Polycyclic aromatic hydrocarbons and petroleum biomarkers in Sao Sebastiao Channel, Brazil: Assessment of petroleum contamination

Polycyclic aromatic hydrocarbons (PAHs) and non-aromatic hydrocarbons (NAHs), including n-alkanes, isoprenoids and petroleum biomarkers (terpanes, hopanes, steranes and diasteranes), were quantified by gas chromatography with flame ionization and mass spectrometer detectors in sediment samples collected from the Sao Sebastiao Channel (SSC), Brazil, where the largest Brazilian maritime petroleum terminal is located The concentrations of total PAHs. total n-alkanes and petroleum biomarkers ranged from below the detection limits to 370 ng g(-1,) 28 mu g g(-1), 2200 ng g(-1) (dry weight), respectively. The analysis of PAN distribution suggested combustion sources of PAHs as the main input for these compounds with smaller amount from petroleum contamination The distribution of petroleum biomarkers undoubtedly demonstrated petroleum as a source of anthropogenic contamination throughout the region. The assessment of petrogenic sources of contamination in marine sediment is more challenging if only PAH analysis were carried out, which demonstrates that more stable hydrocarbons such as petroleum biomarkers are useful for investigating potential presence of petroleum (C) 2009 Elsevier Ltd. All rights reserved.

Historical record of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in marine sediment cores from Admiralty Bay, King George Island, Antarctica

This paper describes the first results of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in sediment cores of Admiralty Bay, Antarctica. These markers were used to assess the local input of anthropogenic materials (particulate and organic compounds) as a result of the influence of human occupation in a sub-Antarctic region and a possible long-range atmospheric transport of combustion products from sources in South America. The highest SCPs and PAHs concentrations were observed during the last 30 years, when three research stations were built in the area and industrial activities in South America increased. The concentrations of SCPs and PAHs were much lower than those of other regions in the northern hemisphere and other reported data for the southern hemisphere. The PAH isomer ratios showed that the major sources of PAHs are fossil fuels/petroleum, biomass combustion and sewage contribution generally close to the Brazilian scientific station. (C) 2009 Elsevier Ltd. All rights reserved.

Chlorinated pesticides, polychlorinated biphenyls and polycyclic aromatic hydrocarbons in the fat tissue of seabirds from King George Island, Antarctica

Antarctic Brazilian Program (PROANTAR)

Polycyclic aromatic hydrocarbons (PAHs) in a large South American industrial coastal area (Santos Estuary, Southeastern Brazil): Sources and depositional history

Located in southeastern Brazil, the Santos Estuary has the most important industrial and urban population area of South America. Since the 1950`s, increased urbanization and industrialization near the estuary margins has caused the degradation of mangroves and has increased the discharge of sewage and industrial effluents. The main objectives of this work were to determine the concentrations and sources of polycyclic aromatic hydrocarbons (PAHs) in sediment cores in order to investigate the input of these substances in the last 50 years. The PAHs analyses indicated multiple sources of these compounds (oil and pyrolitic origin), basically anthropogenic contributions from biomass, coal and fossil fuels combustion. The distribution of PAHs in the cores was associated with the formation and development of Cubatao industrial complex and the Santos harbour, waste disposal, world oil crisis and the pollution control program, which results in the decrease of organic pollutants input in this area. (C) 2011 Elsevier Ltd. All rights reserved.

Characterization of cuticular hydrocarbons of diploid and haploid males, workers and queens of the stingless bee Melipona quadrifasciata

Males, queens and workers of stingless bees show differences in external morphology, behaviour and roles within a colony. In addition, each individual has a cuticular chemical signature responsible for mutual communication that is essential for maintaining the integrity of the colony. In this paper we characterize the cuticular hydrocarbon composition of newly emerged diploid and haploid males, workers and virgin queens of Melipona quadrifasciata by gas chromatography-mass spectrometry (GC/MS) analysis. This is the first time that the cuticular profile of diploid males in a species of stingless bee has been characterized. We found differences in the cuticular hydrocarbon composition among males, workers and virgin queens, recording both qualitative and quantitative differences among individuals of different phenotypes. However, no compound was found exclusively in diploid males. The cuticular chemical profiles of haploid and diploid males were very similar to those of workers. Moreover, the cuticular lipids of males and workers were significantly different from those of queens. Tricosane, pentacosene-2 and 7-methyl-heptacosane were the compounds responsible for this significant separation. This result correlates with the behavioural and morphological differences among these phenotypes.

Subcritical crack growth and in vitro lifetime prediction of resin composites with different filler distributions

Objectives. Verify the influence of different filler distributions on the subcritical crack growth (SCG) susceptibility, Weibull parameters (m and sigma(0)) and longevity estimated by the strength-probability-time (SPT) diagram of experimental resin composites. Methods. Four composites were prepared, each one containing 59 vol% of glass powder with different filler sizes (d(50) = 0.5; 0.9; 1.2 and 1.9 mu m) and distributions. Granulometric analyses of glass powders were done by a laser diffraction particle size analyzer (Sald-7001, Shimadzu, USA). SCG parameters (n and sigma(f0)) were determined by dynamic fatigue (10(-2) to 10(2) MPa/s) using a biaxial flexural device (12 x 1.2 mm; n = 10). Twenty extra specimens of each composite were tested at 10(0) MPa/s to determine m and sigma(0). Specimens were stored in water at 37 degrees C for 24 h. Fracture surfaces were analyzed under SEM. Results. In general, the composites with broader filler distribution (C0.5 and C1.9) presented better results in terms of SCG susceptibility and longevity. C0.5 and C1.9 presented higher n values (respectively, 31.2 +/- 6.2(a) and 34.7 +/- 7.4(a)). C1.2 (166.42 +/- 0.01(a)) showed the highest and C0.5 (158.40 +/- 0.02(d)) the lowest sigma(f0) value (in MPa). Weibull parameters did not vary significantly (m: 6.6 to 10.6 and sigma(0): 170.6 to 176.4 MPa). Predicted reductions in failure stress (P-f = 5%) for a lifetime of 10 years were approximately 45% for C0.5 and C1.9 and 65% for C0.9 and C1.2. Crack propagation occurred through the polymeric matrix around the fillers and all the fracture surfaces showed brittle fracture features. Significance. Composites with broader granulometric distribution showed higher resistance to SCG and, consequently, higher longevity in vitro. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Correlation between mandibular gland secretion and cuticular hydrocarbons in the stingless bee Melipona quadrifasciata

We investigated whether Melipona quadrifasciata worker mandibular gland secretions contribute directly to their cuticular hydrocarbon profile. The mandibular gland secretion composition and cuticular surface compounds of newly emerged worker bees, nurse bees, and foragers were determined by gas chromatography and mass spectrometry and compared. Both the mandibular gland secretions and the cuticular surface compounds of all worker stages were found to be composed almost exclusively of hydrocarbons. Although the relative proportion of hydrocarbons from the cuticular surface and gland secretion was statistically different, there was a high similarity in the qualitative composition between these structures in all groups of bees.

Leaves of Lolium multiflorum 'Lema' and tropical tree species as biomonitors of polycyclic aromatic hydrocarbons

This study extends the current knowledge regarding the use of plants for the passive accumulation of anthropogenic PAHs that are present in the atmospheric total suspended particles (TSP) in the tropics and sub-tropics. It is of major relevance because the anthropic emissions of TSP containing PAHs are significant in these regions, but their monitoring is still scarce. We compared the biomonitor efficiency of Lolium multiflorum 'Lema' and tropical tree species (Tibouchina pukka and Psidium guajava 'Paluma') that were growing in an intensely TSP-polluted site in Cubatao (SE Brazil), and established the species with the highest potential for alternative monitoring of PAHs. PAHs present in the TSP indicated that the region is impacted by various emission sources. L. multiflorum showed a greater efficiency for the accumulation of PAH compounds on their leaves than the tropical trees. The linear regression between the logBCF and logKoa revealed that L. multiflorum is an efficient biomonitor of the profile of light and heavy PAHs present in the particulate phase of the atmosphere during dry weather and mild temperatures. The grass should be used only for indicating the PAHs with higher molecular weight in warmer and wetter periods. (C) 2012 Elsevier Inc. All rights reserved.

Subcritical fatigue in fuse networks

We obtain the Paris law of fatigue crack propagation in a fuse network model where the accumulated damage in each resistor increases with time as a power law of the local current amplitude. When a resistor reaches its fatigue threshold, it burns irreversibly. Over time, this drives cracks to grow until the system is fractured into two parts. We study the relation between the macroscopic exponent of the crack-growth rate -entering the phenomenological Paris law-and the microscopic damage accumulation exponent, gamma, under the influence of disorder. The way the jumps of the growing crack, Delta a, and the waiting time between successive breaks, Delta t, depend on the type of material, via gamma, are also investigated. We find that the averages of these quantities, <Delta a > and <Delta t >/< t(r)>, scale as power laws of the crack length a, <Delta a > proportional to a(alpha) and <Delta t >/< t(r)> proportional to a(-beta), where < t(r)> is the average rupture time. Strikingly, our results show, for small values of gamma, a decrease in the exponent of the Paris law in comparison with the homogeneous case, leading to an increase in the lifetime of breaking materials. For the particular case of gamma = 0, when fatigue is exclusively ruled by disorder, an analytical treatment confirms the results obtained by simulation. Copyright (C) EPLA, 2012

Acceptance Threshold Hypothesis is Supported by Chemical Similarity of Cuticular Hydrocarbons in a Stingless Bee, Melipona asilvai

The ability to discriminate nestmates from non-nestmates in insect societies is essential to protect colonies from conspecific invaders. The acceptance threshold hypothesis predicts that organisms whose recognition systems classify recipients without errors should optimize the balance between acceptance and rejection. In this process, cuticular hydrocarbons play an important role as cues of recognition in social insects. The aims of this study were to determine whether guards exhibit a restrictive level of rejection towards chemically distinct individuals, becoming more permissive during the encounters with either nestmate or non-nestmate individuals bearing chemically similar profiles. The study demonstrates that Melipona asilvai (Hymenoptera: Apidae: Meliponini) guards exhibit a flexible system of nestmate recognition according to the degree of chemical similarity between the incoming forager and its own cuticular hydrocarbons profile. Guards became less restrictive in their acceptance rates when they encounter non-nestmates with highly similar chemical profiles, which they probably mistake for nestmates, hence broadening their acceptance level.

Influence of urban activities on polycyclic aromatic hydrocarbons in precipitation: Distribution, sources and depositional flux in a developing metropolis, Fortaleza, Brazil

We measured polycyclic aromatic hydrocarbons (PAHs) in bulk precipitation in the Fortaleza metropolitan area, Ceara, Brazil, for the first time. Because little information is available concerning PAHs in tropical climatic regions, we assessed their spatial distribution and possible sources and the influence of urban activities on the depositional fluxes of PAHs in bulk precipitation. The concentrations of individual and total PAHs (Sigma(PAHs)) in bulk precipitation ranged from undetectable to 133.9 ng.L-1 and from 202.6 to 674.8 ng.L-1, respectively. The plume of highest concentrations was most intense in a zone with heavy automobile traffic and favorable topography for the concentration of emitted pollutants. The depositional fluxes of PAHs in bulk precipitation calculated in this study (undetectable to 0.87 mu g.m(-2).month(-1)) are 4 to 27 times smaller than those reported from tourist sites and industrial and urban areas in the Northern Hemisphere. Diagnostic ratio analyses of PAH samples showed that the major source of emissions is gasoline exhaust, with a small percentage originating from diesel fuel. Contributions from coal and wood combustion were also found. Major economic activities appear to contribute to pollutant emissions. (C) 2011 Elsevier B.V. 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.

Cuticular Hydrocarbons Discriminate Distinct Colonies of Melipona marginata (Hymenoptera, Apinae, Meliponini)

The aim of the present study was to characterize the variation of the chemical profiles among workers in different colonies of the stingless bee Melipona marginata. We used gas chromatography and mass spectrometry (CG-MS) and multivariate analysis of the bees' chemical from three colonies of two localities in southeast Brazil. The results showed that cuticular hydrocarbon profiles clearly separated distinct colonies. We show here the importance of using the chemical analyses for characterization of colony membership, in addition of the traditional techniques of diversity analyses.

Comparison of the n-alkanes and polycyclic aromatic hydrocarbons concentrations in the atmosphere during the preparation of warm and hot mixtures asphalt for pavements

O asfalto é utilizado na produção de misturas asfálticas a quente (HMA) para a pavimentação e, devido às altas temperaturas empregadas, gera fumos que contêm n-alcanos e hidrocarbonetos policíclicos aromáticos (HPAs). As misturas asfálticas preparadas em temperaturas mais baixas, como as misturas asfálticas mornas (WMA), podem contribuir na redução das emissões daqueles compostos e economizar energia. Este trabalho investiga os n-alcanos e os HPAs nas partículas totais em suspensão durante a preparação de uma WMA, em comparação com uma HMA, em laboratório. Os resultados mostraram que os n-alcanos da WMA e da HMA apresentaram Cmáx no n-C26 e n-C28, respectivamente, e o teor de n-alcanos total foi maior na HMA do que na WMA. Ademais, verificou-se que o benzo[b]fluoranteno e benzo[a]antraceno constituíam os maiores HPAs na WMA, enquanto as temperaturas mais altas da HMA volatilizaram todos seus grandes HPAs, demonstrando maior potencial de exposição por inalação.