Advanced multivariate analysis to assess remediation of hydrocarbons in soils

Accurate monitoring of degradation levels in soils is essential in order to understand and achieve complete degradation of petroleum hydrocarbons in contaminated soils. We aimed to develop the use of multivariate methods for the monitoring of biodegradation of diesel in soils and to determine if diesel contaminated soils could be remediated to a chemical composition similar to that of an uncontaminated soil. An incubation experiment was set up with three contrasting soil types. Each soil was exposed to diesel at varying stages of degradation and then analysed for key hydrocarbons throughout 161 days of incubation. Hydrocarbon distributions were analysed by Principal Coordinate Analysis and similar samples grouped by cluster analysis. Variation and differences between samples were determined using permutational multivariate analysis of variance. It was found that all soils followed trajectories approaching the chemical composition of the unpolluted soil. Some contaminated soils were no longer significantly different to that of uncontaminated soil after 161 days of incubation. The use of cluster analysis allows the assignment of a percentage chemical similarity of a diesel contaminated soil to an uncontaminated soil sample. This will aid in the monitoring of hydrocarbon contaminated sites and the establishment of potential endpoints for successful remediation.

Emission of polycyclic aromatic hydrocarbons from gasohol and ethanol vehicles

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20-25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A - Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application. Results showed that the total PAH emission factor varied from 41.9 mu g km(-1) to 612 mu g km(-1) in the gasohol vehicle, and from 11.7 mu g km(-1) to 27.4 mu g km(-1) in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 mu g TEQ km(-1) to 4.61 mu g TEQ km(-1) for the gasohol vehicle and from 0.0117 mu g TEQ km(-1) to 0.0218 mu g TEQ km(-1) in the ethanol vehicle. For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission. (c) 2008 Elsevier Ltd. All rights reserved.

Selective preying of the sphecid wasp Trachypus boharti on the meliponine bee Scaptotrigona postica: potential involvement of caste-specific cuticular hydrocarbons

The specialist digger wasp Trachypus boharti Rubio-Espina preys exclusively on males of the stingless bee Scaptotrigona postica Latreille 1807, although the hunting attacks involve both male and worker bees of S. postica and members of its own species. To understand the mechanism of prey selection, the cuticular hydrocarbon patterns of workers and males of S. postica are analyzed in detail, and the mandibular secretion of males is examined. The cuticular profiles of males and workers are distinctively different. The major group of cuticular compounds, heptacosene isomers, is twice as abundant in workers as in males. There is no clear distinction between worker and male mandibular secretions. Such a distinct and straightforward caste-specific difference in cuticular hydrocarbons could function as a recognition cue by which T. boharti distinguishes between workers and males of S. postica.

On the catalytic hydrogenation of polycyclic aromatic hydrocarbons into less toxic compounds by a facile recoverable catalyst

Here we present the catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) to less toxic mixtures of saturated and partial unsaturated polycyclic hydrocarbons under mild reaction conditions using a magnetically recoverable rhodium catalyst and molecular hydrogen as the exclusive H source. The catalyst is easily recovered after each reaction by placing a permanent magnet on the reactor wall and it can be reused in successive runs without any significant loss of catalytic activity. As an example, anthracene was totally converted into the saturated polycyclic hydrocarbon form (ca. 60%) and the partially hydrogenated form, 1,2,3,4,5,6,7,8-octahydroanthracene (ca. 40%). The catalyst operates in a broad range of temperature and H(2) pressure in both organic and aqueous/organic solutions of anthracene and it also exhibits significant activity at low substrate concentrations (20 ppm). This can be an efficient recycling process for hydrogenation of PAHs present in contaminated fluid waste streams. (C) 2009 Elsevier B.V. All rights reserved.

NMR study of slow motions of HDA hydrocarbons chains inside lamellar structures

Measurements of H-1 and C-13 Nuclear Magnetic Resonance (NMR) for the nano-composite materials formed by the intercalation of hexadecylamine (HDA) in metal oxides (TiO2, V2O5 and MoO3), are reported. The H-1 NMR spin-lattice relaxation in the rotating frame was described by using the spectral density due to Davidson and Cole, which incorporates a distribution of correlation times characterized by a width parameter epsilon. The fitting of the data was obtained for epsilon = 0.74, indicating that the correlation times are distributed over a narrow range in this system. High-resolution C-13 NMR techniques were used to resolve the NMR lines of middle-chain methylene groups in the spectra and variable contact time cross-polarization {H-1-}C-13 experiments were employed to analyze the reorientation dynamics of the CH3 and CH2 groups in the HDA chains.

Catalytic oxidation of hydrocarbons by trinuclear mu-oxo-bridged ruthenium-acetate clusters: Radical versus non-radical mechanisms

The [Ru(3)O(H(3)CCO(2))(6)(py)(2)(L)]PF(6) clusters, where L=methanol or dimethyl sulfoxide, can be activated by peroxide or oxygen donor species, such as tert-butyl hydroperoxide (TBHP) or iodosylbenzene (PhIO), respectively, generating reactive intermediates of the type [Ru(3)(IV,IV,III)=0](+). In this way, they catalyse the oxidation of cyclohexane or cyclohexene by TBHP and PhIO, via oxygen atom transfer, rather than by the alternative oxygen radical mechanism characteristic of this type of complexes. In addition to their ability to perform efficient olefin epoxydation catalysis, these clusters also promote the cleavage of the C-H bond in hydrocarbons, resembling the oxidation catalysis by metal porphyrins. (C) 2008 Elsevier Inc. All rights reserved.

Improving the Fluorescence Detectability of Polycyclic Aromatic Hydrocarbons for Evaluation of Workplace Environments of Cement Industries Processing Organic Residues

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.

Action mechanisms of petroleum hydrocarbons present in waters impacted by an oil spill on the genetic material of Allium cepa root cells

Chromosomal aberration (CA) assays have been widely used, not only to assess the genotoxic effects of chemical agents, but also to evaluate their action mechanisms on the genetic material of exposed organisms. This is of particular interest, since such analyses provide a better knowledge related to the action of these agents on DNA. Among test organisms, Allium cepa is an outstanding species due to its sensitivity and suitable chromosomal features, which are essential for studies on chromosomal damage or disturbances in cell cycle. The goal of the present study was to analyze the action mechanisms of chemical agents present in petroleum polluted waters. Therefore, CA assay was carried out in A. cepa meristematic cells exposed to the Guaeca river waters, located in the city of Sao Sebastiao, SP, Brazil, which had its waters impacted by an oil pipeline leak. Analyses of the aberration types showed clastogenic and aneugenic effects for the roots exposed to the polluted waters from Guaeca river, besides the induction of cell death. Probably all the observed effects were induced by the petroleum hydrocarbons derived from the oil leakage. (C) 2008 Elsevier B.V. All rights reserved.

Alternant and BCH codes over certain rings

Alternant codes over arbitrary finite commutative local rings with identity are constructed in terms of parity-check matrices. The derivation is based on the factorization of x s - 1 over the unit group of an appropriate extension of the finite ring. An efficient decoding procedure which makes use of the modified Berlekamp-Massey algorithm to correct errors and erasures is presented. Furthermore, we address the construction of BCH codes over Zm under Lee metric.

Radon in groundwater contaminated by dissolved hydrocarbons in Santa Barbara d'Oeste, São Paulo State, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Atmospheric particulate polycyclic aromatic hydrocarbons from road transport in southeast Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Polycyclic aromatic hydrocarbons (PAHs) in raw cane sugar (rapadura) in Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Contribution of sugar-cane harvesting season to atmospheric contamination by polycyclic aromatic hydrocarbons (PAHs) in Araraquara city, Southeast Brazil

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

Polycyclic aromatic hydrocarbons from wood pyrolyis in charcoal production furnaces

Polycyclic aromatic hydrocarbons (PAH) were measured in smoke samples from wood carbonization during charcoal production, in both particulate matter (PM) and gaseous phases. Samples were acquired using a medium-volume air sampler at 1.5 m distance from the furnace. Particle-bound PAH were collected on Fluoropore polytetrafluoroethylene filters and gas-phase PAH were collected into sorbent tubes with XAD-2 resin. PAH were extracted with dichloromethane-methanol and analyzed using gas chromatography-mass spectrometry. The results showed total emission from the furnace of 26 mu g/m(3) for the 16 PAH and 2.8 mu g/m(3) for the 10 genotoxic PAH (from fluoranthene to benzo[g,h,i]perylene). High emission of 16 PAH in the first 8 h of wood carbonization was detected (64 mu g/m(3); 56% of the total emission). Associated with PM, 11% of the total emission of 16 PAH (in both phases) and 60% of 10 genotoxic PAH were found. Relative ratios (for example, [Phe]/[Phe] + [Ant]) for the PAH of the same molecular weight were obtained and compared with the published data. The concentrations of benzo[a]pyrene equivalent (BaPeq) were estimated using the list of toxic equivalent factors suggested by Nisbet and LaGoy, 1992. The values of 0.30 and 0.06 mg/m3 were obtained for the total concentrations of BaPeq in PM and gaseous phase, respectively. (c) 2006 Elsevier B.V. All rights reserved.

Identification of polycyclic aromatic hydrocarbons and methoxylated phenols in wood smoke emitted during production of charcoal

More than 130 organic substances in dichloromethane-methanol (4: 1) extracts of particulate matter and the gaseous phase from wood burning for the production of charcoal have been identified by capillary gas chromatography coupled with low-resolution mass spectrometry (GC-MS), use of GC retention indices, and comparison with authentic standards. Many of the substances identified are methoxyphenols (derivatives of syringol and guaiacol), polycyclic aromatic hydrocarbons (PAH), oxidized PAH (oxy-PAH), and levoglucosan, the last being a monosoccharide derivative from the thermal breakdown of cellulose. The amount of unsubstituted PAH was greater than that of methyl- and dimethyl-substituted homologs.