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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

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 PM

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 PM

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)

Submitted by Guilherme Lemeszenski (guilherme@nead.unesp.br) on 2013-08-22T18:49:24Z No. of bitstreams: 1 S0100-46702010000400015.pdf: 244002 bytes, checksum: 93026127eaf20554d319bb8064b0ccaf (MD5) Made available in DSpace on 2013-08-22T18:49:24Z (GMT). No. of bitstreams: 1 S0100-46702010000400015.pdf: 244002 bytes, checksum: 93026127eaf20554d319bb8064b0ccaf (MD5) Previous issue date: 2010-01-01 Made available in DSpace on 2013-09-30T19:09:37Z (GMT). No. of bitstreams: 2 S0100-46702010000400015.pdf: 244002 bytes, checksum: 93026127eaf20554d319bb8064b0ccaf (MD5) S0100-46702010000400015.pdf.txt: 22810 bytes, checksum: ba93b1a43cd3db10be4b6533df3db78e (MD5) Previous issue date: 2010-01-01 Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-20T14:19:53Z No. of bitstreams: 2 S0100-46702010000400015.pdf: 244002 bytes, checksum: 93026127eaf20554d319bb8064b0ccaf (MD5) S0100-46702010000400015.pdf.txt: 22810 bytes, checksum: ba93b1a43cd3db10be4b6533df3db78e (MD5) Made available in DSpace on 2014-05-20T14:19:53Z (GMT). No. of bitstreams: 2 S0100-46702010000400015.pdf: 244002 bytes, checksum: 93026127eaf20554d319bb8064b0ccaf (MD5) S0100-46702010000400015.pdf.txt: 22810 bytes, checksum: ba93b1a43cd3db10be4b6533df3db78e (MD5) Previous issue date: 2010-01-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Este trabalho teve como objetivo otimizar e validar uma metodologia analítica para determinação de 1-hidróxipireno em urina de trabalhadores envolvidos na colheita da cana-de-açúcar. O método utilizado para determinação de 1-hidroxipireno em urina humana utilizado consiste na hidrólise enzimática, extração e clean-up por extração em fase sólida (SPE) e quantificação por cromatografia líquida de alta eficiência com detector de fluorescência (CLAE/Flu). Quatro tipos de cartuchos foram testados para verificação da porcentagem de recuperação. Urina de cortadores de cana-de-açúcar (não-fumantes e de ambos os sexos) foram coletadas no período da safra (n=39) e entressafra (n=34) da cana-de-açúcar. Os melhores resultados de recuperação foram atribuídos aos cartuchos C18. Os mesmos apresentaram recuperação entre 79% e 108%, com coeficiente de variação entre 5% e 10%. O limite de quantificação do método foi de 74 ng de 1-hidroxipireno por litro de urina. A metodologia otimizada e validada foi utilizada para determinação de amostras reais. Os resultados encontrados na urina dos trabalhadores no período da safra variaram de 0,026 a 2,3 μmol de 1-hidroxipireno por mol de creatinina. No período da entressafra os resultados variaram de 0,0023 a 0,38 μmol de 1-hidroxipireno por mol de creatinina. A metodologia validada mostrou-se adequada para determinação de 1-hidroxipireno em urina humana. Os dados obtidos permitem concluir que há forte correlação entre excreção de 1-hidroxipireno e os períodos de safra e entressafra da cana de açúcar. This study aimed to optimize and validate an analytical methodology for determination of 1-hydroxypyrene in urine of workers involved in harvesting sugar cane. The method used for determining 1-hydroxypyrene in human urine is the enzymatic hydrolysis, extraction and clean-up by solid phase extraction (SPE) and quantified by high performance liquid chromatography with fluorescence detection (HPLC / Flu). Four types of cartridges were tested to verify the percentage of recovery. Urine of sugar-cane workers (non-smokers and of both sexes) were collected during the harvest (n = 39) and non-harvest season (n = 34) of cane sugar. The best recovery results were attributed to the C18 cartridges. They presented recovery between 79% and 108%, with a coefficient of variation between 5% and 10%. The limit of quantification was 74 ng of 1-hydroxypyrene per liter of urine. The optimized and validated methodology was used for determination of real samples. The results found in the urine of workers at harvest period ranged from 0.026 to 2.3 μmol of 1-hydroxypyrene per mol creatinine. During the non-harvesting season the results ranged from 0.0023 to 0.38 μmol of 1-hydroxypyrene per mol creatinine. The validated methodology proved suitable for determination of 1-hydroxypyrene in human urine. The data indicate that there is strong correlation between excretion of 1-hydroxypyrene and the periods during and between harvests of sugar cane. Universidade Estadual Paulista Instituto de Química Departamento de Química Analítica Universidade Estadual Paulista Instituto de Química Departamento de Química Orgânica Universidade Estadual Paulista Instituto de Biociências, Letras e Ciências Exatas Laboratório de Epidemiologia Molecular Universidade Estadual Paulista Instituto de Química Departamento de Química Analítica Universidade Estadual Paulista Instituto de Química Departamento de Química Orgânica Universidade Estadual Paulista Instituto de Biociências, Letras e Ciências Exatas Laboratório de Epidemiologia Molecular

Made available in DSpace on 2018-12-11T16:51:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-04-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Purpose: A comparison was made between three chemical methods to predict bioaccessibility of triclosan (TCS), bisphenol A (BPA), and 17α-ethynylestradiol (EE2) in marine sediments, involving an exchangeable (E) value, butanol extractions, and hydroxypropyl-β-cyclodextrin (β-HPCD) extractions. Materials and methods: A 60-day batch experiment was undertaken where the aqueous phase was analyzed by GC-MS/MS. The bioaccessibility study based on the E value model involved monitoring stable isotopes exchanging with the bioaccessible phase, while this exchangeability was also estimated with sediment extractions with butanol and β-HPCD, respectively. Results and discussion: Based on the E value method, TCS was readily exchangeable for up to 7 days, while after this period become virtually non-exchangeable (not detected in aqueous phase). This trend was also evident for butanol and β-HPCD extractions, suggesting TCS was strongly complexed with the matrix. For BPA and EE2, the fraction considered exchangeable was higher after 14 days and the extraction efficiency was slightly higher for the butanol treatment. Conclusions: Chemical methods to predict bioaccessibility in marine sediments have demonstrated differences between selected contaminants, but agreement between methods. Triclosan shows the highest affinity with tested sediments, some exchangeability in the first days of interaction of E value experiment as well as observed for extraction methods. However, the highest capacity to be extracted from already-sorbed phase was observed for BPA, showed in both extraction methods, and confirming its mobility and bioaccessibility in sediments over the time. Institute of Chemistry Univ. Estadual Paulista - UNESP Chemistry Department State University of Londrina - UEL CSIRO Land and Water Institute of Chemistry Univ. Estadual Paulista - UNESP FAPESP: 12/17898-7 FAPESP: 13/09437-2

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

Huge amounts of waste containing flame retardants reach landfills annually, which can result in environmental contamination if this type of solid residues is not properly managed. This study presents data concerning the occurrence of organophosphorus flame retardants (OPFRs), polybrominated diphenyl ethers (PBDEs) and new brominated flame retardants (NBFRs) in soil, dust, leachate and well water samples from a landfill in Brazil. Samples were collected in different points of the landfill site, including offices, concierge, electronic waste storage area, bulk waste storage area, a place where a recycling cooperative operates, leachate pound and wells. Most of the flame retardants (FRs) were quantified in soil samples (up to 2500 ng g−1). The tris(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were present at the highest levels in the site where bulk waste was disposed in the open air. The most abundant brominated FRs in soil samples were BDE-99, BDE-209, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and the highest levels were observed in the samples collected from the electronic waste storage area. Concerning dust samples, the highest levels of brominated FRs were observed in the electronic waste storage area, while the highest levels of OPFRs were observed in the landfill office. TCIPP, TDCIPP and tris(2-choroethyl) phosphate (TCEP) were quantified in the well water sample collected downstream the bulk waste area. Finally, six OPFRs were quantified in leachate at concentrations ranging from 14 to 965 ng L−1. In conclusion, this study demonstrates that an improper management of wastes containing FRs in landfills can potentially contaminate the surrounding environment and groundwater., The authors acknowledges the National Council for Scientific and Technological Development (CNPq – Brazil, grant number 401756/2013-0), the Program Science Without Borders (Brazil, grant number 313856/2013-3), the Foundation for Support of Science, Technology and Education (FACTE, Brazil), and the Spanish Research Council, Spain. This study has been done in the frame of the Spain-Brazil cooperation project COOP-B20361.

Made available in DSpace on 2018-12-11T17:21:22Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-12-10 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Among the new technologies developed for the heavy-duty fleet, the use of Selective Catalytic Reduction (SCR) aftertreatment system in standard Diesel engines associated with biodiesel/diesel mixtures is an alternative in use to control the legislated pollutants emission. Nevertheless, there is an absence of knowledge about the synergic behaviour of these devices and biodiesel blends regarding the emissions of unregulated substances as the Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs, both recognized for their carcinogenic and mutagenic effects on humans. Therefore, the goal of this study is the quantification of PAHs and Nitro-PAHs present to total particulate matter (PM) emitted from the Euro V engine fuelled with ultra-low sulphur diesel and soybean biodiesel in different percentages, B5 and B20. PM sampling was performed using a Euro V – SCR engine operating in European Stationary Cycle (ESC). The PAHs and Nitro-PAHs were extracted from PM using an Accelerated Solvent Extractor and quantified by GC–MS. The results indicated that the use of SCR and the largest fraction of biodiesel studied may suppress the emission of total PAHs. The Toxic Equivalent (TEQ) was lower when using 20% biodiesel, in comparison with 5% biodiesel on the SCR system, reaffirming the low toxicity emission using higher percentage biodiesel. The data also reveal that use of SCR, on its own, suppress the Nitro-PAHs compounds. In general, the use of larger fractions of biodiesel (B20) coupled with the SCR aftertreatment showed the lowest PAHs and Nitro-PAHs emissions, meaning lower toxicity and, consequently, a potential lower risk to human health. From the emission point of view, the results of this work also demonstrated the viability of the Biodiesel programs, in combination with the SCR systems, which does not require any engine adaptation and is an economical alternative for the countries (Brazil, China, Russia, India) that have not adopted Euro VI emission standards. Environmental Engineering Department Federal University of Paraná Mathematics Department Federal University of Technology Paraná Federal University of São Paulo Institute of Technology for Development Lactec Chemical Engineering Department Federal University of Paraná Analytical Chemistry Department Institute of Chemistry São Paulo State University - UNESP Division of Chemistry and Environmental Science School of Science and the Environment Manchester Metropolitan University Molecular Science Institute School of Chemistry University of the Witwatersrand Analytical Chemistry Department Institute of Chemistry São Paulo State University - UNESP CNPq: 402391/2009-8 CNPq: 558697/2012-0

In this study, an in vitro antileishmanial assessment of plant extracts from 12 genera and 46 species growing in Cuba belonging to Solanaceae family was performed. A total of 226 extracts were screened against promastigotes of Leishmania amazonensis, and cytotoxicity of active extracts [median inhibitory concentration (IC50 ) promastigotes 5 were then assayed against intracellular amastigote. Metabolomics analysis of promissory extracts was performed using chemical profile obtained by ultra performance liquid chromatography. Only 11 extracts (4.9%) from nine plants were selected as potentially actives: Brunfelsia cestroides A. Rich, Capsicum annuum L., Capsicum chinense Jacq., Cestrum nocturnum L., Nicotiana plumbaginifolia Viv., Solanum havanense Jacq., Solanum myriacanthum Dunal, Solanum nudum Dunal and Solanum seaforthianum And., with IC50 5. Metabolomics analysis demonstrated significant differences in the chemical profiles with an average of 42.8 (range 31-88) compounds from m/z 104 to 1477, which demonstrated the complex mixture of compounds. In addition, no common markers among active extracts were identified. The results demonstrate the importance of the Solanaceae family to search new antileishmanial agents, particularly in unexplored species of this family. Copyright © 2016 John Wiley & Sons, Ltd.

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

Made available in DSpace on 2018-12-11T16:52:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-04-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Submarine sewage outfalls (SSOs) are considered the main input source of contaminants of emerging concern continuously released in coastal areas, with the potential to cause adverse effects for aquatic organisms. This work presents the investigation of nine endocrine disrupting chemicals (EDCs) and 26 pharmaceutically active chemicals (PhACs) in marine sediments within the vicinities of 7 SSOs along the São Paulo State Coast (Brazil). Method optimization for the multi-residue determination by GC–MS/MS and LC-MS/MS using QuEChERS extraction/clean-up are discussed. Results demonstrate the occurrence of EDCs in concentrations ranging from less than method quantification limits (MQL) to 72.5 ng g−1 in sediments. All PhACs were

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.

Particulate matter with an aerodynamic diameter below 2.5 μm (PM2.5), present in polluted air, has been associated with a large spectrum of health impairments, mainly because of its deep deposition into the lungs. Araraquara City (Southeast Brazil) is surrounded by sugar-cane plantations, which are burned to facilitate the harvesting; this process causes environmental pollution due to the large amounts of soot that are released into the atmosphere. In this work, the elemental composition of PM2.5 was studied in two scenarios, namely in sugar-cane harvesting (HV) and in non-harvesting (NHV) seasons. The sampling strategy included one campaign in each season. PM2.5 was collected using a dichotomous sampler (10 L·min-1, 24 h) with PTFE filters. Information concerning the bulk elemental concentration was provided by energy-dispersive X-ray fluorescence. Enrichment factor analysis indicated that S, Cl, K, Cr, Ni, Cu, Zn, As, Cd and Pb were highly enriched relative to their crustal ratios (to Al). Principal component analysis was used to get some insight about the sources of the elements. Principal component 1 (PC1) explained 30.5% of data variance. The elements that had high loading (>0.7) were: S, Cr, As, and Pb; these are associated with combustion of fossil fuels. In principal component 2 (PC2), Cl, Cu, Zn, and Cd showed high loadings; these elements are associated with biomass burning. The Ni concentration found is three times larger than the threshold of risk for lung cancer, as recommended by the World Health Organization.

Made available in DSpace on 2018-12-11T17:12:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-01-01 The concomitant exposure to low doses of various pesticides is one of the most relevant issues in human toxicology today. An experimental toxicology study was developed to evaluate the effects of this type of exposure on the reproductive capacity of females of three species of rats that were exposed to mixtures of dicofol, dieldrin, endosulfan and permethrin at low doses (LOAEL and NOAEL). In this context, we have developed a method for determining pesticides in adipose tissue (0.5 g, 49% lipid) associated with the ovaries, based on the QuEChERS (quick, easy, cheap, effective, rugged and safe) strategy. The method quantification limit (LOQ) was 0.5 mg/kg for dicofol and permethrin, 0.05 mg/kg for endosulfan and dieldrin and 0.2 mg/kg for diclorobenzophenone. Mean recoveries ranged from 75% to 93% with a relative standard deviation

This paper presents the optimization of a method based on solid–liquid extraction followed by low-temperature partition (SLE-LTP) for the determination of persistent organic pollutants (organochlorinated pesticides and PCBs) in the eggs of the Pantanal caiman (Caiman yacare). The chemometric approach included a 24 factorial design and a triplicate central point. The extractor solvent volume (8–10 mL), vortexing time (1–5 min), centrifugation time (5–15 min) and freezing time (4–12 h) were the variables considered and were tested at three levels, including triplicate tests at the central point. The evaluated response was the average recovery for all the analytes. The data showed the extractor volume and the vortex time to be the main factors that affect recovery. The optimized method includes12 mL of extractor solvent, 5 min of vortexing time, 5 min of centrifugation time and 12 h of freezing time. Under these conditions the average recovery was 61% with a precision expressed as relative standard deviation (RSD) of 15% for sample with 22.5 ng g− 1 of sample. A GC-ECD was used for the determination of POPs. The experimental design was an important statistical tool for defining the experimental parameters in the use of this method for the extraction of organochlorine pesticides and PCBs.

Tributyltin exposure is the primary cause of imposex development in gastropods, making them excellent bioindicators. The present research represents the first examination of butyltin (BT) contamination in surface sediments associated with imposex in Leucozonia nassa and L. ocellata in a harbour complex area in Espirito Santo, southeastern Brazil. The objectives of this study were to evaluate the organotin pollution in the area and to assess the sensitivity of both species to BT pollution through imposex development. Specimens were collected between 2007 and 2010 and the sediments were sampled in 2007. Imposex intensity was evaluated based on the percentage of imposexed females, the relative penis length index (RPLI) and the average value of the vas deferens sequence index (VDSI). BTs were analysed using gas chromatography equipped with a pulsed flame photometric detector (PFPD). The results demonstrated the occurrence of elevated concentrations of BTs in the sediment ranging from 383.7 to 7172.9 n...

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.

Analytical Chemistry Department Institute of Chemistry Universidade Estadual Paulista (UNESP), Araraquara, Sao Paulo

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

Made available in DSpace on 2018-12-11T17:02:36Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-08-01 Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OPESR) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OPESR results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100 cm-1 and 1600 cm-1 indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation. Environmental Engineering Department Federal University of Parana Division of Chemistry and Environmental Science School of Science and the Environment Manchester Metropolitan University LAVIE - Institute of Chemistry São Paulo State University - UNESP Chemical Engineering Department Federal University of Parana Vehicle Emissions Laboratory Institute of Technology for Development (LACTEC) Analytical Chemistry Department Institute of Chemistry São Paulo State University - UNESP Laboratory of Experimental Air Pollution Department of Pathology School of Medicine University of São Paulo Department of Natural and Earth Sciences Federal University of São Paulo LAVIE - Institute of Chemistry São Paulo State University - UNESP Analytical Chemistry Department Institute of Chemistry São Paulo State University - UNESP

Made available in DSpace on 2018-11-26T15:28:38Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-01-01. Added 1 bitstream(s) on 2021-07-15T15:01:00Z : No. of bitstreams: 1 S0103-50532016000100109.pdf: 646578 bytes, checksum: 7262b38086fc440223b7630250af4215 (MD5) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Instituto Nacional de Ciencia e Tecnologia de Bioanalitica (INCTBio) Fundacao Araucaria - Parana Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) It is well known that selectivity of molecularly imprinted polymers (MIPs) depends on adequate choice of functional monomer before the experimental synthesis. Computational simulation seems to be an ideal way to produce selective MIPs. In this work, we have proposed the use of semi-empirical simulation to obtain the best monomer able to strongly interact with ciprofloxacin. Twenty functional monomers were evaluated through semi-empirical quantum chemistry method and three MIPs were synthesized using the monomers acrylamide (M5), acrylic acid (M4) and 1-vinylimidazole (M16), yielding the maximum adsorption capacities of 282.0, 223.8 and 202.5 mu mol g(-1), respectively, as predicted by the computational simulation. From competitive adsorption studies in the presence of structurally similar compounds, the MIP synthesized with acrylamide was found to possess higher specific selectivity factors (S) if compared to non-imprinted polymer (NIP), thus indicating good recognition selectivity for the ciprofloxacin. Univ Estadual Paulista, Inst Quim, BR-14800900 Araraquara, SP, Brazil Inst Fed Parana, BR-84269090 Telemaco Borba, PR, Brazil Univ Estadual Londrina, Dept Quim, BR-86050482 Londrina, PR, Brazil Univ Estadual Paulista, Inst Quim, BR-14800900 Araraquara, SP, Brazil

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

Tributyltin (TBT) contamination affects the reproductive system of many species of invertebrates worldwide. The present study was designed to evaluate the effects of exposure to TBT pollution on the reproduction of the hermit crab Clibanarius vittatus. An orthogonal experiment was designed with two treatments: contamination (with or without TBT in the food) and crab sex (males and females). The animals were reared in the laboratory for nine months, and macroscopic and histological analyses of reproductive organs were carried out after the end of the experiment. Tributyltin was recorded in exposed crabs, but no morphological alterations were detected in the gonads of males, regardless of whether they were exposed to TBT. In contrast, females exposed to TBT displayed disorganization and atrophy of their ovaries, thus directly affecting reproduction in this hermit crab species. This effect observed in female hermit crabs may harm populations located in harbor regions, where TBT concentration is high, even after the worldwide TBT ban.

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.

This paper reports theoretical and experimental studies of gas-phase fragmentation reactions of four naturally occurring isoflavones. The samples were analyzed in negative ion mode by direct infusion in ESI-QqQ, ESI-QqTOF and ESI-Orbitrap systems. The MS/MS and MS(n) spectra are in agreement with the fragmentation proposals and high-resolution analyses have confirmed the formulae for each ion observed. As expected, compounds with methoxyl aromatic substitution have showed a radical elimination of •CH(3) as the main fragmentation pathway. A second radical loss (•H) occurs as previously observed for compounds which exhibit a previous homolytic •CH(3) cleavage (radical anion) and involves radical resonance to stabilize the anion formed. However, in this study we suggest another mechanism for the formation of the main ions, on the basis of the enthalpies for each species. Compounds without methoxy substituent dissociate at the highest energies and exhibit the deprotonated molecule as the most intense ion. Finally, energy-resolved experiments were carried out to give more details about the gas-phase dissociation reaction of the isoflavones and the results are in agreement with the theoretical approaches.

Rapadura is the commercial name for unrefined dehydrated sugarcane juice. Rapadura is produced in 25 countries, for an estimated total of 13 million tons per year. It is considered a basic food for the School Meals Program (PNAE) in Brazil, which serves 37 million meals to schoolchildren each day. During the production of rapadura, carcinogenic compounds including polycyclic aromatic hydrocarbons (PAHs) may enter this food. A simple and rapid method was optimized and validated for the determination of 16 PAHs in commercial rapadura by high performance liquid chromatography with fluorescence detection (HPLC-FL). PAHs were measured in 80% of the samples ( n = 21) at levels ranging from 0.07 to 4.03 μg kg −1 . These data reveal a wide variability in PAH concentrations in the samples, indicated that sugar-cane burning and/or production are important for introduction of these contaminants into rapadura. In Brazil, there are no maximum acceptable PAH levels in this food.

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

In Brazil, sugar-cane crops are burned to facilitate harvesting, and this causes environmental pollution from the large amounts of smoke and soot that are released into the atmosphere. The smoke and soot contain numerous organic compounds such as PAHs. In this study, PM 10 and PAH concentrations in the air of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugar-cane plantations) were determined during the harvest and non-harvest seasons. The sampling strategy included two campaigns in each season, with 20 samples per season. PM 10 was collected using a Hi-vol sampler with Teflon™ – coated glass fiber filters. PM 10 ranged from 41 to 181 μg m −3 during the harvest season, and from 12 to 47 μg m −3 during the non-harvest season. The mean total concentration of PAHs was 2.5 ng m −3 (non-harvest season) and 11.6 ng m −3 (harvest season). In all sampling periods, the most abundant polycyclic aromatic hydrocarbons were phenanthrene and fluoranthrene, and the least abundant was anthracene. The cluster analysis of the total PAH concentrations for each day of sampling and the corresponding meteorological data suggested that the atmospheric concentration of PAHs was independent of the differences in the weather between the seasons. For both sampling seasons, the statistical treatment (PCA, Varimax rotation and HCA) indicated the presence of vehicle sources (diesel, gasoline, and natural-gas engines); but for the harvest season, the main source was attributed to sugar-cane burning. The data generated by this study indicated the burning of sugar-cane as the main contributor to the high levels of PAHs detected in samples during the sugar-cane harvest season.

Contamination by butyltin compounds (BTs) has been reported in estuarine environments worldwide, with serious impacts on the biota of these areas. Considering that BTs can be degraded by varying environmental conditions such as incident light and salinity, the short-term variations in such factors may lead to inaccurate estimates of BTs concentrations in nature. Therefore, the present study aimed to evaluate the possibility that measurements of BTs in estuarine sediments are influenced by different sampling conditions, including period of the day (day or night), tidal zone (intertidal or subtidal), and tides (high or low). The study area is located on the Brazilian southeastern coast, Sao Vicente Estuary, at Pescadores Beach, where BT contamination was previously detected. Three replicate samples of surface sediment were collected randomly in each combination of period of the day, tidal zone, and tide condition, from three subareas along the beach, totaling 72 samples. BTs were analyzed by GC-PFPD using a tin filter and a VF-5 column, by means of a validated method. The concentrations of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) ranged from undetectable to 161 ng Sn g−1 (d.w.). In most samples (71%), only MBT was quantifiable, whereas TBTs were measured in only 14, suggesting either an old contamination or rapid degradation processes. DBT was found in 27 samples, but could be quantified in only one. MBT concentrations did not differ significantly with time of day, zones, or tide conditions. DBT and TBT could not be compared under all these environmental conditions, because only a few samples were above the quantification limit. Pooled samples of TBT did not reveal any difference between day and night. These results indicated that, in assessing contamination by butyltin compounds, surface-sediment samples can be collected in any environmental conditions. However, the wide variation of BTs concentrations in the study area, i.e., over a very small geographic scale, illustrates the need for representative hierarchical and composite sampling designs that are compatible with the multiscalar temporal and spatial variability common to most marine systems. The use of such sampling designs will be necessary for future attempts to quantitatively evaluate and monitor the occurrence and impact of these compounds in nature.

The use of inks containing organic solvents by the offset printing process implies in the release of volatile organic compounds to the work environment. Many of these compounds such as benzene, toluene, ethylbenzene, and the xylene isomers (well known by the acronym BTEX) are extremely toxic. In this study, the BTEX concentrations were determined in two different printing plants that use distinct types of inks: the conventional and the so-called ecological, which is manufactured based on vegetal oil. Concentration ranges were 4384, 153,480, 2133, 5459, and 2236 μg m−3 for benzene, toluene, ethylbenzene, m + p-xylene, and o-xylene, respectively, for the conventional printing plant. At the ecological printing plant, concentration ranges were below limit of detection (

This work reports on the development and validation of a small-scale and efficient SPE-HPLC-UV method for the simultaneous determination of the most used herbicides (diuron, hexazinone, and tebuthiuron) applied to soil and soil treated with sugar cane vinasse (soil-vinasse) in areas where sugar cane crops are grown in the state of Sao Paulo, Brazil. The analytical procedure was optimized for solvent extraction and HPLC-UV conditions. Extraction and clean-up were combined in a single step employing solid-phase extraction, avoiding sophisticated techniques, organic–solvent–water mixtures and consequently a longer concentration step. Recovery studies with soil and soil-vinasse samples spiked at two herbicides levels (around 0.25 and 2.0 mg kg −1 ) and sample stability (sample frozen for 20 days before analysis) were applied as parameters to control the efficiency of the method. Good accuracy and precision were achieved with average recoveries ranging from 78% to 120% and relative standard deviations less than 10% throughout the whole recovery test. The method's limit of detection ranged between 0.025 and 0.050 mg kg −1 for diuron, hexazinone, and tebuthiuron in soil and soil-vinasse. The feasibility of this method was applied to determine the herbicide half-lives ( t 1/2 ) in soil and soil-vinasse in a laboratory study. Sugar cane vinasse added to soil increased the degradation of diuron and tebuthiuron ( p t 1/2 from 80 to 7 days and 128 to 73 days, respectively. This method is presented as an alternative which could be applied to assess herbicide behavior in soil in order to prevent water contamination and to contribute to establish pesticide limits in soil.

The burning of organic residues and wastes in furnaces of cement industries has been an attractive and lucrative approach to eliminate stocks of these pollutants. There is a potential risk for producing PAH in the workplace of industries burning organic wastes, so that highly sensitive analytical methods are needed for monitoring the air quality of these environments. An official method for determination of PAH is based on liquid chromatography with fluorescence detection at fixed excitation and emission wavelengths. We demonstrate that a suitable choice of these wavelengths, which are changed during the chromatographic run, significantly improves the detectability of PAH in atmosphere and particulate matter collected in cement industries.

Estrogenic hormones are steroids produced naturally by humans and animals or synthesized for application as drugs. When excreted and discharged into the environment, they show biological activity in concentrations above 1 ng L-1. Nevertheless, processes such as biodegradation, photolysis and absorption contribute to partial removal of the hormones leaching into the water sources. There is evidence that human exposure to estrogenic hormones contributes to reduction in male fertility and an increased incidence of breast cancer. For the ecological biota, the consequences are the feminization of male fish and a reduction in plant growth. While the efficiency of conventional water treatments has not been clarified, advanced treatments demonstrate removal efficiencies of over 90%. Sewage treatment shows different efficiencies for the removal of these substances

Submitted by Guilherme Lemeszenski (guilherme@nead.unesp.br) on 2013-08-22T18:48:39Z No. of bitstreams: 1 S0100-40422007000300031.pdf: 595317 bytes, checksum: 3e06c998bf26b9fcd0157b6db386e226 (MD5) Made available in DSpace on 2013-08-22T18:48:39Z (GMT). No. of bitstreams: 1 S0100-40422007000300031.pdf: 595317 bytes, checksum: 3e06c998bf26b9fcd0157b6db386e226 (MD5) Previous issue date: 2007-06-01 Made available in DSpace on 2013-09-30T19:38:40Z (GMT). No. of bitstreams: 2 S0100-40422007000300031.pdf: 595317 bytes, checksum: 3e06c998bf26b9fcd0157b6db386e226 (MD5) S0100-40422007000300031.pdf.txt: 46636 bytes, checksum: 850515b4b1c0ae4650e14643384adf73 (MD5) Previous issue date: 2007-06-01 Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-20T15:10:22Z No. of bitstreams: 2 S0100-40422007000300031.pdf: 595317 bytes, checksum: 3e06c998bf26b9fcd0157b6db386e226 (MD5) S0100-40422007000300031.pdf.txt: 46636 bytes, checksum: 850515b4b1c0ae4650e14643384adf73 (MD5) Made available in DSpace on 2014-05-20T15:10:22Z (GMT). No. of bitstreams: 2 S0100-40422007000300031.pdf: 595317 bytes, checksum: 3e06c998bf26b9fcd0157b6db386e226 (MD5) S0100-40422007000300031.pdf.txt: 46636 bytes, checksum: 850515b4b1c0ae4650e14643384adf73 (MD5) Previous issue date: 2007-06-01 A discussion about groundwater contamination is presented in this work. Contamination by agricultural activity, more specifically by pesticides is emphasized. Indirect and direct estimates could be used to predict pesticide behavior in soil, and consequently, to evaluate the potential of groundwater contamination. These results could be applied to advise about the possibility of groundwater contamination by pesticides, and to provide subsidies for making decisions more quickly and efficiently. Centro Universitário de Araraquara Universidade Estadual de Campinas Instituto de Geociências Universidade Estadual Paulista Instituto de Química Universidade Estadual Paulista Instituto de Química