Estudo do comportamento térmico do inseticida HCH com perspectivas para aplicação em descontaminação térmica de solos

Pós-graduação em Química - IBILCE

Ocorrência de poluentes orgânicos persistentes em ovos de Caiman yacare (jacaré-do-Pantanal)

Pós-graduação em Química - IQ

Poluentes orgânicos persistentes em ar interior: desenvolvimento de método de extração em adsorvente para amostragem ativa

Persistent Organic Pollutants (POPs) are chemical substances extraordinarily toxic and persistent in the environment. Due to these properties, POPs are targets of the Stockholm Convention which aims to provide means to eliminate production and use by encouraging the reduction and, where possible, eliminating the release of these contaminants to the environment. One of the articles of this _Convention aims to assess the basal levels of such substances in the environment to monitor both the reduction of release to the environment, and to assess human exposure, using analyzes of milk and air for example. Although efforts to control POPs production and release to the environment have been made, data about their levels in Brazil are still scarce, mainly in the atmosphere or indoor environment. Considering the permanence of people inside its house, this study presents a method for POP extraction from XAD-2 sorbent employed in indoor air sampling, with identification and quantification by GC-ECD. GC-ECD linear range of the studied analytes, congeners of polychlorinated biphenyls (PCB) (28, 52, 101, 118, 138, 153 and 180), DDTs and their metabolites (DDDs, DDEs) and endosullan (isomers c - and 13 - and metabolite endosulfan sulfate) ranged between 0.5 and 16.0 ng mL-I with r2 > 0.967. The method developing consist of selecting the extraction solvent system by agitation (90 rpm, 1 hour) with n-hexan,e (2 mL) or n-hexane:acetone (1:1, v/v) (2 mL), concentration the extract with a gentle N2 stream, and evaluation of breakthrough with passage or air through the fortified XAD-2 cartridge before extraction, employing a low volume air suction pump (Pump Model 224 universal-PCXR8; 5-5000 mL min-1, SKC Inc., Eighty Four, PA, USA), Calibrator Dry-Cal DC-Lite (BIOS, Butler, NJ, USA)). Two fortification levels were employed, 15 and 30 ng. After selecting n-hexane as extraction solvent, with accuracy and precision ranging...

A novel HS-SBSE system coupled with gas chromatography and mass spectrometry for the analysis of organochlorine pesticides in water samples

A methodology to analyze organochlorine pesticides (OCPs) in water samples has been accomplished by using headspace stir bar sorptive extraction (HS-SBSE). The bars were in house coated with a thick film of PDMS in order to properly work in the headspace mode. Sampling was done by a novel HS-SBSE system whereas the analysis was performed by capillary GC coupled mass spectrometric detection (HS-SBSE-GC-MS). The extraction optimization, using different experimental parameters has been established by a standard equilibrium time of 120 min at 85 degrees C. A mixture of ACN/toluene as back extraction solvent promoted a good performance to remove the OCPs sorbed in the bar. Reproducibility between 2.1 and 14.8% and linearity between 0.96 and 1.0 were obtained for pesticides spiked in a linear range between 5 and 17 ng/g in water samples during the bar evaluation.

Accumulation of semivolatile organic compounds in Antarctic vegetation: A case study of polybrominated diphenyl ethers

Antarctic plant communities are dominated by lichens and mosses which accumulate semivolatile organic compounds (SOCs) such as polybrominated diphenyl ethers (PBDEs) directly from the atmosphere. Differences in the levels of PBDEs observed in lichens and mosses collected at King George Island in the austral summers 2004-05 and 2005-06 are probably explained by environmental and/or plant parameters. Contamination of lichens showed a positive correlation with local precipitation, suggesting that wet deposition processes are a major mechanism controlling the uptake of most PBDE congeners. These findings are in agreement with physical-chemical data supporting that tetra- through hepta-BDEs in the Antarctic atmosphere are basically bound to aerosols. Conversely, accumulation of PBDEs in mosses appears to be controlled by other environmental factors and/or plant-specific characteristics. Model simulations demonstrated that an ocean-atmosphere coupling may have played a role in the long-range transport of less volatile SOCs such as PBDEs to Antarctica. According to simulations, the atmosphere is the most important transport medium for PBDEs while the surface ocean serves as a temporary storage compartment, boosting the deposition/volatilization ""hopping"" effect similarly to vegetation on continents. (C) 2011 Elsevier B.V. All rights reserved.

Levels of persistent organic pollutants and residual pattern of DDTs in small cetaceans from the coast of Sao Paulo, Brazil

The State of Sao Paulo is the most developed area in Brazil and was impacted by persistent organic pollutants for several decades. This study investigated organochlorines in five species of small cetaceans (Pontoporia blainvillei, Stenella frontalis, Sotalia guianensis, Tursiops truncatus and Steno bredanensis) found dead along the coast of Sao Paulo between 1997 and 2003. DDTs (15.9 mu g g(-1) lipid: mean for all pooled individuals) and PCBs (8.08 mu g g(-1)) exhibited the highest concentrations in the animals, reflecting large amounts formerly used in Brazil. Lower levels of mirex (0.149 mu g g(-1)), HCB (0.051 mu g g(-1)), CHLs (0.008 mu g g(-1)) and HCHs (0.007 mu g g(-1)) were detected in all species. Residual pattern of DDTs in dolphins suggests that o,p`-DDT is more recalcitrant than p,p`-DDT in the body of the animals and/or the environment. In contrast to p,p`-DDT, residues of o,p`-DDT seem to be preferentially converted into o,p`-DDD rather than op-DDE. (C) 2010 Elsevier Ltd. All rights reserved.

Occurrence of organochlorine compounds in Euphausia superba and unhatched eggs of Pygoscelis genus penguins from Admiralty Bay (King George Island, Antarctica) and estimation of biomagnification factors

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are compounds that do not occur naturally in the environment and are not easily degraded by chemical or microbiological action. In the present work, those compounds were analysed in unhatched penguin eggs and whole krill collected in Admiralty Bay, King George Island, Antarctica in the austral summers of 2004-2005 and 2005-2006. The compounds found in higher levels (in a wet weight basis) were, in most of the egg samples, the PCBs (2.53-78.7 ng g(-1)), DDTs (2.07-38.0 ng g(-1)) and HCB (4.99-39.1 ng g(-1)) and after Kruskal-Wallis ANOVA, the occurrence seemed to be species-specific for the Pygoscelis genus. In all of the cases, the levels found were not higher than the ones in Arctic birds in a similar trophic level. The krill samples analysis allowed estimating the biomagnification factors (which resulted in up to 363 for HCB, one order of magnitude higher than DDTs and chlordanes and two orders of magnitude higher than the other groups) of the compounds found in eggs, whose only source of contamination is the female-offspring transfer. (C) 2009 Elsevier Ltd. All rights reserved.

Diversity of hydrocarbon-degrading Klebsiella strains isolated from hydrocarbon-contaminated estuaries

To investigate the diversity and the catabolic capacity of oil-degrading Klebsiella strains isolated from hydrocarbon-contaminated sediments in Santos-Sao Vicente estuary systems in Brazil. Klebsiella strains obtained from the estuary were characterized using 16S rRNA gene sequencing and BOX-PCR patterns, testing their catabolic capacity to degrade toluene, xylene, naphthalene and nonane, and identifying the catabolic genes present in the oil-degrading strains. Results show that Klebsiella strains were widespread in the estuary. Twenty-one isolates from the Klebsiella genus were obtained; 14 had unique BOX patterns and were further investigated. Among four distinct catabolic genes tested (todC1, ndoB, xylE and alkB1), only the todC1 gene could be amplified in two Klebsiella strains. The biodegradation assay showed that most of the strains had the ability to degrade all of the tested hydrocarbons; however, the strains displayed different efficiencies. The oil-degrading Klebsiella isolates obtained from the estuary were closely related to Klebsiella pneumoniae and Klebsiella ornithinolytica. The isolates demonstrated a substantial degree of catabolic plasticity for hydrocarbon degradation. The results of this study show that several strains from the Klebsiella genus are able to degrade diverse hydrocarbon compounds. These findings indicate that Klebsiella spp. can be an important part of the oil-degrading microbial community in estuarine areas exposed to sewage.

Contamination by chlorinated pesticides, PCBs and PBDEs in Atlantic spotted dolphin (Stenella frontalis) in western South Atlantic

Chlorinated pesticides, PCBs and PBDEs were analysed in nine blubber samples of Atlantic spotted dolphins, Stenella frontalis, incidentally captured during fishing operations in southern and southeastern Brazil between 2005 and 2007. The majority of compounds analysed were detected, suggesting widespread contamination over the region. Although the samples came from a location far from main coastal industrial areas, the results revealed an influence from such sources. Therefore, levels of PCBs (774-23659 ng g(-1) lipid wt.) and PBDEs (23-1326 ng g(-1) lipid wt.) detected seem to be related to the movement of individuals throughout near-shore and offshore waters. The sample from a lactating female exhibited a lower level of contamination and a distinct pattern, indicating selective transfer favouring less lipophilic compounds.

PCBs, PBDEs and organochlorine pesticides in crabs Hepatus pudibundus and Callinectes danae from Santos Bay, State of Sao Paulo, Brazil

The occurrence of persistent organic pollutants (POPS) as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDE) in crabs Hepatus pudibundus and Callinectes danae was assessed from two different places inside of the Santos Bay and Moela Island near one of the most economically important metropolitan areas in Southern Brazil. Among POPs analyzed, Sigma PCBs (222-923 ng g(-1) lipid weight) and Sigma DDTs (154-410 ng g(-1) lw) exhibited the highest concentrations in the crabs. Sigma HCHs ranged from 10.3 to 30.9 ng g(-1), lw and were found in all individuals. Other OCPs found in lower concentration was Mirex (7.6-41.6 ng g(-1) lw) and HCB (5.83-16.9 ng g(-1) lw). Sigma PBDEs (24.1 ng g(-1) lw) were only found in one male individual from the species C. danae collected near to the submarine sewage of Santos. Male crabs showed higher POP concentrations than female crabs for those two species. (C) 2011 Elsevier Ltd. All rights reserved.

Organochlorine contaminants in albatrosses and petrels during migration in South Atlantic Ocean

Albatrosses and petrels (Procellariiformes) are migratory oceanic birds of considerable conservational interest. Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed in the subcutaneous fat, liver and muscle of 100 birds belonging to eight species of Procellariiformes collected during their migration period in southern Brazil, one of the most important feeding areas for these species. Although the profiles of PCBs and OCPs were similar among the individuals, with predominance of penta, hexa and heptachlorobiphenyls and p'p-DDE, organochlorine concentrations exhibited a high degree of intra-species variability. The influence of body condition during the migration period in the distribution of organochlorine contaminants was also evaluated, showing that it is a significant factor in the variation and redistribution of these compounds in the tissues of these birds. The intense use of lipid reserves associated to the contamination from organochlorine compounds could be a troubling factor for seabirds with extended breeding periods and that spend most of their lives at sea migrating long distances, such as most of Procellariiformes. Studies on contamination are necessary to improve the knowledge of the threats to these birds and their populations as well as to contribute with information about persistent organic pollutants in the South Atlantic marine environment.

Exploiting the enzymatic machinery of Arthrobacter atrocyaneus for oxidative kinetic resolution of secondary alcohols

We evaluated Arthrobacter atrocyaneus (R1AF57) as producer of oxidoreductases for oxidative kinetic resolution of racemic secondary alcohols via oxidation reaction. This bacterium was isolated from Amazon soil samples using medium enriched with (RS)-1-(4-methylphenyl)ethanol as a carbon source. The kinetic resolution of several secondary alcohols through enantioselective oxidation mediated by resting cells and growing cells of A. atrocyaneus was efficiently achieved for the most alcohols. In general, it was possible to obtain only the (S)-enantiomer from (RS)-1-arylethanols.

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.

Levels of selected persistent organic pollutants in blood from delivering women in seven selected areas of Sao Paulo State, Brazil

Persistent organic pollutants (POPS) present in the living environment are thought to have detrimental health effects on the population, with pregnant women and the developing foetus being at highest risk. We report on the levels of selected POPs in maternal blood of 155 delivering women residing in seven regions within the Sao Paulo State, Brazil. The following selected POPs were measured in the maternal whole blood: 12 polychlorinated biphenyls (PCBs) congeners (IUPAC Nos. 99, 101, 118, 138, 153, 156, 163, 170, 180, 183, 187, 194); dichlordiphenyltrichloroethane p,p'-DDT, diphenyldichloroethylene p,p'-DDE and other pesticides such as hexachlorocyclohexanes (alpha-HCH, beta-HCH, gamma-HCH), hexachlorobenzene (HCB), chlordane derivatives cis-chlordane, trans-chlordane. oxy-chlordane, cis-nonachlor and trans-nonachlor. Statistical comparisons between regions were performed only on compounds having concentrations above LOD in 70% of the samples. PCB118 congener was found to be highest in the industrial site (mean 4.97 ng/g lipids); PCB138 congener concentration was highest in the Urban 3 site (mean 4.27 ng/g lipids) and congener PCB153 was highest in the industrial and Urban 3 sites with mean concentration of 7.2 ng/g lipids and 5.89 ng/g lipids respectively. Large differences in levels of p,p'-DDE between regions were observed with the Urban 3 and industrial sites having the highest concentrations of 645 ng/g lipids and 417 ng/g lipids, respectively; beta-HCH was found to be highest in the Rural 1 site; the gamma-HCH in Rural 1 and industrial; the HCB in the Rural 1 and industrial sites and oxy-chlordane and t-NC in the Rural 2 sites. An association between levels of some contaminants and maternal age and parity was also found. (C) 2011 Elsevier Ltd. All rights reserved.

Models of the Distribution of Persistent Organic Pollutants in the Marine Environment

Persistent organic pollutants (POPs) is a group of chemicals that are toxic, undergo long-range transport and accumulate in biota. Due to their persistency the distribution and recirculation in the environment often continues for a long period of time. Thereby they appear virtually everywhere within the biosphere, and poses a toxic stress to living organisms. In this thesis, attempts are made to contribute to the understanding of factors that influence the distribution of POPs with focus on processes in the marine environment. The bioavailability and the spatial distribution are central topics for the environmental risk management of POPs. In order to study these topics, various field studies were undertaken. To determine the bioavailable fraction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated naphthalenes (PCNs), and polychlorinated biphenyls (PCBs) the aqueous dissolved phase were sampled and analysed. In the same samples, we also measured how much of these POPs were associated with suspended particles. Different models, which predicted the phase distribution of these POPs, were then evaluated. It was found that important water characteristics, which influenced the solid-water phase distribution of POPs, were particulate organic matter (POM), particulate soot (PSC), and dissolved organic matter (DOM). The bioavailable dissolved POP-phase in the water was lower when these sorbing phases were present. Furthermore, sediments were sampled and the spatial distribution of the POPs was examined. The results showed that the concentration of PCDD/Fs, and PCNs were better described using PSC- than using POM-content of the sediment. In parallel with these field studies, we synthesized knowledge of the processes affecting the distribution of POPs in a multimedia mass balance model. This model predicted concentrations of PCDD/Fs throughout our study area, the Grenlandsfjords in Norway, within factors of ten. This makes the model capable to validate the effect of suitable remedial actions in order to decrease the exposure of these POPs to biota in the Grenlandsfjords which was the aim of the project. Also, to evaluate the influence of eutrophication on the marine occurrence PCB data from the US Musselwatch and Benthic Surveillance Programs are examined in this thesis. The dry weight based concentrations of PCB in bivalves were found to correlate positively to the organic matter content of nearby sediments, and organic matter based concentrations of PCB in sediments were negatively correlated to the organic matter content of the sediment.