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Made available in DSpace on 2021-06-25T11:14:48Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 To access the sources of air pollutants is crucial to control atmospheric pollution in urban areas, minimizing human exposure. Particulate matter is a pollutant of great concern making its chemical and morpho-structural characterization of enormous importance. The present work aims at the characterization of atmospheric PM10 and PM2.5. Data of the aerosol mass concentration was correlated by multivariate analysis with water-soluble ion fraction composition accessed by ion chromatography (IC), as well as with meteorological information and air mass backward trajectories. The gravimetric analysis presented average values 3 to 4 times higher than the guide values recommended by the World Health Organization (WHO). A morpho-structural analysis by SEM/FEG coupled to EDS was also carried out identifying the coarse fraction elements from minerals and from soil resuspension organic spherical particles that originated from combustion processes as well as Ti, associated with long-distance transportation. In the fine fraction, Zn with origin probably in tires and vehicle brakes was found. These origins were confirmed by the air masses’ backward trajectories obtained by the HYSPLIT model (NOAA). This study contributes to a better understanding of the complex composition of the particulate material in the atmosphere of Araraquara City, resulting from the combination of local and long-distance sources, and serves as a basis for the comparison with future studies related to the air quality at this and other regions in Brazil and in the world. Graphical abstract: [Figure not available: see fulltext.] São Paulo State University (Unesp) Institute of Chemistry Centro de Química Estrutural Faculdade de Ciências Universidade de Lisboa, Edif. C8, Campo Grande São Paulo State University (Unesp) Biosciences Languages and Exact Sciences Institute, Ibilce Área Departamental de Engenharia Química do Instituto Superior de Engenharia de Lisboa ISEL-ADEQ, Rua Conselheiro Emídio Navarro, 1 São Paulo State University (Unesp) Institute of Chemistry São Paulo State University (Unesp) Biosciences Languages and Exact Sciences Institute, Ibilce

Made available in DSpace on 2021-06-25T11:10:34Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 The importance of studying the atmospheric pollution due to its effects on human health and other ecosystems, the inexistence of national production of equipment for air sample collection, and the high cost of the imported equipment (especially in developing countries) led the authors of the present work to construct a low-cost Gent type sampler. The construction of the sampler was carried out by combining low-cost materials with good mechanical strength (such as nylon 6.0), hydraulic piping PVC, and the use of a 3D printer. The innovation of the present work is the employment of a 3D printer using ABS polymer to create the grids that cannot be machined. In addition to the sampler, the system is composed of a vacuum pump, a gas meter, and a rotameter. The total cost of the sampling system amounted at about 1200 USD, and the cost of the manufactured Gent type sampler did not reach 100 USD. The results obtained while using this set for sampling atmospheric aerosol for a period of 11 months were compared with the mass concentration of PM10 obtained from the official environmental company, CETESB of São Paulo State, Brazil, showing good correlation with those from CETESB — which confirmed its effectiveness and suitability for use. The low cost, easy operation, and versatility of the built Gent type sampler enable its use for scientific and academic purposes. The equipment can be useful in environmental monitoring networks, in low-income regions, and as an instrument for environmental education used in universities. Graphical abstract: [Figure not available: see fulltext.]. São Paulo State University (UNESP) Institute of Chemistry Centro de Química Estrutural Faculdade de Ciências Universidade de Lisboa, C8 Campo Grande Instituto Nacional de Pesquisas Espaciais – INPE São Paulo State University (Unesp) Biosciences Languages and Exact Sciences Institute Ibilce São Paulo State University (UNESP) Institute of Chemistry São Paulo State University (Unesp) Biosciences Languages and Exact Sciences Institute Ibilce

Made available in DSpace on 2020-12-12T01:52:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-03-01 Air pollution causes deleterious effects on human health with aerosols being among the most polluting agents. The objective of this work is the characterization of the PM2.5 and PM10 aerosol mass in the atmosphere. The methods of analysis include WD-XRF and EDS. Data were correlated with meteorological information and air mass trajectories (model HYSPLIT) by multivariate analysis. A morphological structural analysis was also carried out to identify the probable sources of atmospheric aerosols in the city of São José do Rio Preto, Brazil. The mean mass concentration values obtained were 24.54 μg/m3 for PM10, above the WHO annual standard value of 20 μg/m3 and 10.88 μg/m3 for PM2.5 whose WHO recommended limit is 10 μg/m3. WD-XRF analysis of the samples revealed Si and Al as major components of the coarse fraction. In the fine fraction, the major elements were Al and S. The SEM-FEG characterization allowed identifying the morphology of the particles in agglomerates, ellipsoids and filaments in the PM10, besides spherical in the PM2.5. The analysis by EDS corroborated WD-XRF results, identifying the crustal elements, aluminosilicates and elements of anthropogenic origin in the coarse fraction. For the fine fraction crustal elements were also identified; aluminosilicates, black carbon and spherical particles (C and O) originating from combustion processes were predominant. The use of multivariate analysis to correlate air mass trajectories with the results of the morpho-structural characterization of the particulate matter allowed confirmation of the complex composition of the particles resulting from the combination of both local and long-distance sources. São Paulo State University (Unesp), Chemistry Institute, Analytical Chemistry Department, Araraquara, SP, 14800-060, Brazil; Centro de Química Estrutural - Faculdade de Ciências da Universidade de Lisboa, Edif. C8, Campo Grande, 1749-016 Lisboa, Portugal São Paulo State University (Unesp) Chemistry Institute Analytical Chemistry Department Federal University of São Carlos - UFSCAr Chemistry Department Chemistry and Environmental Sciences Department Biosciences Languages and Exact Sciences Institute Ibilce São Paulo State University (Unesp) São Paulo State University (Unesp), Chemistry Institute, Analytical Chemistry Department, Araraquara, SP, 14800-060, Brazil; Chemistry and Environmental Sciences Department, Biosciences, Languages and Exact Sciences Institute, Ibilce, São Paulo State University (Unesp), São José do Rio Preto, SP, 15054-000, Brazil Centro de Química Estrutural - Faculdade de Ciências da Universidade de Lisboa Edif. C8 São Paulo State University (Unesp) Chemistry Institute Analytical Chemistry Department Chemistry and Environmental Sciences Department Biosciences Languages and Exact Sciences Institute Ibilce São Paulo State University (Unesp)

Made available in DSpace on 2018-12-11T17:07:57Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-02-01 Federación Española de Enfermedades Raras The presence of estrogenic mycotoxins, such as zearalenone (ZEN), in surface waters is an emerging environmental issue. Little is known about its phototransformation behavior, which may influence its environmental fate. In this context, the phototransformation of ZEN was investigated in pure water, river water and estuarine water using simulated sunlight irradiation. Kinetic studies revealed that two concomitant processes contribute to the fate of ZEN under solar irradiation: photoisomerization and photodegradation. This phototransformation followed a pseudo-first order kinetics. ZEN degrades quickly in natural waters and slowly in deionized water, with half-lives (t1/2) of 28 ± 4 min (estuarine water), 136 ± 21 min (river water) and 1777 ± 412 min (deionized water). The effects of different water constituents on the phototransformation of ZEN in aqueous solution have been assessed (NaCl, Ca2+, Mg2+, Fe3+, NO3 − and oxalate ions, synthetic seawater, Fe(III)-oxalate and Mg(II)-oxalate complexes, humic acids, fulvic acids and XAD-4 fraction). In the presence of synthetic seawater salt (t1/2 = 18 ± 5 min) and Fe(III)-oxalate complexes (t1/2 = 61 ± 9 min), the transformation rate increased considerably in relation to other water constituents tested. The solution pH also had a considerable effect in the kinetics with maximum transformation rates occurring around pH 8.5. These results allow us to conclude that phototransformation by solar radiation can be an important degradation pathway of ZEN in natural waters. Analytical Chemistry Department Chemistry Institute São Paulo State University-UNESP Department of Chemistry and CESAM (Centre for Environmental and Marine Studies) University of Aveiro, Campus de Santiago Analytical Chemistry Department Chemistry Institute São Paulo State University-UNESP Federación Española de Enfermedades Raras: PT2020

Made available in DSpace on 2018-12-11T17:15:54Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-06-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Indoor dust is considered an important human exposure route to flame retardants (FRs), which has arised concern due the toxic properties of some of these substances. In this study, ten organophosphorus flame retardants (OPFRs), eight polybrominated diphenyl ethers (PBDEs) and four new brominated flame retardants (NBFRs) were determined in indoor dust from different places in Araraquara-SP (Brazil). The sampled places included houses, apartments, offices, primary schools and cars. The analysis of the sample extracts was performed by gas chromatography coupled to mass spectrometry and two ionization techniques were used (electron ionization – EI; electron capture negative ionization – ECNI). OPFRs were the most abundant compounds and tris(2-butoxyethyl) phosphate (TBOEP), tris(phenyl) phosphate (TPHP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP) and tris(2-chloroisopropyl) phosphate (TCIPP) were present at the highest concentrations. Among the brominated FRs, the most ubiquitous compounds were BDE-209, bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP) and decabromodiphenyl ethane (DBDPE). Statistical analysis revealed that there were differences among dust typologies for TBOEP, TDCIPP, ethylhexyl diphenyl phosphate (EHDPHP), BDE-209, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB), BEH-TEBP and DBDPE, which were attributed to different construction materials in each particular environment and to the age of the buildings. The highest levels of brominated FRs were observed in offices, TBOEP was at high concentration in primary schools, and TDCIPP was at high concentration in cars. A preliminary risk assessment revealed that toddlers were exposed to TBOEP levels higher than the reference dose when considering the worst case scenario. The results obtained in this study showed for the first time that although Brazil does not regulate the use of FRs, these substances are present in indoor dust at levels similar to the observed in countries that have strict fire safety standards, and that humans are exposed to complex mixtures of these contaminants via indoor dust. PBDEs, NBFRs and OPFRs were detected in indoor dust from houses, apartments, schools, offices and cars, and a risk associated to TBOEP exposure was estimated for toddlers. Department of Analytical Chemistry Institute of Chemistry UNESP - Univ Estadual Paulista, Professor Francisco Degni 55 Department of Environmental Chemistry IDAEA-CSIC, Jordi Girona 18-26 Department of Analytical Chemistry Institute of Chemistry UNESP - Univ Estadual Paulista, Professor Francisco Degni 55 CNPq: 401756/2013-0

Ultraviolet (UV) filters are widely used in the formulation of personal care products (PCPs) to prevent damage to the skin, lips, and hair caused by excessive UV radiation. Therefore, large amounts of these substances are released daily into the aquatic environment through either recreational activities or the release of domestic sewage. The concern regarding the presence of such substances in the environment and the exposure of aquatic organisms is based on their potential for bioaccumulation and their potential as endocrine disruptors. Although there are several reports regarding the occurrence and fate of UV filters in the aquatic environment, these compounds are still overlooked in tropical areas. In this study, we investigated the occurrence of the organic UV filters benzophenone-3 (BP-3), ethylhexyl salicylate (ES), ethylhexyl methoxycinnamate (EHMC), and octocrylene (OC) in six water treatment plants in various cities in Southeast Brazil over a period of 6 months to 1 year. All of the UV filters studied were detected at some time during the sampling period; however, only EHMC and BP-3 were found in quantifiable concentrations, ranging from 55 to 101 and 18 to 115 ng L(-1), respectively. Seasonal variation of BP-3 was most clearly noticed in the water treatment plant in Araraquara, São Paulo, where sampling was performed for 12 months. BP-3 was not quantifiable in winter but was quantifiable in summer. The levels of BP-3 were in the same range in raw, treated and chlorinated water, indicating that the compound was not removed by the water treatment process.

Butyltin (BT) contamination was evaluated in hermit crabs from 25 estuaries and in sediments from 13 of these estuaries along about 2,000 km of the Brazilian coast. BT contamination in hermit crabs ranged from 2.22 to 1,746 ng Sn g(-1) of DBT and 1.32 to 318 ng Sn g(-1) of TBT. In sediment samples, the concentration also varied widely, from 25 to 1,304 ng Sn g(-1) of MBT, from 7 to 158 ng Sn g(-1) of DBT, and from 8 to 565 ng Sn g(-1) of TBT. BTs are still being found in surface sediments and biota of the estuaries after the international and Brazilian bans, showing heterogeneous distribution among and within estuaries. Although hermit crabs were previously tested as an indicator of recent BT contamination, the results indicate the presence of contamination, probably from resuspension of BTs from deeper water of the estuary.

The toxicity of butyltin compounds (BTs), mainly tributyltin (TBT), has been reported in different organisms. However, such an analysis in fish after field exposure with reference to the related biomarkers has not been commonly observed in the literature. This study presents the uptake of BTs in the liver of a neotropical marine catfish Cathorops spixii in Paranagua Bay, an important estuarine system located in southern Brazil. Two different areas, close to and distant from the harbor, were used for chemical analysis evaluation of hepatotoxicity through genetic, enzymatic, and histopathological biomarkers. The presence of polycyclic aromatic hydrocarbons in bile was also considered as a biomarker. The results showed a significant relationship between TBT levels and the inhibition of biotransformation enzymes and high occurrence of melanomacrophages in fish collected close to the harbor site. These effects were linked to the absence of TBT metabolites in the liver. In the second site, the presence of DBT was associated with an increase in EROD and GST activity. The larger amount of DNA damage as well as the highest oxidative stress was noted in fish from the less TBT-polluted area, where DBT and bile PAHs occurred. These findings showed different impact levels due to or increased by the chronic exposure of biota to BTs.

This study reports the influence of sugar cane vinasse on the persistence, sorption and leaching potential of diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), hexazinone (3-cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) in both a clay and sandy soil from a tropical area of Brazil. The experiments were conducted out under controlled laboratory conditions. The addition of sugarcane vinasse to soil influenced the persistence and sorption of the herbicides in both the studied clay and sandy soils, with a considerable decrease in the diuron DT₅₀ values in clay soil. The Ground Water Ubiquity Score (GUS) Index classifies the herbicides as leachers in both soils and treatments, with the exception of diuron, which is classified as a non-leacher in clay soil-vinasse and as a transient herbicide in sandy soil. These results suggest that special attention should be given to areas such as those where the sandy soil was collected in this study, which is a recharge area of the Guarani Aquifer and is likely to experience groundwater contamination due to the high leaching potential of the applied pesticides.

Made available in DSpace on 2018-11-26T16:54:53Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-08-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Sao Paulo State Foundation for Science, Technology and Education Support (FACTE) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Butyltin compounds (BTs), including tributyltin (TBT) and its degradation products, dibutyltin and monobutyltin, have been found in a diversity of aquatic systems and causing toxic effects in target and nontarget organisms. They enter in coastal systems through different sources (as antifouling paints, industrial effluents, etc.) where they interact with biotic and abiotic components, and their distribution is commonly determined by the morphological and hydrodynamic conditions of the coastal systems. In this study, we discuss the contamination by BTs on a spatial scale (eight estuaries with three subareas each) and in different compartments of the estuaries (sediments, suspended particulate matter (SPM), and estuarine catfish tissues (liver and gills). Lower concentrations of BTs were found in the sediments (n.d. to 338 ng g(-1)) in comparison to studies before a ban of TBT in antifouling paints was enacted, mostly indicating an old input or preservation related with sediment properties and composition. For SPM samples (n.d. to 175 ng L-1) as well as in fish tissues (n.d. to 1426 ng g(-1)), the presence of these compounds was frequent, especially in the fish due to their movement throughout the estuaries and the potential to assess point sources of BTs. These results indicate that BTs persist in the environment, with variation in amounts between investigated estuaries and even at locations inside the same estuary, because of ideal preservation conditions, transport to remote areas, and input from different sources. Univ Estadual Paulista, Inst Chem, Dept Analyt Chem, R Francisco Degni 55, BR-14800900 Araraquara, SP, Brazil Univ Sao Paulo, Oceanog Inst, Dept Phys Chem & Geol Oceanog, Sao Paulo, Brazil Univ Sao Paulo, Oceanog Inst, Dept Biol Oceanog, Sao Paulo, Brazil Univ Estadual Paulista, Inst Chem, Dept Analyt Chem, R Francisco Degni 55, BR-14800900 Araraquara, SP, Brazil FAPESP: 2012/17898-7

The designation of biodiesel as an environmental-friendly alternative to diesel oil has improved its commercialization and use. However, most biodiesel environmental safety studies refer to air pollution and so far there have been very few literature data about its impacts upon other biotic systems, e.g. water, and exposed organisms. Spill simulations in water were carried out with neat diesel and biodiesel and their blends aiming at assessing their genotoxic potentials should there be contaminations of water systems. The water soluble fractions (WSF) from the spill simulations were submitted to solid phase extraction with C-18 cartridge and the extracts obtained were evaluated carrying out genotoxic and mutagenic bioassays [the Salmonella assay and the in vitro MicroFlow® kit (Litron) assay]. Mutagenic and genotoxic effects were observed, respectively, in the Salmonella/microsome preincubation assay and the in vitro MN test carried out with the biodiesel WSF. This interesting result may be related to the presence of pollutants in biodiesel derived from the raw material source used in its production chain. The data showed that care while using biodiesel should be taken to avoid harmful effects on living organisms in cases of water pollution.

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.

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.

This work presents the influence of sugarcane burning on PAH levels and their profiles at a residence located in Araraquara (SP, Brazil), a city surrounded by sugarcane plantations. The average concentrations of total PAHs (ΣPAHs) associated with atmospheric particulate matter were higher during the burning period (ΣPAHs 22.9 ng m(-3)) than in the non-burning period (ΣPAH 2.35 ng m(-3)). A comparison of our results with previous studies regarding PAH levels and their profiles in Araraquara outdoor air indicated that sugarcane burning was the main PAH air source in the indoor harvesting season samples. The benzo[a]pyrene equivalent (BaP(eq)) was used for cancer risk assessment, and higher average values were obtained in the harvesting season air samples (1.7 ng m(-3)) than in the non-harvesting air samples (0.07 ng m(-3)). These findings suggest that sugarcane burning during the harvesting season can represent a public health risk in affected cities.

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (alpha -HCH, beta -HCH, gamma -HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three São Paulo State cities: Araras, Araraquara and São Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (beta -HCH, gamma -HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, and p,p'-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake.