O objetivo deste trabalho foi avaliar a biodisponibilidade de HPAs na água do mar no sistema estuarino de Santos e no sistema lagunar de Cananéia-Iguape, para isso foi feita a exposição de membranas semipermeáveis (SPMD) e de bivalves (Crassostrea brasiliana) a fim de se obter um melhor panorama das concentrações desse poluente nessas duas regiões. De forma complementar foram analisadas também amostras de água, material particulado em suspensão (MPS) e sedimentos. A bioacumulação de HPAs no tecido de bivalves foi cerca de quatro vezes superior às suas concentrações iniciais para a região de Santos. Foram também estimadas as concentrações de HPA na água do mar através das concentrações encontradas nos SPMDs e nos bivalves transplantados. Essas concentrações foram comparáveis às concentrações encontradas nas amostras de água. Através da análise de componentes principais juntamente com índices diagnósticos foi possível estabelecer as possíveis fonte de HPAs para as matrizes analisadas, identificando assim a predominância de HPAs pirolíticos em bivalves e sedimentos, enquanto que na água, MPS e SPMDs há predominância de HPAs petrogênicos. A comparação entre compartimentos mostrou a importância da avaliação de múltiplas matrizes, em função da concentração de HPAs cada grupo de compostos e de seus diferentes padrões de acumulação. Não foram observadas diferenças significativas entre as concentrações médias de HPAs nas duas regiões de estudo. O Complexo de Cananéia - Iguape antes considerada como área controle, apresentou concentrações de HPAs elevadas, indicando influencia antrópica para a região. / The aim of this work was to evaluate PAH\'s bioavailability in the sea water in Santos Estuarine System and Cananéia - Iguape Lagoon System. SemiPermeable Membrane Devices (SPMD) and bivalves (Crassostrea brasiliana) were deployed in both areas to obtain an overview of all these pollutants concentration, further than the potential of bioaccumulation of contaminants. Aiming comparative purposes, samples of water, suspended particulate matter (SMP) and sediments were also analyzed. PAHs bioaccumulation in bivalves tissues after deployment represented fourfold the initial concentration for Santos region. The estimated concentration of 16 priority PAHs in the water SPMD- and bivalve-based were within the concentration of PAH analyzed in the water samples, demonstrating the effectiveness of those tools to assessment of PAH in water. Through the Principal Components Analysis (PCA), and the diagnostic ratios it was possible to establish the potential sources of PAHs for analyzed compartments, identifying the pyrolytic PAH influence for bivalves and sediments under, while for water, MPS and SPMDs the mainly PAHs source were from petrogenic PAHs. Comparison between compartments showed the importance of multiple tools analyzes due to the concentration of PAH of each compound group and the different pattern of accumulation. It was not observed significant difference between the mean concentrations of PAHs in both studied regions. Cananéia - Iguape Complex was first considered as control area reported PAHs concentration higher PAH concentrations, suggesting anthropic influence in this area.

O objetivo deste trabalho foi avaliar a biodisponibilidade de HPAs na água do mar no sistema estuarino de Santos e no sistema lagunar de Cananéia-Iguape, para isso foi feita a exposição de membranas semipermeáveis (SPMD) e de bivalves (Crassostrea brasiliana) a fim de se obter um melhor panorama das concentrações desse poluente nessas duas regiões. De forma complementar foram analisadas também amostras de água, material particulado em suspensão (MPS) e sedimentos. A bioacumulação de HPAs no tecido de bivalves foi cerca de quatro vezes superior às suas concentrações iniciais para a região de Santos. Foram também estimadas as concentrações de HPA na água do mar através das concentrações encontradas nos SPMDs e nos bivalves transplantados. Essas concentrações foram comparáveis às concentrações encontradas nas amostras de água. Através da análise de componentes principais juntamente com índices diagnósticos foi possível estabelecer as possíveis fonte de HPAs para as matrizes analisadas, identificando assim a predominância de HPAs pirolíticos em bivalves e sedimentos, enquanto que na água, MPS e SPMDs há predominância de HPAs petrogênicos. A comparação entre compartimentos mostrou a importância da avaliação de múltiplas matrizes, em função da concentração de HPAs cada grupo de compostos e de seus diferentes padrões de acumulação. Não foram observadas diferenças significativas entre as concentrações médias de HPAs nas duas regiões de estudo. O Complexo de Cananéia - Iguape antes considerada como área controle, apresentou concentrações de HPAs elevadas, indicando influencia antrópica para a região. / The aim of this work was to evaluate PAH\'s bioavailability in the sea water in Santos Estuarine System and Cananéia - Iguape Lagoon System. SemiPermeable Membrane Devices (SPMD) and bivalves (Crassostrea brasiliana) were deployed in both areas to obtain an overview of all these pollutants concentration, further than the potential of bioaccumulation of contaminants. Aiming comparative purposes, samples of water, suspended particulate matter (SMP) and sediments were also analyzed. PAHs bioaccumulation in bivalves tissues after deployment represented fourfold the initial concentration for Santos region. The estimated concentration of 16 priority PAHs in the water SPMD- and bivalve-based were within the concentration of PAH analyzed in the water samples, demonstrating the effectiveness of those tools to assessment of PAH in water. Through the Principal Components Analysis (PCA), and the diagnostic ratios it was possible to establish the potential sources of PAHs for analyzed compartments, identifying the pyrolytic PAH influence for bivalves and sediments under, while for water, MPS and SPMDs the mainly PAHs source were from petrogenic PAHs. Comparison between compartments showed the importance of multiple tools analyzes due to the concentration of PAH of each compound group and the different pattern of accumulation. It was not observed significant difference between the mean concentrations of PAHs in both studied regions. Cananéia - Iguape Complex was first considered as control area reported PAHs concentration higher PAH concentrations, suggesting anthropic influence in this area.

<p>Air pollutants pose a high risk for humans, and the environment, and this pollution is one of the major environmental problems facing modern society. Active air sampling is the technique that has been traditionally used to monitor nonpolar aromatic air pollutants. However, active high volume samplers (HiVols) require a power supply, maintenance and specialist operators, and the equipment is often expensive. Thus, there is a need to develop new, less complicated sampling techniques that can increase the monitoring frequency, the geographical distribution of the measurements, and the number of sites used in air monitoring programs. In the work underlying this thesis, the use of semipermeable membrane devices (SPMDs) as tools for monitoring gas phase concentrations of nonpolar aromatic compound was evaluated using the compound classes polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs) and nitrated PAHs (nitro-PAHs) as test compounds. </p><p>High wind-speeds increased the uptake and release in SPMDs of PAHs and PCBs with log K_OA values > 7.9, demonstrating that the uptake of most nonpolar aromatic compounds is controlled by the boundary layer at the membrane-air interface. The use of a metal umbrella to shelter the SPMDs decreased the uptake of PAHs and PCBs by 38 and 55 percent, respectively, at high wind/turbulence, and thus reduced the wind effect. Further, the use of performance reference compounds (PRCs) to assess the site effect of wind on the uptake in SPMDs reduced the between-site differences to less than 50 percent from as much as three times differences in uptake of PCBs and PAHs. However, analytical interferences reduced the precision of some PRCs, showing the importance of using robust analytical quality control.</p><p>SPMDs were shown to be efficient samplers of gas phase nonpolar aromatic compounds, and were able to determine local, continental and indoor spatial distributions of PAHs, alkyl- PAHs and nitro-PAHs. In addition, the use of the SPMDs, which do not require electricity, made sampling possible at remote/rural areas where the infrastructure was limited. SPMDs were also used to determine the source of PAH pollution, and different approaches were discussed. Finally, SPMDs were used to estimate the importance of the gas phase exposure route to the uptake of PAHs in plants. The results demonstrate that SPMDs have several advantages compared with HiVols, including integrative capacity over long times, reduced costs, and no need of special operators, maintenance or power supply for sampling. However, calibration data of SPMDs in air are limited, and spatial differences are often only semi-quantitatively determined by comparing amounts and profiles in the SPMDs, which have limited their use in air monitoring programs. In future work, it is therefore important that SPMDs are properly sheltered, PRCs are used in the sampling protocols, and that calibrated sampling rate data, or the SPMD-air partition data, of specific compounds are further developed to make determination of time weighted average (TWA) concentrations possible.</p>

Air pollutants pose a high risk for humans, and the environment, and this pollution is one of the major environmental problems facing modern society. Active air sampling is the technique that has been traditionally used to monitor nonpolar aromatic air pollutants. However, active high volume samplers (HiVols) require a power supply, maintenance and specialist operators, and the equipment is often expensive. Thus, there is a need to develop new, less complicated sampling techniques that can increase the monitoring frequency, the geographical distribution of the measurements, and the number of sites used in air monitoring programs. In the work underlying this thesis, the use of semipermeable membrane devices (SPMDs) as tools for monitoring gas phase concentrations of nonpolar aromatic compound was evaluated using the compound classes polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs) and nitrated PAHs (nitro-PAHs) as test compounds. High wind-speeds increased the uptake and release in SPMDs of PAHs and PCBs with log KOA values &gt; 7.9, demonstrating that the uptake of most nonpolar aromatic compounds is controlled by the boundary layer at the membrane-air interface. The use of a metal umbrella to shelter the SPMDs decreased the uptake of PAHs and PCBs by 38 and 55 percent, respectively, at high wind/turbulence, and thus reduced the wind effect. Further, the use of performance reference compounds (PRCs) to assess the site effect of wind on the uptake in SPMDs reduced the between-site differences to less than 50 percent from as much as three times differences in uptake of PCBs and PAHs. However, analytical interferences reduced the precision of some PRCs, showing the importance of using robust analytical quality control. SPMDs were shown to be efficient samplers of gas phase nonpolar aromatic compounds, and were able to determine local, continental and indoor spatial distributions of PAHs, alkyl- PAHs and nitro-PAHs. In addition, the use of the SPMDs, which do not require electricity, made sampling possible at remote/rural areas where the infrastructure was limited. SPMDs were also used to determine the source of PAH pollution, and different approaches were discussed. Finally, SPMDs were used to estimate the importance of the gas phase exposure route to the uptake of PAHs in plants. The results demonstrate that SPMDs have several advantages compared with HiVols, including integrative capacity over long times, reduced costs, and no need of special operators, maintenance or power supply for sampling. However, calibration data of SPMDs in air are limited, and spatial differences are often only semi-quantitatively determined by comparing amounts and profiles in the SPMDs, which have limited their use in air monitoring programs. In future work, it is therefore important that SPMDs are properly sheltered, PRCs are used in the sampling protocols, and that calibrated sampling rate data, or the SPMD-air partition data, of specific compounds are further developed to make determination of time weighted average (TWA) concentrations possible.