained. The greenness of the method was demonstrated using the Analytical GREEnness (AGREE) tool. The method was applied for analyzing PASHs in PM 2.5 samples collected in three time intervals per day from years with different sulfur contents in the diesel: S-500 (≤500 ppm sulfur) and S-50 (≤50 ppm sulfur). Fourteen PASHs were quantified with the highest concentrations observed for 2,8-DMDBT and 4,6-DMDBT, which are recalcitrant compounds. The ANOVA test indicated significant differences between sampling periods during the day. The reduction of diesel S-500 to S-50 corresponded to a 28 % decrease in the total sum of PASHs (∑PASHs) evaluated. Spearman's rank correlations allowed for verifying that BTs and DBTs were highly correlated, suggesting that they were derived from similar sources. A weak correlation of 2,1-BNT and 2,3-BNT with BTs and DBTs indicates that these compounds are a chemical proxy for the emission of diesel engines during the combustion process., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Liquid-phase microextraction (LPME) is a simple, low-cost, and eco-friendly technique that enables the detection of trace concentrations of organic contaminants in water samples. In this work, a novel customized microextraction device was developed for the LPME extraction and preconcentration of nine illicit drugs in surface water and influent and effluent wastewater samples, followed by analysis by GC-MS without derivatization. The customized device was semi-automated by coupling it with a peristaltic pump to perform the collection of the upper layer of the organic phase. The extraction parameters affecting the LPME efficiency were optimized. The optimized conditions were: 100 µL of a toluene/DCM/EtAc mixture as extractor solvent; 30min of extraction time under vortex agitation (500rpm) and a solution pH of 11.6. The limits of detection and quantification ranged from 10.5ng L -1 (ethylone) to 22.0ng L -1 (methylone), and from 34.9ng L -1 to 73.3ng L -1 for these same compounds, respectively. The enrichment factors ranged from 39.7 (MDMA) to 117 (cocaethylene) and the relative recoveries ranged from 80.4% (N-ethylpentylone) to 120% (cocaine and cocaine-d 3 ). The method was applied to real surface water, effluent, and influent wastewater samples collected in Salvador City, Bahia, Brazil. Cocaine was the main drug detected and quantified in wastewater samples, and its concentration ranged from 312ng L -1 to 1,847ng L -1 . Finally, the AGREE metrics were applied to verify the greenness of the proposed method, and an overall score of 0.56 was achieved, which was considered environmentally friendly., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Emerging polycyclic aromatic nitrogen heterocycles (PANHs) contributes significantly to the health risk associated with inhaling polluted air. However, there is a lack of analytical methods with the needed performance to their determination. This study presents the optimization and validation for the first time of a green microscale extraction procedure for the determination of twenty-one PANHs, including carbazole, indole, and quinolone classes, in particulate matter (PM 2.5 ) samples by gas chromatography-mass spectrometry. A simplex-centroid mixture design and full factorial design (2 3 ) were employed to optimize the following extraction parameters: type and volume of solvent, sample size, extraction time, and necessity of a cleanup step. Low limits of detection and quantification (LOD < 0.97 pg m -3 and LOQ < 3.24 pg m -3 , respectively) were obtained in terms of matrix-matched calibration. The accuracy and precision of the method were adequate, with recoveries in three levels between 73 to 120% and intraday and interday relative standard deviations from 2.0 to 12.9% and 7.3 to 18.9%, respectively. The green character of the method was evaluated using the Analytical Greenness (AGREE) tool, where a score of 0.69 was obtained, indicating a great green procedure. The method was applied to PM 2.5 samples collected from sites with different characteristics; the concentrations ranged from 69.3 pg m -3 (2-methylcarbazole) to 11,874 pg m -3 (carbazole) for individual PANHs and from 2306 to 24,530 pg m -3 for ∑21PANHs. Principal component analysis (PCA) and hierarchical clustering enabled discrimination of the sampling sites according to the PANHs concentrations. The score plots formed two distinct groups, one with samples containing higher concentrations of PANHs, corresponding to sites with a major influence from diesel emissions, and another group with minor PANH contents, corresponding to sites impacted by emissions from urban traffic and industrial activities., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Wastewater-based epidemiology (WBE) becomes an interesting epidemiological approach to monitoring the prevalence of SARS-CoV-2 broadly and non-invasively. Herein, we employ for the first time WBE, associated or not with the PEG 8000 precipitation method, for the detection of SARS-CoV-2 in samples of raw or treated wastewater from 22 municipal wastewater treatment stations (WWTPs) located in Salvador, the fourth most populous city in Brazil. Our results demonstrate the success of the application of WBE for detecting SARS-CoV-2 in both types of evaluated samples, regardless of the usage of PEG 8000 concentration procedure. Further, an increase in SARS-CoV-2 positivity rate was observed in samples collected in months that presented the highest number of confirmed COVID-19 cases (May/2021, June/2021 and January/2022). While PEG 8000 concentration step was found to significantly increase the positivity rate in treated wastewater samples (p < 0.005), a strong positive correlation (r: 0.84; p < 0.002) between non-concentrated raw wastewater samples with the number of new cases of COVID-19 (April/2021-February/2022) was observed. In general, the present results reinforce the efficiency of WBE approach to monitoring the presence of SARS-CoV-2 in either low- or high-capacity WWTPs. The successful usage of WBE even in raw wastewater samples makes it an interesting low-cost tool for epidemiological surveillance., (© 2023. Springer Nature Limited.)

Background: Aspirin is widely used as secondary prophylaxis for acute ischemic stroke. However, its influence on the risk of spontaneous hemorrhagic transformation (HT) is still unclear. Predictive scores of HT have been proposed. We hypothesized that an increased aspirin dose might be harmful in patients at a high risk of HT. This study aimed to analyze the relationship between in-hospital daily aspirin dose (IAD) and HT in patients with acute ischemic stroke., Methods: We conducted a retrospective cohort study of patients admitted to our comprehensive stroke center between 2015 and 2017. The attending team defined IAD. All included patients underwent either computed tomography or magnetic resonance imaging within 7 days of admission. The risk of HT was assessed using the predictive score of HT in patients not undergoing reperfusion therapies. Regression models were used to evaluate the correlations between HT and IAD., Results: A total of 986 patients were included in the final analysis. The prevalence of HT was 19.2%, and parenchymatous hematomas type-2 (PH-2) represented 10% (n=19) of these cases. IAD was not associated with HT ( P =0.09) or PH-2 ( P =0.06) among all patients. However, in patients at a higher risk for HT (patients not undergoing reperfusion therapies ≥3), IAD was associated with PH-2 (odds ratio 1.01,95% CI 1.001-1.023, P =0.03) in an adjusted analysis. Taking 200 versus 300 mg aspirin was protective against PH-2 (odds ratio 0.102, 95% CI 0.018-0.563, P =0.009)., Conclusion: An increased in-hospital aspirin dose is associated with intracerebral hematoma in patients at a high risk of HT. Stratifying the risk of HT may lead to individualized daily aspirin dose choices. However, clinical trials on this topic are required., Competing Interests: The authors declare no conflict of interest., (Copyright © 2023 Wolters Kluwer Health, Inc. All rights reserved.)

This work reports the quantification of total mercury in sediments collected in periods with and without rain from the Joanes River, Bahia, Brazil. Determinations were made using Direct Mercury Analysis (DMA), the accuracy of which was confirmed with two certified reference materials. The highest total mercury concentrations were found at the sampling point close to commercial areas and large residential condominiums. On the other hand, the lowest levels were found in the site close to a mangrove region. The geoaccumulation index was applied to the total mercury results, evidencing low contamination in the region studied. The contamination factor showed that of the seven stations investigated, four samples collected in the rainy season showed moderate contamination. The results of the ecological risk assessment were utterly consistent with the contamination factor data. This study showed that the smaller sediment particles concentrate more mercury, corroborating what has been predicted by the adsorption processes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The impact of petroleum exploitation and oil spills in marine ecosystems has increased over time. Among the concerns regarding these events, the impact on coral reefs stand out because this ecosystem has ecological and economic importance and is globally threatened. We performed a systematic review and bibliometric analysis of studies that determine polycyclic aromatic hydrocarbons (PAHs) in coral reefs, attempting to answer how the studies were distributed around the globe, the main environmental matrices and species of coral studied, the main PAHs found and their mean concentrations, and the methodology used. A bibliographic search resulted in 42 studies with worldwide distribution. The bibliometric results presented more explored terms, such as sediments and toxicology, and newly investigated terms, which should encourage a new area of study, such as those related to zooxanthellae and mucus. The main matrices studied in coral reefs are sediments, corals, and water, whereas air and other invertebrates have rarely been studied. Approximately 45 species of corals with several morphotypes have been reported. PAHs recommended by the United States Environmental Protection Agency (US EPA) were analyzed in all studies, while additional compounds were analyzed in only five. The methods used to determine hydrocarbons are predominantly the most traditional; however, for corals, studies have tended to separate tissue, zooxanthellae, skeleton, and mucus. In the future, we recommend investment in improving the capacity to detect non-conventional PAHs, more studies in regions that are rarely explored in developing countries, and the creation of databases to facilitate management planning on marine coasts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

We investigated if pristine and functionalized fullerenes could be actual constituents of fine atmospheric aerosols. Comprehensive profiles of fullerenes from 1 µL extracts were made through matrix laser desorption ionization Time-of-Flight Mass Spectrometry (MALDI-MS) within a few minutes. The ion with m/z 720, corresponding to [C 60 ] -• , was identified as fullerene after 1 µL of α-cyano-4-hydroxycinnamic acid matrix solution was spotted over the dried extracts. The ions with the m/z corresponding to C 70 , C 76 , C 84 , C 100 , C 118 , C 128 , and C 130 were also attributed to other fullerene species detected within the samples. The ion m/z 878 was found to be the fullerene derivative diethyl methano[60]fullerene dicarboxylate. Since ions of fragmented fullerene molecules were not detected even at high laser energies, we considered the fullerenes' occurring as original constituents of real atmospheric particle matrices instead of being formed as artifacts of the laser action on samples. Therefore, this protocol would be helpful in the understanding of the distribution of either pristine or functionalized fullerenes in the environment and their participation in atmospheric chemistry under typical conditions, as well as its application in vitro and in vivo (eco)toxicity studies., (© 2023. The Author(s).)

In the present study, the Hg levels in freshly collected polychaete species and their associated sediments were evaluated from Todos os Santos Bay, Northeastern Brazil. Additionally, it was also measured the Hg distribution along the annelids' body parts (anterior region, abdomen, and posterior region). Total Hg concentration was as follows: 13.6-144 μg kg -1 (Scolelepis chilensis, deposit feeder), 8.2-122 μg kg -1 (Laeonereis acuta, deposit feeder), 95-612 μg kg -1 (Armandia agilis, deposit feeder); 96.6-206 μg kg -1 (Lumbrineris sp., carnivorous), 75.3-112 μg kg -1 (Goniada echinulate, carnivorous), and 115-198 μg kg -1 (Branchiomma sp., suspension feeder). In turn, Hg levels in sediments ranged from 2.77 ± 0.24 to 6.38 ± 0.15 μg kg -1 . Hg concentrations found in polychaete soft tissues were higher than those found in the sediments. Specific habits, feeding behavior, trophic level, and stressful environmental conditions are the main factors affecting the Hg levels in the species studied. The bioaccumulation factor (BAF), contamination factor (CF), and ecological risk assessment (Er) were calculated. The BAF values were higher than 1 for all studied species, indicating Hg bioaccumulation in the annelids, but the low levels of CF e Er showed those Hg levels present low to no significant ecological risk for the biota and benthonic organisms living in the sediments. Finally, no statistically significant difference was observed for Hg concentration levels along the polychaete body parts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In this study, a green microscale solid-liquid extraction method using a miniaturized device combined with cleanup via dispersive micro-solid-phase extraction (MSLE-DµSPE) was developed for the determination by gas chromatography-quadrupole mass spectrometry (GC-MS) of n-alkanes in marine sediments. The main factors affecting the performance of this novel method were optimized using multivariate statistical tools. The MSLE-DµSPE method was validated considering the matrix-matched calibration, recovery, detection and quantification limits, ruggedness and accuracy. Under the optimum conditions, the method detection limits for n-alkanes ranged from 0.0051 to 0.0279 mg kg -1 , and the quantification limits ranged from 0.0171 to 0.0930 mg kg -1 . Correlation coefficients (R 2 ) ≥0.99 were obtained for all compounds within the linear region (0.0025-0.200 mg L -1 ). The mean recovery for most n-alkanes ranged from 60.6 to 119%, with intraday and interday relative standard deviation (RSD) <20%. Evaluation of the MSLE-DµSPE method using Analytical Eco-Scale, Green Analytical Procedure (GAPI), and Analytical Greenness (AGREE) assessment metrics demonstrated the green potential of the developed method. Finally, the proposed method was successfully applied to marine sediment samples and the n-alkanes from C 12 to C 40 were detected with total concentrations in the range of 0.98-7.61 mg kg -1 . This study represents the first application of a green microscale procedure to the analysis of n-alkanes in marine sediments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

There are only a few established methods to determine the concentration of encapsulated viruses, such as SARS-CoV-2, in water matrices, limiting the application of wastewater-based epidemiology (WBE)-an important tool for public health research. The present study compared four methods that are commonly used to concentrate non-encapsulated enteric viruses for determining SARS-CoV-2 concentration in wastewater and wastewater-enriched river water samples. The four methods tested were electronegative membrane with Mg +2 addition, aluminum hydroxide-based precipitation, polyethylene glycol (PEG) 8000 precipitation, and ultrafiltration (with porosity of 10 and 50 kDa). Prior to the concentration step, filtration or centrifugation was performed to remove suspended particles from the samples (pretreatment). To evaluate the recovery efficiency (%), samples of SARS-CoV-2 from nasopharyngeal swabs obtained from RT-qPCR-positive patients were used as spiked samples. The second part of the analysis involved the quantification of the SARS-CoV-2 copy number in analytes without SARS-CoV-2-spiked samples. Among the tested methods, pretreatment via centrifugation followed by ultrafiltration with a 50-kDa cut-off was found the most efficient method for wastewater samples with spiked samples (54.3 or 113.01% efficiency). For the wastewater-enriched river samples with spiked samples, pretreatment via centrifugation followed by filtration using an electronegative membrane was the most efficient method (110.8% and 95.9% for N1 and N2 markers, respectively). However, ultrafiltration of the raw river water samples using 10 or 50 kDa cut-off filters and PEG 8000 precipitation showed the best concentration efficiency based on copy number, regardless of the pretreatment approach or sample type (values ranging from 3 × 10 5 to 6.7 × 10 3 ). The effectiveness of the concentration method can vary depending on the type of sample and concentration method. We consider that this study will contribute to more widespread use of WBE for the environmental surveillance of SARS-CoV-2., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Authors.)

Reliable serological tests for the detection of SARS-CoV-2 antibodies among infected or vaccinated individuals are important for epidemiological and clinical studies. Low-cost approaches easily adaptable to high throughput screenings, such as Enzyme-Linked Immunosorbent Assays (ELISA) or electrochemiluminescence immunoassay (ECLIA), can be readily validated using different SARS-CoV-2 antigens. A total of 1,119 serum samples collected between March and July of 2020 from health employees and visitors to the University Hospital at the University of São Paulo were screened with the Elecsys ® Anti-SARS-CoV-2 immunoassay (Elecsys) (Roche Diagnostics) and three in-house ELISAs that are based on different antigens: the Nucleoprotein (N-ELISA), the Receptor Binding Domain (RBD-ELISA), and a portion of the S1 protein (ΔS1-ELISA). Virus neutralization test (CPE-VNT) was used as the gold standard to validate the serological assays. We observed high sensitivity and specificity values with the Elecsys (96.92% and 98.78%, respectively) and N-ELISA (93.94% and 94.40%, respectively), compared with RBD-ELISA (90.91% sensitivity and 88.80% specificity) and the ΔS1-ELISA (77.27% sensitivity and 76% specificity). The Elecsys ® proved to be a reliable SARS-CoV-2 serological test. Similarly, the recombinant SARS-CoV-2 N protein displayed good performance in the ELISA tests. The availability of reliable diagnostic tests is critical for the precise determination of infection rates, particularly in countries with high SARS-CoV-2 infection rates, such as Brazil. Collectively, our results indicate that the development and validation of new serological tests based on recombinant proteins may provide new alternatives for the SARS-CoV-2 diagnostic market., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Andreata-Santos, Machado, Alves, Sales, Soares, Rodrigues, Silva, Favaro, Rodrigues-Jesus, Yamamoto, Andrade, Fock, Margarido, Carvalho, Boscardin, Durigon and Ferreira.)

This study investigated the concentrations of polycyclic aromatic compounds (PACs), including parent polyaromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives, in 48 sediment samples from the intertidal region of sandy beaches in Baía de Todos os Santos (BTS), Salvador, State of Bahia, Brazil. The total PAH (∑PAH) concentration, total nitro-PAH (∑nitro-PAH) concentration, and total oxy-PAH (∑oxy-PAH) concentration ranged from 2.11 μg g -1 dry weight (dw) to 28.0 μg g -1 dw, 2.58 μg g -1 dw to 30.2 μg g -1 dw, and 0.34 μg g -1 dw to 3.65 μg g -1 dw, respectively. Elevated concentrations of parent PAHs and nitro-PAHs were found in samples from two sites in BTS, which were also characterized by high percentages of fine-medium sand and low organic matter contents. Potent mutagenic 3-nitrobenzanthrone (3-NBA) was found in 86% of the samples at concentrations ranging from 0.200 μg g -1 dw to 0.690 μg g -1 dw. Furthermore, calculations of the benzo[a]pyrene toxicity equivalency (BaPTEQ) indicated that three carcinogenic high-molecular-weight PAHs accounted for 98.7% of the total maximum PAH concentration. Finally, we assessed the possible environmental risks posed to benthic species living in the sediments of BTS. The results showed that the risk quotient for PAHs (RQ PAHs ) was ≥1. In turn, the summed RQ for all PACs (∑RQ mixture ) ranged from 1 to 30, but did not exceed the maximum allowable threshold; thus, the risks posed to benthic species were moderate for all sediment samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A simple method was developed to determine 14 endocrine-disrupting chemicals (EDCs) in bottled waters, based on dispersive micro-solid phase extraction (d-µ-SPE) and liquid chromatography-mass spectrometry (LC-MS). Extraction was optimized using 2  k-1 factorial and Doehlert experimental designs. Optimized conditions were 80 mg C18, 25 min extraction at 1000 rpm, and 6 min desorption time. Repeatability was below 17 % for all EDCs. LOD and LOQ varied from 1.60 ng L -1 (estradiol, E2) to 23.2 ng L -1 (dimethylphthalate, DMP) and from 5.33 ng L -1 (E2) to 77.3 ng L -1 (DMP). We found DMP and bisphenol A (BPA) in samples after the heat treatment. DMP was up to 58.7 µg L -1 , while BPA was up to 1.34 µg L -1 . Tolerance of daily intake (TDI) for DMP were 2.50-2.94 µg kg -1 day -1 (children) and 1.43-1.68 µg kg -1 day -1 (adults). TDI for BPA were 0.03-0.07 µg kg -1 day -1 (children) and 0.01-0.04 µg kg -1 day -1 (adults)., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Carbonyl compounds (CCs) can migrate from bottles to mineral water because of plastic degradation. An exploratory analysis of the presence a significant number of CCs (14) in bottled mineral water with and without gas in polyethylene terephthalate (PET) containers was performed using ultra-fast liquid chromatography coupled to mass spectrometry (UFLC-MS). The data from the analysis was submitted to chemometric treatment (principal component analysis, PCA). Formaldehyde, acetaldehyde, and benzaldehyde were found in all samples (0.07-125 ng mL -1 ). Acrolein and acetone were present in 81% and 75% of the samples, respectively. The concentration of acrolein in carbonated water was up to 3.8 times greater than that measured in non-carbonated water (0.07-0.44 ± 0.01 ng mL -1 ). PCA analysis showed that gasification can influence the composition of CCs present in mineral water and that the plastic material of the bottles is a likely source of CCs. In addition, benzaldehyde levels may be associated with the use of recycled materials., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This paper describes a novel method based on an ultrasound-assisted extraction microscale device (UAE-MSD) for the rapid and simultaneous determination of polycyclic aromatic hydrocarbons (PAH) and polycyclic aromatic sulfur heterocycles (PASH) in marine sediments. Solvent extraction conditions were optimized by applying a simplex-centroid mixture design. Optimum conditions were used to validate and determine the concentrations of 17 PAH and 7 PASH. The best conditions were obtained by extracting sediments with 500 µL of DCM:MeOH (65:35, v:v) over 23 min of sonication. Analytes were determined by gas chromatography/mass spectrometry in selective ion monitoring (GC-MS/SIM). Matrix effects were evaluated, and matrix-matched calibration was used for quantitation. Analytical method validation was carried out using the certified reference material NIST SRM 1941b, as well as sediment spiked with PASH at three concentration levels. Recoveries ranged between 70.0 ± 3.5% and 119 ± 9.1% for PAH and 80.6 ± 10.4% and 120 ± 10% for PASH. Linearity (R 2 ) was ≥0.99 for all compounds. Method detection limits ranged from 8.8 to 30.2 ng g -1 , while limits of quantification ranged from 29.4 to 1011 ng g -1 . UAE-MSD was applied to marine sediments exposed to different anthropogenic impacts collected in Todos os Santos Bay, Brazil. PAH concentrations ranged from -1 , while PASH levels were -1 . Dibenzothiophene was the compound presented in the highest concentration in all samples, with values up to 249 ng g -1 . The results indicated contributions of pyrogenic sources from all compounds. The developed method can potentially be applied to extract trace levels of compounds in different solid matrices to minimize extraction time and solvent consumption., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

Microplastics (MPs) are emerging and ubiquitous contaminants which have been gaining prominence since the last decade to nowadays. This is due to their possible adverse effects in aquatic ecosystems as well as the huge amount of plastic waste exponentially generated around the globe. Plastics may be introduced either directly to water bodies or indirectly to the aquatic systems by being carried by the wind, from emissions of contaminated effluents, and soil leaching, among other processes. In turn, these debris may interact with organic and inorganic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and trace constituents, and with microorganisms. Although the abundance of microplastics from South Atlantic waters is among the highest found worldwide, the number of studies in these marine waters regarding MP contamination is still scarce. Additionally, there still are no consensus on the best sampling conditions, which may be underestimating MPs. In this way, adequate MPs studies regarding their distribution, exposure levels, chemical and biological interactions are highly suggested in order to better understand both environmental and human health potential risks. This review assessed advances in sampling, analytical methodologies, characterization and understanding of MP sources in these marine waters in comparison to data from other regions around the globe., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The use of personal protective equipment (PPE) has been considered the most effective way to avoid the contamination of healthcare workers by different microorganisms, including SARS-CoV-2. A spray disinfection technology (chamber) was developed, and its efficacy in instant decontamination of previously contaminated surfaces was evaluated in two exposure times. Seven test microorganisms were prepared and inoculated on the surface of seven types of PPE (respirator mask, face shield, shoe, glove, cap, safety glasses and lab coat). The tests were performed on previously contaminated PPE using a manikin with a motion device for exposure to the chamber with biocidal agent (sodium hypochlorite) for 10 and 30s. In 96.93% of the experimental conditions analyzed, the percentage reduction was >99% (the number of viable cells found on the surface ranged from 4.3x106 to <10 CFU/mL). The samples of E. faecalis collected from the glove showed the lowest percentages reduction, with 86.000 and 86.500% for exposure times of 10 and 30 s, respectively. The log10 reduction values varied between 0.85 log10 (E. faecalis at 30 s in glove surface) and 9.69 log10 (E. coli at 10 and 30 s in lab coat surface). In general, E. coli, S. aureus, C. freundii, P. mirabilis, C. albicans and C. parapsilosis showed susceptibility to the biocidal agent under the tested conditions, with >99% reduction after 10 and 30s, while E. faecalis and P. aeruginosa showed a lower susceptibility. The 30s exposure time was more effective for the inactivation of the tested microorganisms. The results show that the spray disinfection technology has the potential for instant decontamination of PPE, which can contribute to an additional barrier for infection control of healthcare workers in the hospital environment., Competing Interests: The authors have declared that no competing interests exist.

A dispersive micro-solid phase extraction (d-µ-SPE) procedure was developed for the simultaneous extraction of 39 multiclass pesticides, containing a variety of chemical groups (organophosphate, organochlorine, pyrethroid, strobilurin, thiocarbamate, triazole, imidazole, and triazine), from water samples. A customized d-µ-SPE glass device was combined with a multi-tube platform vortex and a micro-desorption unit (Whatman Mini-UniPrep G2 syringeless filter), which allowed the unique simultaneous desorption, extract filtration, and injection. A simplex-centroid mixture design and Doehlert design were employed to optimize the extraction conditions. The optimized extraction conditions consisted of an extraction time of 30 min, an addition of 6.74 % of NaCl into 100 mL of water sample, and a desorption time of 24 min with 500 µL of EtAc. The procedure provided a low limit of detection (LOD), ranging from 0.51 ng L -1 (4,4-DDE) to 22.4 ng L -1 (dimethoate), and an enrichment factor ranging from 72.5 (dimethoate) to 200 (tebuconazole). The relative recoveries of the pesticides from spiked freshwater and seawater ranged from 74.2 % (endrin) to 123 % (molinate). The proposed procedure was applied to detect the presence of multiclass pesticides in environmental water samples. Three pesticides commonly applied in Brazil, namely, malathion, dimethoate, and lambda-cyhalothrin, were detected in concentrations ranging from -1 (dimethoate)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Air pollution represents a considerable threat to health worldwide. The São Paulo Metropolitan area, in Brazil, has a unique composition of atmospheric pollutants with a population of nearly 20 million people and 9 million passenger cars. It is long known that exposure to particulate matter less than 2.5 µm (PM 2.5 ) can cause various health effects such as DNA damage. One of the most versatile defense mechanisms against the accumulation of DNA damage is the nucleotide excision repair (NER), which includes XPC protein. However, the mechanisms by which NER protects against adverse health effects related to air pollution are largely unknown. We hypothesized that reduction of XPC activity may contribute to inflammation response, oxidative stress and DNA damage after PM 2.5 exposure. To address these important questions, XPC knockout and wild type mice were exposed to PM 2.5 using the Harvard Ambient Particle concentrator. Results from one-single exposure have shown a significant increase in the levels of anti-ICAM, IL-1β, and TNF-α in the polluted group when compared to the filtered air group. Continued chronic PM 2.5 exposure increased levels of carbonylated proteins, especially in the lung of XPC mice, probably as a consequence of oxidative stress. As a response to DNA damage, XPC mice lungs exhibit increased γ-H2AX, followed by severe atypical hyperplasia. Emissions from vehicles are composed of hazardous substances, with polycyclic aromatic hydrocarbons (PAHs) and metals being most frequently cited as the major contributors to negative health impacts. This analysis showed that benzo[b]fluoranthene, 2-nitrofluorene and 9,10-anthraquinone were the most abundant PAHs and derivatives. Taken together, these findings demonstrate the participation of XPC protein, and NER pathway, in the protection of mice against the carcinogenic potential of air pollution. This implicates that DNA is damaged directly (forming adducts) or indirectly (Reactive Oxygen Species) by the various compounds detected in urban PM 2.5 ., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Purpose: To evaluate the effects of stomach and duodenal fluid on enamel surfaces, simulating the action of refluxed liquid in patients with duodenogastric reflux., Methods and Materials: Forty bovine incisors were used to obtain enamel fragments. Only half of the enamel surface was exposed to erosive challenges; the samples were then randomly divided into the following four groups (n = 10): G1: HCl; G2: HCl + pepsin; G3: HCl + ox bile + NaHCO3; and G4: HCl + pancreatin + NaHCO3. The specimens were placed in 37°C solutions, six times per day, for 20 s, over a period of 5 days and then analysed for morphology, surface roughness and the step formed on the dental enamel using confocal laser microscopy. The data were analysed using the Kruskal-Wallis and Dunn's test (p <0.05)., Results: Both analyses revealed a higher step and surface roughness for the G3 group (5.6 μm ± 1.69, 2.2 μm ± 1.61), which were statistically significant compared with the G1 and G2 groups (3.9 μm ± 1.5 μm; 1.0 μm ± 0.18; 3.7 μm ± 1.45; and 0.9 μm ± 0.12) (p <0.05); only the step in the G4 group (4.9 μm ± 1.8 μm) was similar to that of the G3 group (p >0.05). Morphological analysis showed greater structural loss in the G3 and G4 groups., Conclusions: Bile and pancreatin, in combination with hydrochloric acid, may promote a greater loss of structure, increased surface roughness and loss of enamel prismatic anatomy.

This study presents the development and application of a new analytical methodology for determination of free- and bound-carbonyl compounds (CC) (as the CC themselves and as the hydroxyalkylsulfonic acids - HASA, respectively) in airborne particles. Free- and bound-CC determination were done through reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH) and analysis by UFLC-MS. The method was successfully validated, showing good figures for linearity (R 2  ≥ 0.9937), sensibility (3 fg ˂ LOD ˂ 20 fg for methacrolein and heptanal, respectively) and repeatability (5.9% ˂ RSD ˂ 13%). The proposed method was successfully applied in real samples of inhalable atmospheric particulate matter (PM 10 ) and urban dust certified reference material (SRM 1649 b). The main CC determined in the SRM 1649 b was formaldehyde (75.4 μg g -1 in the free form, and 1898 μg g -1 in the bound form). In addition, for the bound-CC form (HASA), concentrations were determined for acetaldehyde (60.3 μg g -1 ), acetone (20.5 μg g -1 ), acrolein (9.15 μg g -1 ), propionaldehyde (17.1 μg g -1 ) and valeraldehyde (12.2 μg g -1 ). For PM 10 samples, formaldehyde (148 μg g -1 ) and acetaldehyde (28.9 μg g -1 ) were quantified as free aldehydes and as HASA (hydroxymethanelsulfonic acid and hydroxyethanesulfonic acid were 432 μg g -1 and 211 μg g -1 , respectively). Other bound-CC were, on average, within 19.2 μg g -1 (acrolein) and 62.1 μg g -1 (valeraldehyde). For all samples, acetone, acrolein, propionaldehyde and valeraldehyde were quantified only as HASA (bound-CC). Therefore, we could identify and quantify six carbonyl compounds using the proposed method. It is worth mentioning the hydrolysis step was crucial for the correct quantification of the HASAs. This was, in turn, what enabled the quantification of a greater number of analytes in the airborne samples. Hence, this procedure was found to be comprehensive, precise, accurate and suitable to be employed for determination of free-CC and HASA (bound-CC) in atmospheric particulate samples., Competing Interests: Declaration of competing interest I declare no conflicts of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this work we report the occurrence of powerful mutagenic 3-nitrobenzanthrone (3-NBA), in addition to 18 polycyclic aromatic hydrocarbons (PAHs), 6 oxygenated PAHs and 27 nitrated PAHs in polychaete worms. Benzanthrone (BA), another important mutagenic polycyclic aromatic compound (PAC) also was detected in the samples. Polychaete annelids have great ecological relevance, being widely distributed in different environmental conditions, from intertidal zones up to seven thousand feet deep areas. They are abundantly found in both contaminated and uncontaminated areas and, therefore, used as indicators of the pollution status of a given area. As we know, so far, most of these PACs has not been previously reported in living organisms before. The 3-NBA concentrations determined in this study were within 0.11-5.18 µg g -1 . Other relevant PACs such as PAHs, quinones and nitro-PAHs were found in maximum concentrations at 0.013 µg g -1 (coronene) to 11.1 µg g -1 (benzo[k]fluoranthene), 0.823 µg g -1 (9,10-phenenthrenequinone) to 12.1 µg g -1 (1,4-benzoquinone) and 0.434 (1-nitronaphthalene) µg g -1 to 19.2 µg g -1 (6-nitrobenzo[a]pyrene), respectively. Principal component analysis (PCA), ternary correlations and diagnostic ratios were employed in order to propose probable sources for PACs. Although statistical analysis preliminarily has indicated both pyrogenic and petrogenic contributions, petrogenic sources were predominant reflecting the impacts of petroleum exploration and intensive traffic of boats in the study area.

This study investigated different combinations of Pd/Mg, as chemical modifier, for sulfur determination, via CS molecule, in shale oil samples by high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS). It was evaluated the mixture Pd/Mg in aqueous solution, Pd/Mg in propan-1-ol and the Pd/Mg in propan-1-ol plus Ru as a permanent modifier. The best sensitivity was achieved with Pd/Mg mixture in propan-1-ol. The high solubility of the samples in propan-1-ol promotes a better interaction with the modifier and, consequently, a more efficient thermal stability of the CS molecules. Due to the high sulfur content in the samples, the analytical line at 258.288 nm was used. Only a minimum sample preparation was required, i.e., a dilution in propan-1-ol by a factor of 1:10 (w/w). Temperatures of 800 °C and 2200 °C were the optimized conditions for pyrolysis and vaporization, respectively. The calibration curve was constructed with l-cysteine aqueous standard solutions. The characteristic mass was 27 ng; detection and quantification limits were 0.012% (w/w) and 0.039% (w/w), respectively. The accuracy of the proposed method was confirmed by the statistical agreement (Student's and Welch's t-test at 95% confidence level) using the certified reference material CRM NIST 1084a and an OTE oil sample whose sulfur content was previously determined by the standard method ASTM D4294. The method was successfully applied in three shale oil samples. The sulfur content in the investigated samples ranged from 1.0% (w/w) to 1.3% (w/w)., (Copyright © 2019. Published by Elsevier B.V.)

Background. There is no gold standard method for human skin odor determination; several techniques can be applied to collect, extract, transfer, and detect human skin odors. However, none of these methods are suitable for field sampling of a large number of individuals. Objective . The present study aimed to develop a simple, fast, non-invasive, and low-cost method for such a purpose. Methods. Considering that hair from legs can act as a retention mesh of volatile organic compounds (VOCs), samples of leg hairs provided by healthy adult males were collected and solid-phase microextraction (SPME), in headspace (HS) mode, coupled to gas chromatography (GC) and mass spectrometry (MS) analysis of the samples was carried out. A pilot test was applied to detect five quality markers that are frequently reported in human skin odors. Then, several steps were performed for method standardization. The method was applied to 36 different individuals (3 sampled under laboratory conditions and 33 under field conditions), aiming to evaluate its applicability in both environments. Findings. A total of 49 VOCs were identified, and 73.5% of these have been reported in previous studies. Main Conclusions. Hair from legs can be considered an efficient tool for human skin odor sampling and a suitable and practical matrix for human skin odor profile determination by using HS-SPME/GC-MS.

We determined depth profiles of total mercury (T-Hg) in six 210 Pb-dated sediment cores from Todos os Santos Bay to reconstruct the history of anthropogenic Hg accumulation. We also assessed superficial sediments samples from five estuaries. T-Hg concentrations (5-3500 μg kg -1 ) presented a large spatial and temporal variability. T-Hg concentrations in Ribeira Bay increased up to 200-fold along time, whereas the fluxes of T-Hg are substantially higher (up to 10,000 fold) than present-day wet deposition for industrialized areas. Sedimentary records indicate that a chlor-alkali plant has been the main source of Hg pollution until the present, although the T-Hg records suggest that harbor, shrimp farming, and oil refinery activities, besides Hg atmospheric depositions, are important across the bay. Sediments in the Ribeira Bay act as an important Hg sink. If sediments are eroded or disturbed, they may release Hg, thus posing a serious risk to wildlife and ecosystem health. CAPSULE: Sedimentary cores provide data on preindustrial levels and also anthropogenic fluxes of Hg for the appraisal of the magnitude, processes and potential risks of the contamination., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Polycyclic aromatic compounds (PACs) are known due to their mutagenic activity. Among them, 2-nitrobenzanthrone (2-NBA) and 3-nitrobenzanthrone (3-NBA) are considered as two of the most potent mutagens found in atmospheric particles. In the present study 2-NBA, 3-NBA and selected PAHs and Nitro-PAHs were determined in fine particle samples (PM 2.5) collected in a bus station and an outdoor site. The fuel used by buses was a diesel-biodiesel (96:4) blend and light-duty vehicles run with any ethanol-to-gasoline proportion. The concentrations of 2-NBA and 3-NBA were, on average, under 14.8 µg g -1 and 4.39 µg g -1 , respectively. In order to access the main sources and formation routes of these compounds, we performed ternary correlations and multivariate statistical analyses. The main sources for the studied compounds in the bus station were diesel/biodiesel exhaust followed by floor resuspension. In the coastal site, vehicular emission, photochemical formation and wood combustion were the main sources for 2-NBA and 3-NBA as well as the other PACs. Incremental lifetime cancer risk (ILCR) were calculated for both places, which presented low values, showing low cancer risk incidence although the ILCR values for the bus station were around 2.5 times higher than the ILCR from the coastal site.

Conventional methods for determination of polycyclic aromatic compounds (PACs) in sediments usually require large sample sizes (grams) and solvent volumes (at least 100 mL) through the employment of Soxhlet extraction, which is both time (hours) and energy consuming, among other disadvantages. We developed a new analytical protocol for the determination of PACs in sediments using microextraction, which requires small sample masses (25 mg), 500 μL of acetonitrile-dichloromethane mix and sonication for 23 min, followed by GC-MS analysis. The method was validated using the certified reference material SRM 1941b - NIST organic marine sediment, as well as internal deuterated standards. Seventeen PAHs, seven nitro-PAHs and one quinone were detected and quantified. The mean concentrations were 90.4 ng g -1 for PAHs, 179.2 ng g -1 for nitro-PAHs and 822.5 ng g -1 for quinones. The proposed method showed good sensitivity, linearity, precision and accuracy for the determination of PAC in sediments samples., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Background: Many studies have investigated what could attract insects of medical importance and a crucial role has lately been attributed to human skin odors. Most of these researches have been concerned with mosquitoes, e.g., vectors of dengue and malaria. Little is known about volatile organic compounds (VOCs) from human skin odors and their effects on leishmania vectors., Objective: The present study aimed to identify the VOCs from human skin that can be attractive to female anthropophilic phlebotomine sandflies., Results: Forty-two VOCs were identified from skin odors of 33 male volunteers, seven of which were tested in wind tunnel assays employing field-captured phlebotomine sandflies (75.4% identified as Lutzomyia intermedia). Hexane and (E)-oct-3-en-1-ol (octenol) were used as negative and positive controls, respectively. 2-Phenylacetaldehyde (hereafter called phenylacetaldehyde), 6-methylhept-5-en-2-one (also known as sulcatone), nonadecane and icosane were found to activate female phlebotomine sandflies, but only phenylacetaldehyde, 6-methylhepten-5-en-2-one and icosane elicited attraction responses., Conclusions: These results suggest that phenylacetaldehyde, 6-methylhepten-5-en-2-one and icosane may be suitable candidates for attractiveness experimentation in the field which can be an important tool to develop strategies concerning human beings protection against phlebotomine sandflies bites and consequently against leishmaniasis., Competing Interests: The authors have declared that no competing interests exist.

This work proposes a method for the determination of free and total sulfur(IV) compounds in coconut water samples, using the high-resolution continuum source molecular absorption spectrometry. It is based on the measurement of the absorbance signal of the SO 2 gas generate, which is resultant of the addition of hydrochloric acid solution on the sample containing the sulfating agent. The sulfite bound to the organic compounds is released by the addition of sodium hydroxide solution, before the generation of the SO 2 gas. The optimization step was performed using multivariate methodology involving volume, concentration and flow rate of hydrochloric acid. This method was established by the sum of the absorbances obtained in the three lines of molecular absorption of the SO 2 gas. This strategy allowed a procedure for the determination of sulfite with limits of detection and quantification of 0.36 and 1.21mgL -1 (for a sample volume of 10mL) and precision expressed as relative standard deviation of 5.4% and 6.4% for a coconut water sample containing 38.13 and 54.58mgL -1 of free and total sulfite, respectively. The method was applied for analyzing five coconut water samples from Salvador city, Brazil. The average contents varied from 13.0 to 55.4mgL -1 for free sulfite and from 24.7 to 66.9mgL -1 for total sulfur(IV) compounds. The samples were also analyzed employing the Ripper´s procedure, which is a reference method for the quantification of this additive. A statistical test at 95% confidence level demonstrated that there is no significant difference between the results obtained by the two methods., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Thermochemical processes can convert the biomass into fuels, such as bio-oil. The biomass submitted to pyrolysis process, such as fibers, are generally rich in silicon, an element that can lead to damages in an engine when there is high concentration in a fuel. High-resolution continuum source atomic absorption spectrometry (HR-CS AAS) is an interesting alternative for Si determination in the products and byproducts of the pyrolysis process because, besides the flame (F) and graphite furnace (GF) atomizers, it has enhanced the application of direct analysis of solid samples (SS) within GF. This study aimed the development of methods to determine Si in biomass samples, their products and byproducts using HR-CS AAS. A high-resolution continuum source atomic absorption spectrometer contrAA 700 equipped with F and GF atomizers was used throughout the study. HR-CS F AAS (λ = 251.611nm, 1 detection pixel, N 2 O/C 2 H 2 flame) was used to evaluate Si content in biomass and ash, after a microwave-assisted acid digestion with HNO 3 and HF. HR-CS GF AAS (T pyr = 1400°C, T atom = 2650°C) has evaluated Si in pyrolysis water and bio-oil at 251.611nm, and in peach pit biomass and ash at 221.174nm using SS, both wavelengths with 1 detection pixel. Rhodium (300μg) was applied as permanent modifier and 10μgPd + 6μg Mg were pipetted onto the standards/samples at each analysis. Three different biomass samples were studied: palm tree fiber, coconut fiber and peach pit, and three certified reference materials (CRM) were used to verify the accuracy of the methods. The figures of merit were LOD 0.09-20mgkg -1 , and LOQ 0.3-20mgkg -1 , considering all the methods. There were no significant differences between the CRM certified values and the determined ones, using a Student t-test with a confidence interval of 95% (n = 5). Si concentration ranged from 0.11-0.92% mm -1 , 1.1-1.7mgkg -1 , 3.3-13mgkg -1 , and 0.41-1.4%mm -1 , in biomass, bio-oil, pyrolysis water and ash, respectively. Si remained mostly in the ash, leading to a mass fraction of up to 103%, even when the Si loss is not considered. Silicon concentration in bio-oil was below 1.7mgkg -1 , which is suitable for its application as a fuel. The developed methods using HR-CS AAS are suitable for Si determination in biomass, bio-oil, pyrolysis water, and ash. The application of bio-oil as an alternative fuel would be possible evaluating its Si content due to its low levels. The mass balance for Si has proved to be an important tool in order to evaluate the correct disposal of pyrolysis process byproducts., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The intensive use of pesticides such as herbicides, insecticides, fungicides and acaricides has been lead to ubiquitous contamination, being present not only in soils, water bodies and/or crops, but also in the atmosphere. Considering the massive amount of pesticides employed globally, together to their persistence, this may be an important concern regarding air quality and human health worldwide. In the present study we developed a green sensitive sample preparation method for determination of nine organophosphates, two pyrethroids, one carbamate, and one strobirulin in PM2.5 collected in a tropical coastal area in the Southern Hemisphere for the first time. Extraction of PM2.5 sample masses, as low as 206 µg, were performed in a miniaturized device using 500 μL of a mixture containing 18% acetonitrile in dichloromethane followed by sonication for 23 minutes and injection into GC-MS. A total of 12 pesticides were identified and quantified successfully, among them, eight banned pesticides. A risk assessment exposure and cancer risk for possible carcinogenic pesticides (bifenthrin, malathion, parathion and permethrin) were performed for exposure of adults, children and infants. Hazard Quotient and cumulative exposure for organophosphate and pyrethroid pesticides were less than 1, showing that cumulative risk is within acceptable range.

Stem cells possess the ability to home in and travel to damaged tissue when injected intravenously. For the cells to exert their therapeutic effect, they must cross the blood vessel wall and enter the surrounding tissues. The mechanism of extravasation injected stem cells employ for exit has yet to be characterized. Using intravital microscopy and a transgenic zebrafish line Tg(fli1a:egpf) with GFP-expressing vasculature, we documented the detailed extravasation processes in vivo for injected stem cells in comparison to white blood cells (WBCs). While WBCs left the blood vessels by the standard diapedesis process, injected cardiac and mesenchymal stem cells underwent a distinct method of extravasation that was markedly different from diapedesis. Here, the vascular wall undergoes an extensive remodeling to allow the cell to exit the lumen, while the injected cell remains distinctively passive in activity. We termed this process Angio-pello-sis, which represents an alternative mechanism of cell extravasation to the prevailing theory of diapedesis. Stem Cells 2017;35:170-180 Video Highlight: https://youtu.be/i5EI-ZvhBps., (© 2016 AlphaMed Press.)

The method allowed simultaneous characterization of PAHs, nitro-PAHs and quinones in atmospheric particulate matter. This method employs a miniaturized micro-extraction step that uses 500 μL of an acetonitrile-dichloromethane mix and instrumental analysis by means of a high-resolution GC-MS. The method was validated using the SRM1649b NIST standard reference material as well as deuterated internal standards. The results are in good agreement with the certified values and show recoveries between 75% and 145%. Limit of detection (LOD) values for PAHs were found to be between 0.5 pg (benzo[a]pyrene) to 2.1 pg (dibenzo[a,h]anthracene), for nitro-PAHs ranged between 3.2 pg (1-nitrobenzo[e]pyrene) and 22.2 pg (3-nitrophenanthrene), and for quinones ranged between 11.5 pg (1,4-naphthoquinone) and 458 pg (9,10-phenanthraquinone). The validated method was applied to real PM10 samples collected on quartz fiber filters. Concentrations in the PM10 samples ranged from 0.06 to 15 ng m(-3) for PAHs, from

A method has been developed for the determination of lead in biomass, bio-oil, pyrolysis aqueous phase, and biomass ashes by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) and direct solid or liquid sample analysis. All measurements were performed without chemical modifier and calibration could be carried out using aqueous standard solutions. A pyrolysis temperature of 800°C and an atomization temperature of 2200°C were applied. The limits of detection and quantification were, respectively, 0.5 µg kg(-1) and 2 µg kg(-1) using the analytical line at 217.001 nm and 6 µg kg(-1) and 19 µg kg(-1) at 283.306 nm. The precision, expressed as relative standard deviation, was between 3% and 10%, which is suitable for direct analysis. The lead concentrations found for the solid samples varied between 0.28 and 1.4 mg kg(-1) for biomass and between 0.25 and 2.3 mg kg(-1) for ashes, these values were much higher than those found for bio-oil (2.2-16.8 µg kg(-1)) and pyrolysis aqueous phase (3.2-18.5 µg kg(-1)). After the determination of lead in the samples, it was possible to estimate the relative distribution of this element in the fractions of the pyrolysis products, and it was observed that most of the lead present in the biomass was eliminated to the environment during the pyrolysis process, with a significant portion retained in the ashes., (Copyright © 2015 Elsevier B.V. All rights reserved.)

An analytical method for the determination of sulfur, as the tin mono-sulfide (SnS) molecule, in crude oil using high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS) has been developed. The molecular absorbance of the SnS has been measured using the wavelength at 271.624 nm and the crude oil samples were prepared as micro-emulsions due to their high viscosity. Several chemical modifiers (Ir, Pd, Ru, Zr) were tested and palladium was chosen, because it exhibited the best performance. The heating program was optimized by comparing the pyrolysis and vaporization curves obtained for an aqueous sulfur standard and a micro-emulsion of a crude oil certified reference material (CRM). The optimum pyrolysis and vaporization temperatures were found to be 600 and 2000°C, respectively. The limit of detection and the characteristic mass using micro-emulsion analysis of crude oil samples were 5.8 and 13.3 ng S. Accuracy and precision of the method has been evaluated using two crude oil CRM (NIST 2721 and NIST 2722), showing good agreement with the informed or certified values., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Unlabelled: Lung diseases are devastating conditions and ranked as one of the top five causes of mortality worldwide according to the World Health Organization. Stem cell therapy is a promising strategy for lung regeneration. Previous animal and clinical studies have focused on the use of mesenchymal stem cells (from other parts of the body) for lung regenerative therapies. We report a rapid and robust method to generate therapeutic resident lung progenitors from adult lung tissues. Outgrowth cells from healthy lung tissue explants are self-aggregated into three-dimensional lung spheroids in a suspension culture. Without antigenic sorting, the lung spheroids recapitulate the stem cell niche and contain a natural mixture of lung stem cells and supporting cells. In vitro, lung spheroid cells can be expanded to a large quantity and can form alveoli-like structures and acquire mature lung epithelial phenotypes. In severe combined immunodeficiency mice with bleomycin-induced pulmonary fibrosis, intravenous injection of human lung spheroid cells inhibited apoptosis, fibrosis, and infiltration but promoted angiogenesis. In a syngeneic rat model of pulmonary fibrosis, lung spheroid cells outperformed adipose-derived mesenchymal stem cells in reducing fibrotic thickening and infiltration. Previously, lung spheroid cells (the spheroid model) had only been used to study lung cancer cells. Our data suggest that lung spheroids and lung spheroid cells from healthy lung tissues are excellent sources of regenerative lung cells for therapeutic lung regeneration., Significance: The results from the present study will lead to future human clinical trials using lung stem cell therapies to treat various incurable lung diseases, including pulmonary fibrosis. The data presented here also provide fundamental knowledge regarding how injected stem cells mediate lung repair in pulmonary fibrosis., (©AlphaMed Press.)

According to the demands of energy saving and carbon emission reduction, the water vs. energy nexus has become a major concern worldwide. Brazil occupies a singular position in the global energy system. A major portion of the Brazilian occupancies has electricity and the energy system expansion that, at first, possesses adequate means for supporting the economic growing may experience some turnovers. The Brazil determination through alternative fuels was a natural choice, given its large hydropower potential and land agricultural base. In the transportation sector Brazil has developed its energy matrix towards an important rate of ethanol and biodiesel. Although those fuels are low carbon emitter, they may probably not be an affordable alternative regarding land use, food security and water footprint. In this way, considering the recent advances in the exploration of oil from Pre-salt (9-15 million barrels) and the discovery of shale gas wells up to 245 tcf, together to unfavorable social and environmental issues associated to biofuels, the Brazilian energy matrix might turn back to the fossil fuels again. These represent challenges to the Brazilian policymakers and how they will be solved will reflect not only in Brazil but also to the world at large.

The aim of this work was to evaluate the concentrations of polycyclic aromatic hydrocarbons (PAHs) in soils to which solid shale materials (SSMs) were added as soil conditioners. The SSMs were derived from the Petrosix pyrolysis process developed by Petrobras (Brazil). An improved ultrasonic agitation method was used to extract the PAHs from the solid samples (soils amended with SSMs), and the concentrations of the compounds were determined by gas chromatography coupled to mass spectrometry (GC-MS). The procedure provided satisfactory recoveries, detection limits, and quantification limits. The two-, three-, and four-ring PAHs were most prevalent, and the highest concentration was obtained for phenanthrene (978 ± 19 μg kg(-1) in a pyrolyzed shale sample). The use of phenanthrene/anthracene and fluoranthene/pyrene ratios revealed that the PAHs were derived from petrogenic rather than pyrogenic sources. The measured PAH concentrations did not exceed national or international limit values, suggesting that the use of SSMs as soil conditioners should not cause environmental damage.

Despite the efficacy of cardiac stem cells (CSCs) for treatment of cardiomyopathies, there are many limitations to stem cell therapies. CSC-derived exosomes (CSC-XOs) have been shown to be responsible for a large portion of the regenerative effects of CSCs. Using a mouse model of doxorubicin induced dilated cardiomyopathy, we study the effects of systemic delivery of human CSC-XOs in mice. Mice receiving CSC-XOs showed improved heart function via echocardiography, as well as decreased apoptosis and fibrosis. In spite of using immunocompetent mice and human CSC-XOs, mice showed no adverse immune reaction. The use of CSC-XOs holds promise for overcoming the limitations of stem cells and improving cardiac therapies.

Visceral leishmaniasis (VL) is a zoonosis whose etiologic agent in the Americas is Leishmania infantum, and dogs are the main host. Research and innovation in diagnostic techniques are essential to improve the surveillance and control of VL in endemic areas. The present study investigates the profile of the volatile organic compounds (VOCs) emitted by healthy dogs and by dogs infected by L. infantum to detect variations in the VOCs that may be used as biomarkers in the diagnosis of VL. In total, 36 dogs were selected from an endemic area and divided into three groups: G1, not infected with L. infantum; G2, infected without clinical signs of VL; and G3, infected with clinical signs of VL. To analyze the profiles of the VOCs emitted by dogs from the three groups, solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS) was used. Variations were observed between the profiles of the VOCs emitted in the three groups studied, and they also differentiated infected animals with or without clinical signs. Six VOCs were identified as potential biomarkers of infection, with significant variations between healthy dogs (G1) and infected dogs (G2 + G3). The detection of variations between groups G2 and G3 suggested that the profiles of some VOCs may be related to the type of immune response and the parasite load of the infected dogs. This study demonstrated the possibility of analysis of VOCs as biomarkers of VL in diagnostic, clinical, and epidemiological work.

The present paper describes the development of a method for the determination of copper in airborne particulate matter using slurry sampling and chemical vapor generation atomic absorption spectrometry (CVG AAS). Chemometric tools were employed to characterize the influence of several factors on the generation of volatile copper species. First, a two-level full factorial design was performed that included the following chemical variables: hydrochloric acid concentration, tetrahydroborate concentration, sulfanilamide concentration and tetrahydroborate volume, using absorbance as the response. Under the established experimental conditions, the hydrochloric acid concentration had the greatest influence on the generation of volatile copper species. Subsequently, a Box-Behnken design was performed to determine the optimum conditions for these parameters. A second chemometric study employing a two-level full factorial design was performed to evaluate the following physical factors: tetrahydroborate flow rate, flame composition, alcohol volume and sample volume. The results of this study demonstrated that the tetrahydroborate flow rate was critical for the process. The chemometric experiments determined the following experimental conditions for the method: hydrochloric acid concentration, 0.208 M; tetrahydroborate concentration, 4.59%; sulfanilamide concentration, 0.79%; tetrahydroborate volume, 2.50 mL; tetrahydroborate flow rate, 6.50 mL min(-1); alcohol volume, 200 µL; and sample volume, 7.0 mL. Thus, this method, using a slurry volume of 500 µL and a final dilution of 7 mL, allowed for the determination of copper with limits of detection and quantification of 0.30 and 0.99 µg L(-1), respectively. Precisions, expressed as RSD%, of 4.6 and 2.8% were obtained using copper solutions at concentrations of 5.0 and 50.0 µg L(-1), respectively. The accuracy was evaluated by the analysis of a certified reference material of urban particulate matter. The copper concentration obtained was 570±63 mg kg(-1), and the certified value was 610±70 mg kg(-1). This method was applied for the determination of copper in airborne particulate matter samples collected in two Brazilian regions of Bahia State, Brazil. The copper contents found varied from 14.46 to 164.31 ng m(-3)., (Copyright © 2014 Elsevier B.V. All rights reserved.)