Resíduos de pesticidas organoclorados e bifenilas policloradas em compostos de resíduos sólidos urbanos: metodologia e aplicação

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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

Toxicologia reprodutiva de ratos adultos expostos ao 2,3,7,8-Tetraclorodibenzo-P-Dioxina (TCDD) in útero

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

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...

Operational and environmental assessment on the use of charcoal in iron ore sinter production

A study was carried out into the use of charcoal as a supplementary fuel in the iron-ore sintering process. The primary fuel was coke breeze and anthracite with 0, 10, 25, 50 and 100% replacement of the energy input with charcoal to produce sinter. This was achieved by considering the carbon content of each fuel and its corresponding participation on fuel blending, in order to have the same carbon input in each test run. An extensive analysis of the environmental impact was carried out regarding the atmospheric pollutants characterization (dust, sulphur dioxide, nitrogen oxides, carbon monoxide, carbon dioxide, methane, total hydrocarbons, and dioxins and furans). Experimental results indicate that fuel blending where 50% of the heat input was provided by charcoal may be comparable with those using 100% coke, under normal sintering conditions, and may result in a 50% reduction on greenhouse gas emission. It was also observed that while dust, methane and hydrocarbons emissions increased, the total dioxins and furans, expressed as polychlorinated dibenzodioxins/furans, decreased approximately 50% when compared with operation with 100% coke.

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.

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.