Diurnal and nocturnal measurements of PAH, nitro-PAH, and oxy-PAH compounds in atmospheric particulate matter of a sugar cane burning region

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Combustion of coal, bagasse and blends thereof Part II: Speciation of PAH emissions

This work reports on emissions of unburned hydrocarbon species from batch combustion of fixed beds of coal, sugar-cane bagasse, and blends thereof in a pre-heated two-stage laboratory furnace operated in the temperature range of 800-1000 degrees C. The effects of fuel blending, combustion staging, and operating furnace temperatures on emissions of pollutants were assessed. Furnace effluents were analyzed for products of incomplete combustion (PICs) including CO, volatile and semi-volatile hydrocarbons, and particulate matter, as has been reported in Ref. [1]. Emitted unburned hydrocarbons include traces of potentially health-hazardous Polycyclic Aromatic Hydrocarbons (PAHs), which are the focus of this work. Under the batch combustion conditions implemented herein, PAH were only generated during the volatile combustion phase of the fuels. The most prevalent species were in descending order: naphthalene, acenaphthylene, phenanthrene, fluoranthene, pyrene, dibenzofuran, benzofuran, byphenyl, fluorene, 9H-fluoren-9-one, acephenantrylene, benzo[b] fluoranthene, 1-methyl-naphthalene; 2-methyl-naphthalene, benz[a] anthracene and benzo[a] pyrene. PAH yields were the highest from combustion of neat bagasse. Combustion of the blends resulted in lower yields of PAH, than combustion of either of their neat fuel constituents. Increasing the furnace operating temperature enhanced the PAH emissions from bagasse, but had little effect on those from the coal or from the blends. Flue gas treatment in a secondary-stage furnace, upon with additional air, typically reduced PAH yields by promoting oxidation of the primary-stage furnace effluents. (C) 2011 Elsevier Ltd. All rights reserved.

Comparison of the n-Alkanes and Polycyclic Aromatic Hydrocarbons Concentrations in the Atmosphere during the Preparation of Warm and Hot Mixtures Asphalt for Pavements

Asphalt binder is used in the production of hot mixes asphalt (HMA) for paving and, due to the high temperatures used, generates fumes thatcontainn-alkanes and polycyclic aromatic hydrocarbons (PAH). Asphalt mixes prepared at lower temperatures, such as warm mixes asphalt (WMA), may contribute to reduce the emissions of those compounds and save energy. This paper investigatesn-alkanes and PAH in the total suspended particles during the preparation of WMA, in comparison with HMA, in laboratory. The results showed that the n-alkanes of the WMA and HMA presented C-max at n-C-26 and n-C-28, respectively; also, the total content of n-alkanes was higher for the HMA than forthe WMA. Besides, benzo[b]fluoranthene and benzo[a]anthracene were the major PAH in the WMA, while the higher temperatures of the HMA were observed to volatilize all larger PAH, demonstrating higher potential of inhalation exposure.

Geochemistry of pockmark sediments from the inner Oslofjord

Pockmarks are geological features that are found on the bottom of lakes and oceans all over the globe. Some are active, seeping oil or methane, while others are inactive. Active pockmarks are well studied since they harbor specialized microbial communities that proliferate on the seeping compounds. Such communities are not found in inactive pockmarks. Interestingly, inactive pockmarks are known to have different macrofaunal communities compared to the surrounding sediments. It is undetermined what the microbial composition of inactive pockmarks is and if it shows a similar pattern as the macrofauna. The Norwegian Oslo Fjord contains many inactive pockmarks and they are well suited to study the influence of these geological features on the microbial community in the sediment. Here we present a detailed analysis of the microbial communities found in three inactive pockmarks and two control samples at two core depth intervals. The communities were analyzed using high-throughput amplicon sequencing of the 16S rRNA V3 region. Microbial communities of surface pockmark sediments were indistinguishable from communities found in the surrounding seabed. In contrast, pockmark communities at 40 cm sediment depth had a significantly different community structure from normal sediments at the same depth. Statistical analysis of chemical variables indicated significant differences in the concentrations of total carbon and non-particulate organic carbon between 40 cm pockmark and reference sample sediments. We discuss these results in comparison with the taxonomic classification of the OTUs identified in our samples. Our results indicate that microbial surface sediment communities are affect by the water column, while the 40 cm communities are affect by local conditions within the sediment.

Caracterização microbiológica, química e presença de poluentes orgânicos em amostras de lodo de esgoto de São Paulo

Objetivou-se com este trabalho avaliar o potencial agrícola do lodo de esgoto produzido no estado de São Paulo, bem como, verificar a possibilidade de interação entre a composição química e a abundância relativa de bactérias no lodo. Foram realizadas coletas de amostra de lodo de esgoto em 19 estações de tratamento de esgoto, em três épocas distintas. Nas amostras provenientes das três épocas foram determinados as concentrações dos 16 hidrocarbonetos policíclicos aromáticos (HPAs) listados como prioritários no monitoramento ambiental pela USEPA (acenafteno, acenaftileno, antraceno, benzo(a)antraceno, benzo(a)pireno, benzo(b)fluoranteno, benzo(ghi)perileno, benzo(k)fluoranteno, criseno, dibenzo(a,h)antraceno, fenantreno, fluoranteno, fluoreno, indeno(1,2,3-cd)pireno, naftaleno e pireno). Nas amostras da segunda época de coleta, além da presença de HPAs, determinou-se as concentrações de poluentes orgânicos emergentes (hormônios, produtos farmacêuticos e produtos de uso industrial), realizou-se a caracterização completa segundo a Resolução CONAMA 375/2006 (umidade, pH, N-Kjeldahl e inorgânico, carbono orgânico, cálcio, potássio, fósforo, magnésio, enxofre, boro, cobre, ferro, níquel, manganês, molibdênio, selênio, zinco, alumínio, arsênio, bário, cádmio, cromo, chumbo, mercúrio e sódio) e a caracterização da comunidade bacteriana através de metodologia independente de cultivo (sequenciamento illumina). Os macronutrientes em maiores concentrações no lodo de esgoto são: N > Ca > S > P > Mg > K. Os elementos inorgânicos Ni e Zn apresentaram concentração superior à máxima permitida para utilização agrícola pela resolução Conama 375/2006 em 1 e 3 amostras, respectivamente. A substância inorgânica que mais limita o enquadramento do lodo de esgoto como adubo orgânico (Instrução Normativa 27/2006) é o Hg. Os compostos benzilparabeno, bisfenol AF (BPAF), ácido perfluorooctanoico (PFOA) e tetrabromobisfenol A (TBBPA) não foram detectados. Por outro lado, cimetidina, metilparabeno, bisfenol A (BPA) e triclocarban foram detectados nas 19 amostras avaliadas. O composto presente em maior concentração é o triclocarban. As concentrações de hidrocarbonetos policíclicos aromáticos são baixas, de acordo com a norma Europeia. Os filos Proteobacteria e Bacteroidetes estão presentes em maior abundância relativa. Existe uma comunidade bacteriana núcleo nas estações de tratamento de esgoto do estado de São Paulo, composta por 81 gêneros, presentes nas 19 ETEs avaliadas, dos quais, os que estão em maior abundância relativa são Treponema, Clostridium, Propionibacterium, Syntrophus e Desulfobulbus. A elevação do pH a valores próximos de 12 reduz a diversidade microbiana. Considerando a abundância relativa e a composição química do lodo de esgoto, as estações podem ser agrupadas em três grupos distintos, sendo que um deles é influenciado principalmente pelos teores de Ca, Zn e Cu, o outro pelos teores de Fe e S e o terceiro grupo que foi influenciado pelos demais fatores avaliados.

Caracterização do material particulado e avaliação do risco ocupacional e mecanismos moleculares associados à queima artesanal da castanha de caju

Brazil is among the largest cashew nut producers of the world. However, the roasting process is still carried out artisanally, especially in the Brazilian semiarid region. In face of this occupational problem, the aim of this study was to perform a physical-chemical characterization of the particulate matter (PM) emitted by the roasting of cashew nuts, as well as to determine the occupational risk and molecular mechanisms associated. The most evident PM characteristics were the prevalence of fine particles, typical biomass burning morphologies such as tar ball and the presence of the elements K, Cl, S, Ca and Fe. In addition, atmospheric modeling analyses suggest that these particles can reach neighboring regions of the emission source. Polycyclic aromatic hydrocarbons (PAHs) with carcinogenic potential, such as benzo[a]pyrene, dibenz[a,h]anthracene, benzo[a]anthracene, benzo[b]fluoranthene, chrysene, benzo[k]fluoranthene, indeno[1,2,3-c,d]pyrene and benzo[j]fluoranthene were the most abundant PAHs found in the two air monitoring campaigns. Among the identified oxy-PAH the benzanthrone (7H-benz[d,e]anthracen-7-one) had the highest concentration and the evaluation of lifetime cancer risk showed an increase of 12 to 37 cases of cancer for every 10,000 exposed people. Chemical analysis of roasted cashew nuts identified the PAHs: phenanthrene, benzo[g,h,i]perylene, pyrene and benzo[a]pyrene, besides the 3-pentadecilfenol allergen (urushiol analogue) as prevalent. Occupational exposure to PAHs was confirmed by the increase of urinary 1-hydroxypyrene levels and genotoxic effects were evidenced by the increase on micronuclei and nuclear bud frequency in exfoliated buccal mucosa cells among the exposed workers. Other biomarkers of effects such as karyorrhexis, pyknotic, karyolytic, condensed chromatin and binucleated cells also have their frequencies increased when compared to an unexposed control group. The investigation of the molecular mechanisms associated with the PM organic extract showed cytotoxicity in human lung cell lines (A549) at concentrations ≥ 4 nM BaPeq. Using non-cytotoxic doses the extract was able to activate proteins involved in the DNA damage response pathway (Chk1 and p53). Moreover, the specific contribution of the four most representative PAHs in the cashew nut roasting sample showed that benzo[a]pyrene was the most efficient to activate Chk1 and p53. Finally, the organic extract was able to increase persistently the mRNA expression involved in the PAHs metabolism (CYP1A1 and CYP1B1), inflammatory response (IL-8 and TNF-α) and cell cycle arrest (CDKN1A) for DNA repair (DDB2). The high PM concentrations and its biological effects associated warn of the serious harmful effects of artisanal cashew nut roasting and urgent actions should be taken to the sustainable development of this activity.

Caracterização do material particulado e avaliação do risco ocupacional e mecanismos moleculares associados à queima artesanal da castanha de caju

Brazil is among the largest cashew nut producers of the world. However, the roasting process is still carried out artisanally, especially in the Brazilian semiarid region. In face of this occupational problem, the aim of this study was to perform a physical-chemical characterization of the particulate matter (PM) emitted by the roasting of cashew nuts, as well as to determine the occupational risk and molecular mechanisms associated. The most evident PM characteristics were the prevalence of fine particles, typical biomass burning morphologies such as tar ball and the presence of the elements K, Cl, S, Ca and Fe. In addition, atmospheric modeling analyses suggest that these particles can reach neighboring regions of the emission source. Polycyclic aromatic hydrocarbons (PAHs) with carcinogenic potential, such as benzo[a]pyrene, dibenz[a,h]anthracene, benzo[a]anthracene, benzo[b]fluoranthene, chrysene, benzo[k]fluoranthene, indeno[1,2,3-c,d]pyrene and benzo[j]fluoranthene were the most abundant PAHs found in the two air monitoring campaigns. Among the identified oxy-PAH the benzanthrone (7H-benz[d,e]anthracen-7-one) had the highest concentration and the evaluation of lifetime cancer risk showed an increase of 12 to 37 cases of cancer for every 10,000 exposed people. Chemical analysis of roasted cashew nuts identified the PAHs: phenanthrene, benzo[g,h,i]perylene, pyrene and benzo[a]pyrene, besides the 3-pentadecilfenol allergen (urushiol analogue) as prevalent. Occupational exposure to PAHs was confirmed by the increase of urinary 1-hydroxypyrene levels and genotoxic effects were evidenced by the increase on micronuclei and nuclear bud frequency in exfoliated buccal mucosa cells among the exposed workers. Other biomarkers of effects such as karyorrhexis, pyknotic, karyolytic, condensed chromatin and binucleated cells also have their frequencies increased when compared to an unexposed control group. The investigation of the molecular mechanisms associated with the PM organic extract showed cytotoxicity in human lung cell lines (A549) at concentrations ≥ 4 nM BaPeq. Using non-cytotoxic doses the extract was able to activate proteins involved in the DNA damage response pathway (Chk1 and p53). Moreover, the specific contribution of the four most representative PAHs in the cashew nut roasting sample showed that benzo[a]pyrene was the most efficient to activate Chk1 and p53. Finally, the organic extract was able to increase persistently the mRNA expression involved in the PAHs metabolism (CYP1A1 and CYP1B1), inflammatory response (IL-8 and TNF-α) and cell cycle arrest (CDKN1A) for DNA repair (DDB2). The high PM concentrations and its biological effects associated warn of the serious harmful effects of artisanal cashew nut roasting and urgent actions should be taken to the sustainable development of this activity.

Remoção de hidrocarbonetos aromáticos policíclicos em águas utilizando subprodutos da indústria da cortiça

Os Hidrocarbonetos Aromáticos Policíclicos (HAPs) são contaminantes persistentes em meio aquoso. Estes compostos são conhecidos pelas suas propriedades carcinogénicas, mutagénicas e genotóxicas. O principal objetivo deste trabalho consistiu na avaliação das potencialidades de subprodutos da indústria corticeira, como adsorventes alternativos para a remoção de cinco HAPs em meio aquoso: benzo(a)pireno, benzo(ghi)perileno, benzo(b)fluoranteno, benzo(k)fluoranteno e indeno(1,2,3-cd)pireno. A metodologia analítica para quantificar os HAPs envolveu a preparação das amostras, através da técnica de extração em fase sólida (SPE), e a quantificação dos compostos analisados por cromatografia líquida com detetor de fluorescência (LC-FLD). O método foi otimizado e validado, obtendo-se limites de quantificação de 0,004 μg/L para todos os HAPs. Os estudos incidiram na utilização de uma amostra de cortiça, pó de aglomerado de cortiça expandida (PACE), obtida por aglutinação de cortiça em condições hidrotérmicas, a qual nos estudos preliminares revelou desempenho semelhante aos carvões ativados. Com exceção do benzo(ghi)perileno, os resultados mostram que o processo de adsorção dos HAPs na amostra PACE segue uma cinética de pseudo-segunda ordem e as isotérmicas ajustam-se ao modelo de Langmuir.

Polyaromatic hydrocarbons in sediments from the Barents and White Seas

Polycyclic aromatic hydrocarbons (PAHs) are common environmental contaminants which can be derived from anthropogenic sources, such as combustion and discharges from extraction and transport, and natural processes, including leakage and erosion of fossil carbon. Natural PAH sources contribute, along with biological activities and terrestrial run-off, to the organic carbon content in sediments.The Barents Sea region is far from many anthropogenic sources of PAH, but production and trans-shipment of hydrocarbons is increasing. We present data for polycyclic aromatic hydrocarbon (PAH) concentrations in bottom sediments from 510 stations in the Barents and White Seas, and along the northern coast of Norway.

Benzothiophene Carboxamide Derivatives as Inhibitors of Plasmodium falciparum Enoyl-ACP Reductase

Benzothiophene derivatives like benzothiophene sulphonamides, biphenyls, or carboxyls have been synthesized and have found wide pharmacological usage. Here we report, bromo-benzothiophene carboxamide derivatives as potent, slow tight binding inhibitors of Plasmodium enoyl-acyl carrier protein (ACP) reductase (PfENR). 3-Bromo-N-(4-fluorobenzyl)-benzo[b]thiophene-2-carboxamide (compound 6) is the most potent inhibitor with an IC(50) of 115 nM for purified PfENR. The inhibition constant (K(i)) of compound 6 was 18 nM with respect to the cofactor and 91 nM with respect to crotonoyl-CoA. These inhibitors showed competitive kinetics with cofactor and uncompetitive kinetics with the substrate. Thus, these compounds hold promise for the development of potent antimalarials. (C) 2011 IUBMB IUBMB Life, 63(12): 1101-1110, 2011

Benzothiophene Carboxamide Derivatives as Novel Antimalarials

Bromo-benzothiophene carboxamide derivatives have been shown in the preceding article to inhibit Plasmodium falciparum Enoyl-ACP reductase. Here, we report bromo-benzothiophene carboxamide derivatives as potent inhibitors of Plasmodium asexual blood-stages in vitro as well as in vivo in the mouse model. These compounds specifically impair the development of metabolically active trophozoite stage of intraerythrocytic cycle and the intravenous administration of 3-bromo-N-(4-fluorobenzyl)-benzo[b]thiophene-2-carboxamide (compound 6) enhances the longevity of P. berghei infected mice by 2 weeks compared to disease control animals thereby preventing the onset of ataxia and convulsions in treated mice. These compounds thus hold promise for the development of potent antimalarials.(C) 2011 IUBMB IUBMB Life, 63(12): 1111-1115, 2011

[Rh-2(COD)(2)(Dppm)(mu(2)-Cl)]BF4: Precursor for a selective hydrogenation catalyst and its recycling by silica entrapment

The synthesis of [Rh-2(COD)(2)(dppm)(mu(2)-Cl)] BF4 (1) (COD) 1,5-cyclooctadiene, dppm) bis(diphenylphosphino) methane) from simple precursors is reported. This is a rare example of a dirhodium complex with an open [Rh-2(mu(2)-dppm)(mu(2)-Cl)] core. The complex has been used to affect the hydrogenation of styrene and benzo[b] thiophene with total selectivity and competitive rates of reaction. The recycling of the catalyst has been achieved by the entrapment of 1 in silica by a sol-gel method to produce a recyclable solid catalyst.

Regio- and stereo-selective dioxygenase-catalysed cis-dihydroxylation of fjord-region polycyclic arenes

Bacterial dioxygenase-catalysed cis-dihydroxylation of the tetracyclic arenes benzo[c]phenanthrene 2, and the isosteric compounds benzo[b]naphtho[1,2-d]furan 8, and benzo[b]naphtho[1,2-d]thiophene 9, has been found to occur exclusively at fjord-region bonds. The resulting cis-dihydrodiols 7, 10 and 11 were found to be enantiopure and of similar absolute configuration. cis-Dihydroxylation was also observed in the pseudo-fjord region of the 8,9,10,11-tetrahydro-precursors (12 and 13) of benzo[b]naphtho[1,2-d]furan 8, and benzo[b]naphtho[1,2-d]thiophene 9, to yield the corresponding enantiopure hexahydro cis-diols 14 and 15. A novel tandem cis-dihydroxylation and bis-desaturation of the tetrahydro-substrate, tetrahydrobenzo[b]naphtho[1,2-d]thiophene 13, catalysed by biphenyl dioxygenase, was found to yield the fjord-region cis-dihydrodiol 17 of benzo[b]naphtho[1,2-d]thiophene 9.

bis-cis-dihydrodiols: A new class of metabolites resulting from biphenyl dioxygenase-catalyzed sequential asymmetric cis-dihydroxylation of polycyclic arenes and heteroarenes

The biphenyl dioxygenase-catalyzed asymmetric mono-cis-dihydroxylation of the tetracyclic arenes chrysene 1A, benzo[c]phenanthridine 1B, and benzo[b]naphtho[2,1-d]thiophene 1C, has been observed to occur exclusively at the bay or pseudo-bay region using the bacterium Sphingomonas yanoikuyae B8/36. The mono-cis-dihydrodiol derivatives 2A and 2C, obtained from chrysene 1A by oxidation at the 3,4-bond (2A) and benzo[b]naphtho[2,1-d]thiophene 1C by oxidation at the 1,2-bond (2C), respectively, have been observed to undergo a further dioxygenase-catalyzed asymmetric cis-dihydroxylation at a second bay or pseudo-bay region bond to yield the corresponding bis-cis-dihydrodiols (cis-tetraols) 4A and 4C, the first members of a new class of microbial metabolites in the polycyclic arene series. The enantiopurities and absolute configurations of the new mono-cis-dihydrodiols 2B, 2C, and 3B were determined by H-1 NMR analyses of the corresponding (R)- and (S)-2-(1-methoxyethyl)benzeneboronate (MPBA) ester derivatives. The structure and absolute configurations of the bis-cis-dihydrodiols 4A and 4C were unambiguously determined by spectral analyses, stereochemical correlations, and, for the metabolite 4C, X-ray crystallographic analysis of the bis-acetonide derivative 7C. These results illustrate the marked preference of biphenyl dioxygenase for the cis-di- and tetra-hydroxylations of polycyclic arenes, at the more hindered bay or pseudo-bay regions, by exclusive addition from the same (si:si) face, to yield single enantiomers containing two and four chiral centers.