There are a number of inherent problems associated with the analysis of polycyclic aromatic compounds (PAC) in airborne particulate matter. The compounds of interest constitute a very small fraction of the total sample, but consist of hundreds of different components. Therefore, analytical techniques with very high resolving power are required. To try to address these problems, methods have been developed and improved to isolate, and subsequently profile, and identify the PAC present in typical airborne particulate samples. Since no single chromatographic technique can provide the desired resolution, a multi-stage clean-up scheme was required prior to analysis. Two methods were investigated in this study. Both methods used a Soxhlet extraction followed by fractionation using an adsorption chromatography step (silica or alumina) and Sephadex LH-20 to isolate the PAC fraction from the other organic constituents. Another problem associated with the analysis of PAC in airborne particulate matter was because of the method of sample collection. It was believed that there were changes in the chemical composition of the particulate and hence the PAC, during sample collection using a Hi-Vol sampler. Artifacts were being formed by reaction of gaseous pollutants with the particulate collected on the filter. An experiment was established to show that the addition of a denuder bundle to a Hi-Vol sampler could reduce this artifact formation during sampling by removing the reactive gases prior to the surface of the filter. The value of the denuder bundle was evaluated by comparison of the PAC from the denuder Hi-Vol with a standard Hi-Vol. Normal-phase HPLC coupled with mass spectrometry was shown to be a good method to compare the PAC in these samples. Some differences between standard and denuder Hi-Vol samples were observed in laboratory experiments, while the results from field sampling were inconclusive. The use of a parallel column gas chromatography-mass spectrometry (GC-MS) (also called third order chromatography) technique was investigated to determine its viability for the identification of the diverse range of PAC present in environmental samples. The PAC . in the NBS urban dust sample (SRM 1649) was analyzed to evaluate the method. To aid in data processing, a semi-automated peak detection routine has been developed. This routine used programs to aid in the data processing by simplifying peak detection and allow calculation of the retention indices of the components. Using the information supplied by the retention indices and the mass spectra, a data base was developed that was applied to a typical airborne particulate sample. / Thesis / Doctor of Philosophy (PhD)

Burning joss paper and incense is a significant Taoist ceremonial practice in Asian countries such as Taiwan and China. The burning of joss paper has been demonstrated to significantly create particulate matters (PM) and to cause air pollution problems. PM in the atmosphere is among the primary air pollutants, and their sources are factories, vehicles, construction fields, combustion, vehicle exhaust dust, and aerosols derived from photochemical reactions. Numerous sources of environmental PM exist. Thus, the ability to rapidly determine the particulate type and source to adjust the controls and develop policies is an important issue for air quality management. This dissertation consists of two parts on the particulate emission control and characteristic identification. In the first part, we study investigates feasible options of air pollution control devices (APCD) for joss paper furnaces in temples, and used a 40 kg/hr joss paper furnace for testing. This paper examined particulate removal efficiencies of two options: a bag house (capacity 30 m3/min at 108 ¢J) and a wet scrubber (capacity 40 m3/min at 150 ¢J). The results indicate that PM in the diluted flue gas at the bag-house inlet were 76.6 ¡Ó 32.7 mg/Nm3 (average ¡Ó standard deviation), and those at the outlet of the bag-house could be reduced to as low as 0.55 ¡Ó 1.28 mg/Nm3. An average PM removal efficiency of 99.3 % could be obtained with a filtration speed of approximately 2.0 m/min evaluated at 108 ¢J. The wet scrubber removed approximately 70 % of PM, with scrubbing intensities higher than 4.0 L/m2.s across the scrubber cross-section. For the duration of the experiment, no visual white smoke (water mist) was observed at the exit of the wet scrubber with a combustion rate of 16 kg/hr of joss paper, and the scrubbing water temperature was automatically sustained at lower than 61 ¢J. The study concluded that both bag filtration and wet scrubbing are suitable techniques to control particulate emission from joss paper furnaces in Taiwanese temples. The bag filtration technique, while achieving higher efficiencies than the wet scrubbing technique, requires more space and cost. Examinations of bottom and fly ashes of combusted joss paper with X-ray diffraction (XRD) revealed the presence of calcium oxide in the fly ash, while certain metals were found in the bottom ash. The second part aimed at the investigates surface characteristics of airborne PM sampled from air pollution control devices of a number of industrial operations. The PM sources selected for this study comprise the following operations or processes: a coke oven, iron ore sintering furnace, blast furnace, and basic oxygen furnace from an integrated steelmaking plant; electric arc furnaces of two secondary steelmaking plants; a municipal solids waste incinerator; two oil-fired boilers; and a coal-fired power plant boiler. The collected PM samples were analyzed using a scanning electronic microscope (SEM) and energy-dispersive X-ray spectroscope (EDS) to determine their chemical composition and surface characteristics. Results for each PM sample regarding size, surface characteristics, and chemical compositions can be used to trace the related emission industrial sources.

Routine monitoring of environmental pollution demands simplicity and speed without sacrificing sensitivity or accuracy. The development and application of sensitive, fast and easy to implement analytical methodologies for detecting emerging and traditional water and airborne contaminants in South Florida is presented. A novel method was developed for quantification of the herbicide glyphosate based on lyophilization followed by derivatization and simultaneous detection by fluorescence and mass spectrometry. Samples were analyzed from water canals that will hydrate estuarine wetlands of Biscayne National Park, detecting inputs of glyphosate from both aquatic usage and agricultural runoff from farms. A second study describes a set of fast, automated LC-MS/MS protocols for the analysis of dioctyl sulfosuccinate (DOSS) and 2-butoxyethanol, two components of Corexit®. Around 1.8 million gallons of those dispersant formulations were used in the response efforts for the Gulf of Mexico oil spill in 2010. The methods presented here allow the trace-level detection of these compounds in seawater, crude oil and commercial dispersants formulations. In addition, two methodologies were developed for the analysis of well-known pollutants, namely Polycyclic Aromatic Hydrocarbons (PAHs) and airborne particulate matter (APM). PAHs are ubiquitous environmental contaminants and some are potent carcinogens. Traditional GC-MS analysis is labor-intensive and consumes large amounts of toxic solvents. My study provides an alternative automated SPE-LC-APPI-MS/MS analysis with minimal sample preparation and a lower solvent consumption. The system can inject, extract, clean, separate and detect 28 PAHs and 15 families of alkylated PAHs in 28 minutes. The methodology was tested with environmental samples from Miami. Airborne Particulate Matter is a mixture of particles of chemical and biological origin. Assessment of its elemental composition is critical for the protection of sensitive ecosystems and public health. The APM collected from Port Everglades between 2005 and 2010 was analyzed by ICP-MS after acid digestion of filters. The most abundant elements were Fe and Al, followed by Cu, V and Zn. Enrichment factors show that hazardous elements (Cd, Pb, As, Co, Ni and Cr) are introduced by anthropogenic activities. Data suggest that the major sources of APM were an electricity plant, road dust, industrial emissions and marine vessels.

The aims and objectives: The aims and objectives of this study were to characterize and compare the airborne particulate matter in the tankhouse and crusher areas of a base metal refinery sampled with two separate methods, in terms of mass concentration, nickel content, and particle size distribution. Methods: Area sampling was conducted in the two areas. Two methods were applied to collect particulate samples. The first is a multi–stage virtual impactor, the Respicon, which was used to determine the three critical particle fractions (inhalable, thoracic and respirable). The NIOSH 7300 method determined the particle concentration and nickel percentage present in each fraction. Using formulas provided by the manufacturers two additional particle–size fractions (extra–thoracic and trachea–bronchial) could be calculated. The second was based on the standard NIOSH 0500 method, which determined particle size distribution depicted as cumulative percentages. The samples were analyzed using laser scattering instrumentation. Results: In the tankhouse the highest level of exposure was to particles bigger than 10 um, with the highest nickel percentage also falling into this range. However, high nickel percentages were present in all three cut–off sizes (4 um, 10 um and > 10 um). The particle concentration for the crusher area was the highest for particulates bigger than 10 um, with the highest nickel percentage present in this fraction. After comparing the tankhouse and crusher areas, it is clear that the particle concentration is much higher in the crusher area according to all sampling methods used. The nickel content present in the analysis of these areas is of great concern. Conclusion: With the knowledge obtained through this research one hopes to establish a basis for particle size sampling in the platinum mining industry. This may lead to the development of health based OEL's and reflect a more accurate evaluation of workers particulate exposure. This information will give a greater understanding of health risks workers are exposed to. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2011.

The aims and objectives: The aims and objectives of this study were to characterize and compare the airborne particulate matter in the tankhouse and crusher areas of a base metal refinery sampled with two separate methods, in terms of mass concentration, nickel content, and particle size distribution. Methods: Area sampling was conducted in the two areas. Two methods were applied to collect particulate samples. The first is a multi–stage virtual impactor, the Respicon, which was used to determine the three critical particle fractions (inhalable, thoracic and respirable). The NIOSH 7300 method determined the particle concentration and nickel percentage present in each fraction. Using formulas provided by the manufacturers two additional particle–size fractions (extra–thoracic and trachea–bronchial) could be calculated. The second was based on the standard NIOSH 0500 method, which determined particle size distribution depicted as cumulative percentages. The samples were analyzed using laser scattering instrumentation. Results: In the tankhouse the highest level of exposure was to particles bigger than 10 um, with the highest nickel percentage also falling into this range. However, high nickel percentages were present in all three cut–off sizes (4 um, 10 um and > 10 um). The particle concentration for the crusher area was the highest for particulates bigger than 10 um, with the highest nickel percentage present in this fraction. After comparing the tankhouse and crusher areas, it is clear that the particle concentration is much higher in the crusher area according to all sampling methods used. The nickel content present in the analysis of these areas is of great concern. Conclusion: With the knowledge obtained through this research one hopes to establish a basis for particle size sampling in the platinum mining industry. This may lead to the development of health based OEL's and reflect a more accurate evaluation of workers particulate exposure. This information will give a greater understanding of health risks workers are exposed to. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2011.

Abstract The results of the comparison of various dissolution methods for sulphur showed, that HNO3 together with H2O2 gave more complete decomposition of organic components than HNO3 alone. The acid procedure with a mixture of HNO3+H2O2 slightly underestimated the S concentrations of plant material. The losses of sulphur were the highest in the dry ashing digestion procedure (HF(DAC)). The Leco combustion technique with infrared (IR) detection gave good precision and accuracy for sulphur. For the determination of heavy metals in plant materials, both the HNO3 and HNO3+H2O2 procedures were especially effective for determining Cr. However, the HNO3+HClO4 procedure gave lower results, and HF and HF(DAC) procedures greater values for Cr. Sulphur accumulation in pine needles around the pulp and paper mills was clearly higher than other points in the Kemi area. For example, within a radius of about 1-1.5 km around the mills of Oy Metsä-Botnia Ab Kemi Mills, the sulphur concentrations for (C) and (C+1) needles were 28 % and 26 % higher than those in the corresponding background samples collected in Kuivaniemi at a distance about 25 km from Kemi. Pine needles do not appeared to be appropriate a method for monitoring the accumulation of Fe, Zn, V and Pb emitted from pulp and paper mills. However, the Ca concentrations in (C+1) needles in the vicinity of the Oy Metsä-Botnia Ab Kemi Mills was 48 % higher than the average Ca concentration calculated from all (C+1) needles; thus it is likely that part of the Ca in the needles is derived from the mills. The regional distribution pattern of Cr and Ni in mosses in the Kemi-Tornio area in 2000 showed clearly that the most polluted area (Cr > 200 μg/g and Ni > 20 μg/g) appeared to lie within a few kilometres of the ferrochrome and stainless steel works of AvestaPolarit Stainless Oy. Within this area, the Cr concentrations in mosses were 4-13 times higher than those outside the urban area of Tornio. The area most polluted by the opencast chromium mining complex (Cr > 200 μg/g and Ni < 20 μg/g) appeared to be in the immediate vicinity of complex. All the 95th percentile values for TSP (total suspended particles) in the mine area of AvestaPolarit Chrome Oy Kemi Mine were below the current Finnish air quality limit value of 300 μg/m3. However, the 98th percentile value exceeded the Finnish air quality guideline value of 120 μg/m3 at one monitoring site. According to leaching studies, the sum of calculated annual airborne pollution impact of water-soluble fraction (H2O) and environmentally mobile (CH3COONH4) fraction from the AvestaPolarit Chrome Oy Kemi Mine was Cr 1.2 kg, Fe 29 kg, Cu 63 kg, Ni 2.5 kg and Cd < 100 mg. According to the homogeneity studies of heavy metal deposition on TSP filters, Cr, Ni, Cu and Fe were non-uniformly distributed over the glass fibre filters. The rsd values varied between 5.4-33.9 % for Cr, between 7.5-35.0 % for Ni, between 3.6-25.9 % for Cu, and between 6.6-19.9 % for Fe.

A emissão de uma grande diversidade de substâncias através dos efluentes industriais gasosos, líquidos ou sólidos acarreta que uma gama de compostos seja introduzida no ambiente atmosférico e aquático de meios urbanos. A exposição a substâncias genotóxicas no ambiente oferece freqüentemente um grande risco à saúde humana. Com essa preocupação, o presente trabalho avaliou a exposição das pessoas à qualidade do ar atmosférico e à da água para abastecimento público de duas cidades urbanas do Rio Grande do Sul (Brasil), que recebem diferentes contribuições antrópicas (cidades-alvo), comparando-as com uma cidade menos impactada - cidade referência. Os extratos orgânicos da água tratada para abastecimento público e das amostras de ar foram testados quanto a mutagenicidade através do ensaio Salmonella/microssoma (linhagens TA98 e TA100 para água e ar, com e sem fração de metabolização e, ainda para ar, YG1021 e YG1024) - marcador de mutagenicidade. As amostras de ar ainda foram analisadas por HPLC para a caracterização de HPAs e algumas amostras também por HRGC-HRMS para a composição dos PCDD/Fs. Para o biomonitoramento humano foram avaliados através do ensaio do cometa e do micronúcleo (MN), em linfócitos e células da mucosa bucal, respectivamente, as pessoas que viviam nas três cidades - biomarcador de efeito. Análises de polimorfismos genéticos (CYP1A1, GSTM1 e GSTT1) foram utilizados como biomarcadores de susceptibilidade. As duas cidades-alvo apresentaram resultados significativos quanto a mutagenicidade da água de abastecimento apresentando todos os resultados positivos, principalmente para mutação de substituição de pares de bases (TA100), indicando a presença de compostos como THMs e MX. Valores de PTS atmosféricos apresentaram-se em algumas amostragens acima dos limites da legislação brasileira (CONAMA, 1990). Os HPAs encontrados em maior quantidade foram indeno(1,2,3-c,d)pireno e benzo(ghi)perileno, sendo que em uma das amostras a análise dos PCDD/Fs, mostrou valores que superaram em dez vezes a outra amostra analisada. As duas cidades alvo apresentaram altas respostas mutagênicas nas amostras de ar tanto por mutágenos de ação direta, como indireta e também altas concentrações de nitro-HPAs. Estes resultados sinalizaram para a necessidade de uma revisão da legislação para material particulado atmosférico, já que dentro dos atuais parâmetros, grande quantidade de compostos mutagênicos foram encontrados. Para os indivíduos estudados quanto aos biomarcadores de efeito, tanto os linfócitos analisados pelo ensaio do cometa quanto às células da mucosa bucal pelo ensaio do MN não apresentaram resultados significativos, sendo que apenas uma cidade alvo apresentou quanto ao ensaio do cometa. Como a maioria dos indivíduos CYP1A1, GSTM1 e GSTT1 apresentaram genótipos prevalentes, pode estar ocorrendo uma eficiência no sistema de detoxificação garantidos pela presença desses genótipos. Este trabalho mostrou a importância de estudos ambientais que relacionem marcadores de mutagenicidade com biomarcadores de efeito e de susceptibilidade, para que haja uma maior compreensão dos efeitos da exposição humana diária à agentes genotóxicos ambientais. / The emission of a great substances amount through gaseous, liquid and solid industrial effluents have been introduced many kinds of chemical compounds in aquatic and atmospheric environments. The environmental exposure to genotoxic substances often brings great risk to human health. Therefore, the aim of this work was make an avaliation of people exposition to atmospheric air and water supply quality in two urban cities in Rio Grande do Sul State (Brazil) which were under influence of different anthropogenic sources (target cities), compared to a less intense influenced urban city (reference city). The organic extracts from supply water and airborne samples were tested to mutagenicity using the Salmonella/microsome assay (TA98 and TA100 strains for water and airborne samples, with and without metabolization fraction, and also, YG1021 and YG1024 strains for airborne) - mutagenicity marker. Moreover, the airborne samples were analysed by HPLC to PAHs composition and by HRGC-HRMS to PCDD/Fs composition. Human biomonitoring was evaluated by samples of lymphocytes and bucal mucosa cells from individuals living in this three cities using the comet and the micronuclei (MN) assays, respectively - effect biomarkers. Analysis of gene polymorphisms (CYP1A1, GSTM1 and GSTT1) was taken as susceptibility biomarkers. Both target cities showed significative results for the water mutagenicity with mutagenic responses for all samples, mainly to base-pair substitution mutation (TA100 strain), denoting the presence of THMs and MX compounds. The TSP concentrations were above the Brazilian Legislation and World Health Organization regulation limits few times. The PAHs detected in greater amout were indeno(1,2,3-c,d)pyrene and benzo(ghi)perylene and one of the samples overcame ten times the values of PCDD/Fs compared to the other analysed. The two target cities showed high mutagenicity response in all airborne samples, both by direct and indirect mutagens, besides high concentrations of nitro-PHAs. Actually, these results indicate a law revision necessity, because great amount of mutagenic compounds were assessed in smaller concentration that those present in current legal parameters. The analysed subjects for effect biomarkers, both limphocytes tested by comet assay and buccal mucosa cells tested by MN, did not show significant results, only one city show increased primary DNA damage detected through comet assay. As the majority of subjects CYP1A1, GSTM1 e GSTT1 showed prevalent genotype, it maybe occuring an efficient system detoxification warranted by these genotypes presence. This work has shown the importance of environmental studies that relate mutagenicity markers with effect and susceptibility biomarkers, thus a greater understanding about environmental genotoxic agents, which people are exposed daily, will be done carefully.

A emissão de uma grande diversidade de substâncias através dos efluentes industriais gasosos, líquidos ou sólidos acarreta que uma gama de compostos seja introduzida no ambiente atmosférico e aquático de meios urbanos. A exposição a substâncias genotóxicas no ambiente oferece freqüentemente um grande risco à saúde humana. Com essa preocupação, o presente trabalho avaliou a exposição das pessoas à qualidade do ar atmosférico e à da água para abastecimento público de duas cidades urbanas do Rio Grande do Sul (Brasil), que recebem diferentes contribuições antrópicas (cidades-alvo), comparando-as com uma cidade menos impactada - cidade referência. Os extratos orgânicos da água tratada para abastecimento público e das amostras de ar foram testados quanto a mutagenicidade através do ensaio Salmonella/microssoma (linhagens TA98 e TA100 para água e ar, com e sem fração de metabolização e, ainda para ar, YG1021 e YG1024) - marcador de mutagenicidade. As amostras de ar ainda foram analisadas por HPLC para a caracterização de HPAs e algumas amostras também por HRGC-HRMS para a composição dos PCDD/Fs. Para o biomonitoramento humano foram avaliados através do ensaio do cometa e do micronúcleo (MN), em linfócitos e células da mucosa bucal, respectivamente, as pessoas que viviam nas três cidades - biomarcador de efeito. Análises de polimorfismos genéticos (CYP1A1, GSTM1 e GSTT1) foram utilizados como biomarcadores de susceptibilidade. As duas cidades-alvo apresentaram resultados significativos quanto a mutagenicidade da água de abastecimento apresentando todos os resultados positivos, principalmente para mutação de substituição de pares de bases (TA100), indicando a presença de compostos como THMs e MX. Valores de PTS atmosféricos apresentaram-se em algumas amostragens acima dos limites da legislação brasileira (CONAMA, 1990). Os HPAs encontrados em maior quantidade foram indeno(1,2,3-c,d)pireno e benzo(ghi)perileno, sendo que em uma das amostras a análise dos PCDD/Fs, mostrou valores que superaram em dez vezes a outra amostra analisada. As duas cidades alvo apresentaram altas respostas mutagênicas nas amostras de ar tanto por mutágenos de ação direta, como indireta e também altas concentrações de nitro-HPAs. Estes resultados sinalizaram para a necessidade de uma revisão da legislação para material particulado atmosférico, já que dentro dos atuais parâmetros, grande quantidade de compostos mutagênicos foram encontrados. Para os indivíduos estudados quanto aos biomarcadores de efeito, tanto os linfócitos analisados pelo ensaio do cometa quanto às células da mucosa bucal pelo ensaio do MN não apresentaram resultados significativos, sendo que apenas uma cidade alvo apresentou quanto ao ensaio do cometa. Como a maioria dos indivíduos CYP1A1, GSTM1 e GSTT1 apresentaram genótipos prevalentes, pode estar ocorrendo uma eficiência no sistema de detoxificação garantidos pela presença desses genótipos. Este trabalho mostrou a importância de estudos ambientais que relacionem marcadores de mutagenicidade com biomarcadores de efeito e de susceptibilidade, para que haja uma maior compreensão dos efeitos da exposição humana diária à agentes genotóxicos ambientais. / The emission of a great substances amount through gaseous, liquid and solid industrial effluents have been introduced many kinds of chemical compounds in aquatic and atmospheric environments. The environmental exposure to genotoxic substances often brings great risk to human health. Therefore, the aim of this work was make an avaliation of people exposition to atmospheric air and water supply quality in two urban cities in Rio Grande do Sul State (Brazil) which were under influence of different anthropogenic sources (target cities), compared to a less intense influenced urban city (reference city). The organic extracts from supply water and airborne samples were tested to mutagenicity using the Salmonella/microsome assay (TA98 and TA100 strains for water and airborne samples, with and without metabolization fraction, and also, YG1021 and YG1024 strains for airborne) - mutagenicity marker. Moreover, the airborne samples were analysed by HPLC to PAHs composition and by HRGC-HRMS to PCDD/Fs composition. Human biomonitoring was evaluated by samples of lymphocytes and bucal mucosa cells from individuals living in this three cities using the comet and the micronuclei (MN) assays, respectively - effect biomarkers. Analysis of gene polymorphisms (CYP1A1, GSTM1 and GSTT1) was taken as susceptibility biomarkers. Both target cities showed significative results for the water mutagenicity with mutagenic responses for all samples, mainly to base-pair substitution mutation (TA100 strain), denoting the presence of THMs and MX compounds. The TSP concentrations were above the Brazilian Legislation and World Health Organization regulation limits few times. The PAHs detected in greater amout were indeno(1,2,3-c,d)pyrene and benzo(ghi)perylene and one of the samples overcame ten times the values of PCDD/Fs compared to the other analysed. The two target cities showed high mutagenicity response in all airborne samples, both by direct and indirect mutagens, besides high concentrations of nitro-PHAs. Actually, these results indicate a law revision necessity, because great amount of mutagenic compounds were assessed in smaller concentration that those present in current legal parameters. The analysed subjects for effect biomarkers, both limphocytes tested by comet assay and buccal mucosa cells tested by MN, did not show significant results, only one city show increased primary DNA damage detected through comet assay. As the majority of subjects CYP1A1, GSTM1 e GSTT1 showed prevalent genotype, it maybe occuring an efficient system detoxification warranted by these genotypes presence. This work has shown the importance of environmental studies that relate mutagenicity markers with effect and susceptibility biomarkers, thus a greater understanding about environmental genotoxic agents, which people are exposed daily, will be done carefully.

A emissão de uma grande diversidade de substâncias através dos efluentes industriais gasosos, líquidos ou sólidos acarreta que uma gama de compostos seja introduzida no ambiente atmosférico e aquático de meios urbanos. A exposição a substâncias genotóxicas no ambiente oferece freqüentemente um grande risco à saúde humana. Com essa preocupação, o presente trabalho avaliou a exposição das pessoas à qualidade do ar atmosférico e à da água para abastecimento público de duas cidades urbanas do Rio Grande do Sul (Brasil), que recebem diferentes contribuições antrópicas (cidades-alvo), comparando-as com uma cidade menos impactada - cidade referência. Os extratos orgânicos da água tratada para abastecimento público e das amostras de ar foram testados quanto a mutagenicidade através do ensaio Salmonella/microssoma (linhagens TA98 e TA100 para água e ar, com e sem fração de metabolização e, ainda para ar, YG1021 e YG1024) - marcador de mutagenicidade. As amostras de ar ainda foram analisadas por HPLC para a caracterização de HPAs e algumas amostras também por HRGC-HRMS para a composição dos PCDD/Fs. Para o biomonitoramento humano foram avaliados através do ensaio do cometa e do micronúcleo (MN), em linfócitos e células da mucosa bucal, respectivamente, as pessoas que viviam nas três cidades - biomarcador de efeito. Análises de polimorfismos genéticos (CYP1A1, GSTM1 e GSTT1) foram utilizados como biomarcadores de susceptibilidade. As duas cidades-alvo apresentaram resultados significativos quanto a mutagenicidade da água de abastecimento apresentando todos os resultados positivos, principalmente para mutação de substituição de pares de bases (TA100), indicando a presença de compostos como THMs e MX. Valores de PTS atmosféricos apresentaram-se em algumas amostragens acima dos limites da legislação brasileira (CONAMA, 1990). Os HPAs encontrados em maior quantidade foram indeno(1,2,3-c,d)pireno e benzo(ghi)perileno, sendo que em uma das amostras a análise dos PCDD/Fs, mostrou valores que superaram em dez vezes a outra amostra analisada. As duas cidades alvo apresentaram altas respostas mutagênicas nas amostras de ar tanto por mutágenos de ação direta, como indireta e também altas concentrações de nitro-HPAs. Estes resultados sinalizaram para a necessidade de uma revisão da legislação para material particulado atmosférico, já que dentro dos atuais parâmetros, grande quantidade de compostos mutagênicos foram encontrados. Para os indivíduos estudados quanto aos biomarcadores de efeito, tanto os linfócitos analisados pelo ensaio do cometa quanto às células da mucosa bucal pelo ensaio do MN não apresentaram resultados significativos, sendo que apenas uma cidade alvo apresentou quanto ao ensaio do cometa. Como a maioria dos indivíduos CYP1A1, GSTM1 e GSTT1 apresentaram genótipos prevalentes, pode estar ocorrendo uma eficiência no sistema de detoxificação garantidos pela presença desses genótipos. Este trabalho mostrou a importância de estudos ambientais que relacionem marcadores de mutagenicidade com biomarcadores de efeito e de susceptibilidade, para que haja uma maior compreensão dos efeitos da exposição humana diária à agentes genotóxicos ambientais. / The emission of a great substances amount through gaseous, liquid and solid industrial effluents have been introduced many kinds of chemical compounds in aquatic and atmospheric environments. The environmental exposure to genotoxic substances often brings great risk to human health. Therefore, the aim of this work was make an avaliation of people exposition to atmospheric air and water supply quality in two urban cities in Rio Grande do Sul State (Brazil) which were under influence of different anthropogenic sources (target cities), compared to a less intense influenced urban city (reference city). The organic extracts from supply water and airborne samples were tested to mutagenicity using the Salmonella/microsome assay (TA98 and TA100 strains for water and airborne samples, with and without metabolization fraction, and also, YG1021 and YG1024 strains for airborne) - mutagenicity marker. Moreover, the airborne samples were analysed by HPLC to PAHs composition and by HRGC-HRMS to PCDD/Fs composition. Human biomonitoring was evaluated by samples of lymphocytes and bucal mucosa cells from individuals living in this three cities using the comet and the micronuclei (MN) assays, respectively - effect biomarkers. Analysis of gene polymorphisms (CYP1A1, GSTM1 and GSTT1) was taken as susceptibility biomarkers. Both target cities showed significative results for the water mutagenicity with mutagenic responses for all samples, mainly to base-pair substitution mutation (TA100 strain), denoting the presence of THMs and MX compounds. The TSP concentrations were above the Brazilian Legislation and World Health Organization regulation limits few times. The PAHs detected in greater amout were indeno(1,2,3-c,d)pyrene and benzo(ghi)perylene and one of the samples overcame ten times the values of PCDD/Fs compared to the other analysed. The two target cities showed high mutagenicity response in all airborne samples, both by direct and indirect mutagens, besides high concentrations of nitro-PHAs. Actually, these results indicate a law revision necessity, because great amount of mutagenic compounds were assessed in smaller concentration that those present in current legal parameters. The analysed subjects for effect biomarkers, both limphocytes tested by comet assay and buccal mucosa cells tested by MN, did not show significant results, only one city show increased primary DNA damage detected through comet assay. As the majority of subjects CYP1A1, GSTM1 e GSTT1 showed prevalent genotype, it maybe occuring an efficient system detoxification warranted by these genotypes presence. This work has shown the importance of environmental studies that relate mutagenicity markers with effect and susceptibility biomarkers, thus a greater understanding about environmental genotoxic agents, which people are exposed daily, will be done carefully.

O material particulado atmosferico é reconhecido como mutagênico. Embora vários compostos já tenham sido identificados nessa matriz, os mesmos não explicam o efeito observado na maioria dos bioensaios realizados. O ensaio de mutagenicidade Salmonella/microssoma tem sido amplamente utilizado para a avaliação de amostras atmosféricas o qual é muito sensível na detecção de vários tipos de mutágenos, pois é realizado com diferentes linhagens de Salmonella typhimurium na presença e ausência de ativação metabólica exógena. O principal objetivo deste trabalho foi verificar a aplicabilidade da utilização de combinações seletivas de linhagens S. typhimurium na caracterização da mutagenicidade de amostras de material particulado total de ar coletado em Limeira, uma cidade do interior do estado de São Paulo sob influência de intenso tráfego, emissões industriais e da agricultura, incluindo o plantio de cana de açúcar. Foram avaliados seis extratos orgânicos obtidos com diclorometano por ultrasonicação, utilizando o método Salmonella/microssoma em microssuspensão na presença e ausência de ativação metabólica (mistura S9) em experimentos de dose-resposta, com quantidade máxima de 50 µg de material orgânico extraído (MOE) por placa. Os pares de linhagens utilizados foram: YG1041/TA98, para verificar a presença de nitrocompostos, como 1- nitropireno e/ou aminas aromáticas; YG5161/TA1538, altamente sensivel aos hidrocarbonetos policíclicos aromáticos (HPA) não substituídos como o benzo[a]pireno (BaP); e YG7108/TA1535, para a indicação de agentes alquilantes. Os resultados indicaram que os compostos que podem melhor explicar os efeitos observados são os nitro e/ou aminas aromáticas e não os HPA não substituídos como o BaP. O par YG7108/TA1535 forneceu respostas negativas para todas as amostras. As combinações seletivas de linhagens S. typhimurium (YG1041/TA98 e YG5161/TA1538) mostraram-se eficientes na caracterização da mutagenicidade de amostras de ar coletadas na cidade de Limeira, podendo ser utilizadas como uma importante ferramenta de auxílio do ensaio Salmonella/microssoma em microssuspensão em estudos de análises quimicas direcionadas pelo efeito biológico (ADEB). As potências mutagênicas observadas com a linhagem TA98 para a cidade de Limeira foram similares aquelas verificadas na Região Metropolitana de São Paulo. A comparação das respostas de mutagenicidade observadas para as amostras analisadas com o perfil de compostos puros, encontrados na literatura, não forneceu candidatos que podem representar a mistura. Mais estudos de mutagenicidade com compostos puros utilizando os pares de linhagens propostos (TA98/YG1041 e TA1538/YG5161) e análises quimicas de extratos fracionados são necessários para verificar se esta abordagem pode ser útil em estudos de ADEB, e consequentemente na descoberta de novos poluentes atmosféricos. / The atmospheric particulate matter is recognized as mutagenic. Although several compounds have been identified in this matrix, they do not explain the observed effect in most bioassays that have been performed. The Salmonella/microsome assay has been widely used for the evaluation of atmospheric samples, The assay is very sensitive in the detection of various types of mutagens, because it is performed with different strains of Salmonella typhimurium in the presence and absence of exogenous metabolic activation. The main objective of this work was to verify the applicability of selective combination of strains in the characterization of mutagenicity of total airborne particulate matter collected in Limeira, a São Paulo State city in a site influenced by heavy traffic, industrial and agricultural emissions, including sugar cane plantations. We tested six extracts obtained with methylene chloride by ultrasonication using the Salmonella/microsome microsuspension protocol in the presence and absence of rat liver S9 in dose response experiments, using 50 µg of extractable organic matter (EOM) as a maximum dose per plate. The following pairs of strains were used: YG1041/TA98, to verify the presence of nitro-compounds, as 1-nitropyrene and/or aromatic amines; YG5161/TA1538, highly sensitive to non-substituted polycyclic aromatic hydrocarbons (PAHs) as benzo[a]pyrene (BaP); and YG7108/TA1535, for the indication of alkylating agents. The results indicated that the compounds that can better explain the observed effect are the nitro and/or aromatic amines and not nonsubstituted PAHs such as BaP. The pair YG7108/TA1535 provided negative responses for all the samples. Selective combinations of S. typhimurium strains (YG1041/TA98 and YG5161/TA1538) proved efficient in the characterization of mutagenicity of airborne samples collected in the city of Limeira and can be used as an important tool for the Salmonella/microsome microsuspension assay in effect directed chemical analysis (EDA) studies. The mutagenic potencies observed with TA98 strain for the city of Limeira were similar to those verified in the Metropolitan Region of São Paulo. The comparison of the observed mutagenicity responses for the samples analyzed with the profiles of pure compounds found in the literature did not provide any candidates that could alone represent the mixture. More mutagenicity studies with pure compounds using the proposed pair of strains (TA98/YG1041 and TA1538/YG5161) along with chemical analysis of fractioned extracts are needed to verify if this approach can be useful in EDA studies, and consequently in the discovery of new air priority pollutants.