[pt] Amostras de precipitação foram coletadas em dois locais distintos (Gávea e Parque Nacional da Serra dos Órgãos - PARNASO) no estado do Rio de Janeiro, no período de abril de 2022 a abril de 2023. As amostras foram analisadas quanto aos constituintes iônicos por cromatografia de íons (CI) e quanto aos elementos traço por ICP-MS para a determinação de suas concentrações e identificação das fontes potenciais. A concentração dos íons (microequivalentes L-1 ) das amostras da Gávea foi (oxalato) < fluoreto < (malonato) < (brometo) < (acetato) < (sulfato) < (nitrato) < Cle (potássio) < (magnésio) < (amônia)< (cálcio) < (sódio) , enquanto nas do PARNASO foi (brometo) < (oxalato) < (acetato) < (oxalato)< (nitrato) < (fosfato) < Cle (cálcio) < (magnésio) < (potássio) < (sódio) . Já a concentração (miligrama por litro) dos elementos traço na Gávea foi (cromo) = (níquel) = (estanho) < (manganês) < (cobre) < (ferro) < (chumbo) < (zinco), enquanto no PARNASO foi (cromo) < (manganês) < (níquel) < (ferro) < (estanho) < (chumbo) < (cobre) < (zinco). As amostras da Gávea apresentaram um pH médio de 5,73 e uma condutividade média de 21,9 microsiemens cm-1 , enquanto as do PARNASO um pH de 6,05 e uma condutividade de 21,4 microsiemens cm-1 . (Sódio) e (Cloreto) foram os íons mais abundantes na precipitação em ambos os locais, tendo sua origem fortemente associada ao spray marinho. Correlações significativas, fatores de enriquecimento, frações não marinhas e fracionamento de fontes foram realizados para sugerir a origem das espécies iônicas determinadas. A região urbana da Gávea sofreu um maior impacto das fontes antropogênicas (52 por cento), enquanto a região preservada do PARNASO das fontes naturais (62 por cento). Os elementos traço principais foram avaliados a partir da comparação com estudos anteriores presentes na literatura. (Estanho) e (chumbo) foram associados ao desgaste de componentes veiculares, aditivos de combustível e tráfego. As altas de (ferro), (níquel) e (zinco) no PARNASO sugeriram a contribuição, respectivamente, do solo, dos combustíveis líquidos/carvão e dos materiais vegetais geológicos/micronutrientes. Assim, foi confirmada a eficácia da água da chuva como outra ferramenta de avaliação da qualidade do ar de uma região. Além disso, comprovou-se, conforme esperado, que a poluição na Gávea foi maior do que no PARNASO. / [en] Precipitation samples were collected in two different locations (Gávea and Serra dos Órgãos National Park - PARNASO) in the state of Rio de Janeiro, from April 2022 to April 2023. The samples were analyzed for ionic constituents by ionchromatography (IC) and to trace elements by ICP-MS to determine their concentrations and identify potential sources. The ion concentration (microequivalents L-1) of the Gávea samples was (oxalate) < (fluoride)< (malonate)< (bromide)< (acetate)< (sulfate)< (nitrate) < (chloride) and (potassium) < (magnesium) < (ammonium) < (calcium) < (sodium), while in PARNASO it was (bromide)< (oxalate)<(acetate)< (sulfate) < (nitrate) < (phosphate)< Cl and (calcium) < (magnesium) < (sulfate) < (potassium) < (sodium). The concentration (milligram per liter) of the trace elements in Gávea was (chrome) = (nickel)= (tin) < (manganese) < (copper)< (iron) < (lead) < (zinc), while in PARNASO it was (chrome) < (manganese) < (nickel) < (iron) < (tin)< (lead)< (copper) <(zinc). The samples from Gávea had an average pH of 5.73 and an average conductivity of 21.9 (microsiemens) cm-1, while those from PARNASO had a pH of 6.05 and a conductivityof 21.4 (microsiemens) cm-1. (sodium) e (chloride) were the most abundant ions in precipitation in bothlocations, having their origin strongly associated with sea spray. Significant correlations, enrichment factors, non-marine fractions and source fractio nation were performed to suggest the origin of the determined ionic species. The urban region of Gávea suffered a greater impact fro man thropogenic sources (52 percent), while the preserved region of PARNASO from natural sources (62 percent). The main trace elements were evaluated based on comparison with previous studies in the literature. (Tin) and (lead) have been linked to wear on vehicle components, fuel additives, and traffic. The increases in (iron), (nickel) and (zinc) in PARNASO suggested the contribution, respectively, of soil, liquid fuels/coal and geological plant materials/micronutrients. Thus, the effectiveness of rainwater as another tool for assessing air quality in a region was confirmed. Furthermore, it was proven, as expected, that pollution in Gávea was greater than in PARNASO.

[pt] Este trabalho tem como finalidade determinar a concentração em massa, caracterizar quimicamente as espécies presentes e identificar as possíveis fontes das amostras de material particulado (MP10 e MP2,5) coletados em locais com (Gericinó, Lagoa e Copacabana) e sem (Botafogo) a influência dos Jogos Olímpicos, no Rio de Janeiro. As amostras de MP foram disponibilizadas pelo Instituto Estadual do Ambiente (INEA) referente ao ano de 2016, sendo os meses de julho a setembro considerados como a temporada Olímpica. A caracterização química das amostras foi realizada por ICP-MS e Cromatografia de Íons (CI). Durante a temporada Olímpica, em 2016, foram reduzidos cerca de 26 porcento de MP10, quando comparados aos anos anteriores na mesma época do ano, por outro lado, o MP2,5 não foi reduzido. De todos os íons solúveis em água analisados, as maiores concentrações foram obtidas para o NO3-, SO4 2- e Na positivo nas duas frações de MP. As altas concentrações dos íons NO3 - e SO4 2- sugerem a presença de fontes antropogênicas. A partir do cálculo de nss (non-sea salt) foi possível observar que os íons Ca2 positivo, K positivo e SO4 2- tiveram uma contribuição marinha baixa. Os metais Fe, Cu e Ti foram os majoritários em todas as amostras nas duas frações de MP, enquanto que elementos como Mn, Pb, V e Ni foram detectados como minoritários. Correlações acima de 0,90 foram observadas entre Ti-Mn e Ti-Fe, sugerindo emissões de ressuspensão do solo e fortes correlações entre V-Ni e VPb mostram a influencia veicular como principal fonte. Finalmente, foi possível observar que houve uma influência dos Jogos Olímpicos na concentração em massa e de algumas espécies no MP2,5, enquanto que no MP10 não foi observada qualquer correlação. / [en] The main aim of this work was to determine the mass concentration, chemically characterize the species present and identify the possible sources of samples of particulate matter (PM10 e PM2.5) collected at sites with (Gericinó, Lagoa e Copacabana) and without (Botafogo) the influence of the Olympic Games in Rio de Janeiro. The PM samples were obtained from the Instituto Estadual do Ambiente (INEA) relative to the year 2016. The Olympic seasons considered were July to September of 2016. The chemical characterization of the samples was performed by ICP-MS and ion chromatography (IC). PM10 during the Olympic period were reduced 26 percent, when compared to previous years at the same time of the year. On the other hand, PM2.5 was not reduced during the Olympic period. Of all the water-soluble ions analyzed, the highest concentrations were obtained for NO3-, SO42- and Na plus in both fractions of PM. High concentrations of NO3 - and SO4 2- suggest the presence of anthropogenic sources. From calculation of non-sea salt was possible to observe that Ca2 plus, K plus and SO4 2- had a low marine contribution. Fe, Cu and Ti were the majority metals of all samples in both fractions of PM, while Mn, Pb, V and Ni were detected as minorities. Correlations above 0.90 are observed between Ti-Mn and Ti-Fe, suggested soil resuspension emissions. Strong correlations coefficients between V-Ni and V-Pb show the vehicular influence as the main source. Finally, it was possible to observe an influence of the Olympic Games in mass concentration and some species in PM2.5, while in PM10 no correlation was observed.

[pt] O objetivo deste estudo foi determinar a concentração de metais, compostos orgânicos e inorgânicos por suspensão aquosa e análise dos metais por abertura ácida presentes nas amostras de PM10 coletadas em áreas urbanas, industrial e rural da Região Metropolitana do Rio de Janeiro. A concentração de PM10 foi determinada por análise gravimétrica. Espécies inorgânicas e orgânicas presentes nos extratos aquosos foram determinadas por cromatografia de íons e carbono orgânico total (TOC). Os extratos ácidos, e também os aquosos, foram analisados por ICP-MS (espectrometria de massa com plasma indutivamente acoplado) e por ICP OES (espectrometria de emissão óptica com plasma indutivamente acoplado) para determinar a concentração de metais. As correlações entre as concentrações de PM10 e de metais foram avaliadas, considerando os dados meteorológicos para cada ponto de coleta e origem das massas de ar. Os resultados mostraram que as concentrações médias de PM10 foram de 36 micrograma m-3 na área rural, 50 micrograma m-3 na área urbana e 74 micrograma m-3 na área industrial. A concentração de PM10 medida na área industrial ultrapassou, em geral, o limite estabelecido pela resolução CONAMA, de 50 micrograma m-3. O teor de metais apresentou maior concentração na área industrial, sendo predominantes ferro, zinco, alumínio, titânio, manganês, cromo, níquel, cádmio e chumbo. Na área de maior tráfego, foi detectada a maior concentração de cobre e vanádio. As espécies iônicas foram maiores na área urbana, devido à proximidade do oceano. Na área rural, menores concentrações de espécies antropogênicas, como sulfato, nitrato e alguns metais (Pb, Cr, V e Ni) foram medidas. Assim, as concentrações das espécies estudadas são influenciadas pelas características locais. Porém, também foi observado a influencia do transporte de poluentes de longa distância, como queimadas e poeiras dos desertos do continente africano. Os percentuais dos extratos ácido/aquoso demonstraram que os metais extraídos de forma mais eficiente foram V e Ni (maior que 45 porcento), enquanto que os menos extraídos foram Al e Fe (menor que 3 porcento), conforme o esperado. A fração aquosa é importante para avaliar a biodisponibilidade de metais associados a danos à saúde. / [en] The scope of this study was to measure the concentration of metals and organic and inorganic anions in aqueous and acid extracts of PM10 samples collected in urban, industrial and rural zones of Rio de Janeiro. PM10 concentration was determined by gravimetric analysis and the organic and inorganic species in the aqueous extracts were determined by ion chromatography and total organic carbon (TOC). The aqueous and acid extracts were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and by ICP OES (inductively coupled plasma optical emission spectrometry), in order to determine metal content. Correlations between PM10 and metal concentrations were evaluated, considering meteorological data for each site. Results showed that the average PM10 concentrations were 36 microgram m-3; 50 microgram m-3 and 74 microgram m-3 at the rural, downtown and industrial sites, respectively. The measured PM10 concentration in the industrial site exceeded the limit allowed by the Brazilian law, which is 50 microgram m-3. While industrial area had the highest concentrations of metals, such as Fe, Zn, Al, Ti, Mn, Cr, Ni, Cd and Pb, the highest concentrations of Cu and V were found in areas with higher traffic densities. Ionic species had higher concentrations in the urban site due to the proximity to the ocean. The lowest concentrations of species from anthropogenic sources, such as sulfate, nitrate and some metals (Pb, Cr, V and Ni) were measured in the rural area. Hence, studied species concentrations are influenced by site locations, but the influence by the transportation of long distance pollutants, such as biomass burning and dust from African deserts was also observed. The acid/aqueous percentiles showed that the most efficiently extracted metals in the aqueous phase were V and Ni (greater than 45 percent) while the less efficiently extracted were Al and Fe (less than 3 percent), as expected. The aqueous fraction is important to evaluate the bioavailability of metals that are associated to damage to the human health.

[pt] A espectroscopia de ressonância de plásmon superficial (SPR) é uma técnica óptica baseada na excitação coletiva dos elétrons livres de metais nobres, tradicionalmente utilizada em sensoriamento de analitos de diferente natureza. Neste trabalho foi otimizado o processo de fabricação de sensores plasmônicos baseados em filmes finos de ouro e interfaces ouro-grafeno. As plataformas de sensoriamento SPR foram usadas para a detecção de íons de metais tóxicos pesados de Pb(2+), Hg(2+) e Cd(2+) em concentrações de 0.1ppm até 1ppm. Os sensores baseados em interfaces ouro-grafeno, onde o grafeno foi crescido mediante o método CVD, demonstraram uma sensitividade entre 3 até 6 vezes maior que os sensores constituídos por filmes finos de ouro, apontando para uma absorção química devida à transferência de elétrons do grafeno para os íons. / [en] Surface plásmon resonance (SPR) spectroscopy is an optical technique based on the collective excitation of free electrons of noble metals, traditionally used in sensing different types of analytes. In this work the fabrication process of plásmonic sensors based on thin gold films and gold-graphene interfaces was optimized. SPR sensing platforms were used for the detection of toxic heavy metals ions Pb(2+), Hg(2+) and Cd(2+) in concentrations ranging from 0.1ppm to 1ppm. The sensors based on gold-graphene interfaces, where graphene was grown using the CVD method, demonstrated a sensitivity between 3 and 6 times greater than the sensor made of thin films of gold, pointing to a chemical absorption due to the transfer of electrons from the graphene to the ions.

After introducing fundamentals of catalysis with noble metal surfaces especially Pt metal for CO oxidation and subsequent developments on nano-crystalline Pt metals supported on oxide supports, an idea of Pt ion in reducible oxide supports acting as adsorption sites is proposed in chapter 1. Idea of red-ox cycling of an ion in an oxide matrix is presented taking Cu ion in YBa2Cu3O7 as an example. Noble metal ions in reducible oxides such as CeO2 or TiO2 acting as adsorption sites and hence a red-ox catalyst was arrived at from chemical considerations. Among several reducible oxide supports, TiO2 was chosen from crystal structure and electronic structure considerations. A good redox catalyst for auto exhaust and related applications should have high oxygen storage capacity (OSC). Any new material that can work as a redox catalyst should be tested for its OSC. Therefore we designed and fabricated a temperature programmed reduction by hydrogen (H2¬TPR) system to measure OSC. This is presented in chapter 2. We have synthesized a number of oxides by solution combustion method. Structures were determined by powder XRD and Rietveld refinement methods. Fe2O3, Fe2-xPdxO3-δ, Cu1-xMnAl1+xO4, LaCoO3, LaCo1-xPdxO3-δ, CeO2, Ce1¬xPdxO2-δ, TiO2, Ti1-xPdxO2-δ and many other oxide systems were synthesized and their structures were determined. OSC of these systems were determined employing the H2/TPR system. TPR studies were carried out for several redox cycles in each case. Except Pd ion substituted CeO2 and TiO2 other oxide systems decomposed during redox cycling. Pd ion substituted TiO2 gave highest OSC and also it was stable paving way to choose this system for further study. In chapter 3, we have described lattice oxygen of TiO2 activation by the substitution of Pd ion in its lattice. Ti1-xPdxO2-x (x = 0.01 to 0.03) have been synthesized by solution combustion method crystallizing in anatase TiO2 structure. Pd is in +2 oxidation state and Ti is in +4 oxidation state in the catalyst as seen by XPS. Pd is more ionic in TiO2 lattice compared to Pd in PdO. Oxygen storage capacity defined by ‘amount of oxygen that is used reversibly to oxidize CO’ is as high as 5100 μmol/g of Ti0.97Pd0.03O1.97. Oxygen is extracted by CO to CO2 in absence of feed oxygen even at room temperature. Rate of CO oxidation is 2.75 μmol.g-1.s-1 at 60 0C over Ti0.97Pd0.03O1.97 and C2H2 gets oxidized to CO2 and H2O at room temperature. Catalyst is not poisoned on long time operation of the reactor. Such high catalytic activity is due to activated lattice oxygen created by the substitution of Pd ion as seen from first-principles density functional theory (DFT) calculations with 96 atom supercells of Ti32O64, Ti31Pd1O63, Ti30Pd2O62 and Ti29Pd3O61. The compounds crystallize in anatase TiO2 structure with Pd2+ ion in nearly square planar geometry and TiO6 octahedra are distorted by the creation of weakly bound oxygens. Structural analysis of Ti31Pd1O63 which is close to 3% Pd ion substituted TiO2 shows that bond valence of oxygens associated with both Ti and Pd ions in the lattice is 1.87. A low bond valence of oxygen is characteristic of weak oxygen in the lattice compared to oxygens with bond valence 2 and above in the same lattice. Thus, the exact positions of activated oxygens have been identified in the lattice from DFT calculations. Pt has two stable valencies: +2 and +4. Ti ion in TiO2 is in +4 state. Is it possible to substitute Pt exclusively in +2 or +4 state in TiO2? Implications are that Pt in +2 will have oxide ion vacancies and Pt in +4 states will not have oxide ion vacancies. Indeed we could synthesize Pt ion substituted TiO2 with Pt in +2 and +4 states by solution combustion method. In chapter 4, we have shown the positive role of an oxide ion vacancy in the catalytic reaction. Ti0.97Pt2+0.03O1.97 and Ti0.97Pt4+0.03O2 have been synthesized by solution combustion method using alanine and glycine as the fuels respectively. Both are crystallizing in anatase TiO2 structure with 15 nm average crystallite size. X-ray photoelectron spectroscopy (XPS) confirmed Pt ions are only +2 state in Ti0.97Pt0.03O1.97 (alanine) and only in +4 state in Ti0.97Pt0.03O2 (glycine). CO oxidation rate with Ti0.97Pt2+0.03O1.97 is over 10 times higher compared to Ti0.97Pt4+0.03O2. The large shift in 100 % hydrocarbon oxidation to lower temperature was observed by Pt2+ ion substituted TiO2 from that by Pt4+ ion substituted TiO2. After reoxidation of the reduced compound by H2 as well as CO, Pt ions are stabilized in mixed valences, +2 and +4 states. The role of oxide ion vacancy in enhancing catalytic activity has been demonstrated by carrying out the CO oxidation and H2 + O2 recombination reaction in presence and in absence of O2. There is no deactivation of the catalyst by long time CO to CO2 catalytic reaction. We analyzed the activated lattice oxygens upon substitution of Pt2+ ion and Pt4+ ion in TiO2, using first-principles density functional theory (DFT) calculations with supercells Ti31Pt1O63, Ti30Pt2O62, Ti29Pt3O61 for Pt2+ ion substitution in TiO2 and Ti31Pt1O64, Ti30Pt2O62, Ti29Pt3O61 for Pt4+ ion substitution in TiO2. We find that the local structure of Pt2+ ion has a distorted square planar geometry and that of Pt4+ ion has an octahedral geometry similar to Ti4+ ion in pure TiO2. The change in coordination of Pt2+ ion gives rise to weakly bonded oxygens and these oxygens are responsible in high rates of catalytic reaction. Thus, the high catalytic activity results from synergistic roles of oxide ion vacancy and weakly bonded lattice oxygen. In chapter 5, we have shown high rates of H2 + O2 recombination reaction by Ti0.97Pd0.03O1.97 catalyst coated on honeycomb monolith made up of cordierite material. This catalyst was coated on γ¬Al2O3 coated monolith by solution combustion method using dip-dry-burn process. This is a modified conventional method to coat catalysts on honeycombs. Formation of Ti0.97Pd0.03O1.97 catalyst on monolith was confirmed by XRD. Form the XPS spectra of Pd(3d) core level in Ti1-xPdxO2-δ, Pd ion is the formed to be +2 state. Ti0.97Pd0.03O1.97 showed high rates of H2 + O2 recombination compared to 2 at % Pd(metal)/γ-Al2O3, Ce0.98Pd0.02O2-δ, Ce0.98Pt0.02O2-δ, Ce0.73Zr0.25Pd0.02O2-δ and Ti0.98Pd0.02O1.98. Activation energy of H2 + O2 recombination reaction over Ti0.97Pd0.03O1.97 is 7.8 kcal/mole. Rates of reaction over Ti0.97Pd0.03O1.97 are in the range of 10 – 20 μmol/g/s at 60 0C and 4174 h-1 space velocity. Rate is orders of magnitude higher compared to noble metal catalysts. From the industrial point of view, solvent-free hydrogenation of aromatic nitro compounds to amines at nearly 1 bar pressure is an important process. In chapter 6, we showed that Ti0.97Pd0.03O1.97 is a good –nitro to –amine conversion catalyst under solvent-free condition at 1.2 – 1.3 bar H2 pressure. Nitrobenzene, p-nitrotoluene and 2-chloro-4-nitrotoluene are taken for the catalytic reduction reaction. The amine products were analyzed by gas chromatography and mass spectrometry (GCMS). Further, confirmation of compounds was done by FTIR, 1H NMR and 13C NMR. In presence of alcohol as solvent, 100% conversion of aromatic nitro compounds to amines took place at higher temperature and it required more times. In n-butanol solvent, 100% conversion of nitrobenzene and p-nitrotoluene occurred within 10 h and 12 h at 105 °C respectively. We have compared solvent-free reduction of p-nitrotoluene over different catalysts at 90 °C. Catalytic activity for reduction of p¬nitrotoluene over Ti0.97Pd0.03O1.97 is much higher than that reaction over 3 atom % Pd on TiO2 and Pd metal. Turnover frequencies (TOF) for nitrobenzene and 2-chloro-4-nitrotoluene conversion are 217 and 20 over Ti0.97Pd0.03O1.97 respectively. With increase of temperature, TOF of aromatic nitro compound reduction is also increased. We have compared the solvent-free reduction of aromatic nitro compound over Ti0.97Pd0.03O1.97 with others in the literature. Upto 3 cycles of reduction reaction, there was no degradation of Ti0.97Pd0.03O1.97 catalyst and stability of catalyst structure was analyzed by XRD, XPS and TEM images. Catalyst is stable under reaction condition and the structure is retained with Pd in +2 state. Finally, we have proposed the mechanism of -nitro group reduction reaction based on the structure of Ti0.97Pd0.03O1.97. Instead of handling nano-crystalline materials we proceeded with coating our catalysts on cordierite honeycombs. In chapter 7, we have shown high catalytic activity towards Heck reaction over Ce0.98Pd0.02O2-δ and Ti0.97Pd0.03O1.97 coated on cordierite monolith. XRD patterns of Ce0.98Pd0.02O2¬δ coated on cordierite monolith were indexed to fluorite structure. Heck reaction of aryl halide with olefins over Ce0.98Pd0.02O2-δ and Ti0.97Pd0.03O1.97 coated on cordierite monolith were carried out at 120 °C. The products were first analyzed by GCMS and for the confirmation of compounds, we have recorded 1H NMR and 13C NMR. Heck reaction was carried out with different solvents and different bases for choosing the good base and a solvent. Hence, we have chosen K2CO3 as base and N,N¬dimethylformamide (DMF) as solvent. We have compared the rates of Heck reactions over these two catalysts and Ti0.97Pd0.03O1.97 catalyst showed much higher catalytic activity than Ce0.98Pd0.02O2-δ. With increase of temperature from 65 °C to 120 °C, the catalytic activity of Ti0.97Pd0.03O1.97 on Heck reaction is also increased. The catalyst was reused for next Heck reaction without significant loss of activity. A mechanism for Heck reaction of aryl halide with alkyl acrylate has been proposed based on the structure of Ti0.97Pd0.03O1.97. In chapter 8, we have provided a critical review of the work presented in the thesis. Critical issues such as noble metal ion doping in TiO2 vs noble metal ion substitution, difficulty of proving the substitution of low % noble metal ion in TiO2, need for better experimental methods to study noble metal ion in oxide matrix have been discussed. Finally, conclusions of the thesis are presented.

[pt] Durante o período compreendido entre junho e dezembro de 2014, foram coletadas amostras de MP2.5 e MP10 ao longo da orla marítima do Rio de Janeiro, com a finalidade de caracterizar quimicamente as espécies presentes, identificar as possíveis fontes e avaliar a influência do oceano nas amostras. As amostras foram coletadas por um período de 24 h utilizando Hi-Vol e filtros de fibra de vidro e quartzo. A massa do material particulado (MP) foi determinada por gravimetria. Os filtros com MP foram extraídos com água e/ou HNO3. O extrato ácido foi analisado por Espectrometria de Massas com Plasma Indutivamente Acoplado para a determinação de onze elementos. O extrato aquoso foi analisado por Cromatografia Iônica e Carbono Orgânico Total, para a determinação de íons inorgânicos e de ácidos orgânicos e carbono orgânico. As maiores concentrações de íons inorgânicos, foram obtidas para SO42->Na+>NO3->Cl->C2O42- na maioria das estações monitoradas. Em MP2,5 correlações acima de 0,7 foram observadas entre os íons NO3- e SO42-, além disso, estes aníons também apresentaram coeficientes de correlação significativos com o NH4+, sugerindo fontes antrópicas e a formação de aerossóis secundários. Por outro lado, no MP10 foi possível observar a contribuição marinha nas amostras, através das correlações fortes, entre o Na+, principal traçador de água de mar, com o Cl-, Mg2+ e Ca2+. Finalmente, através da fração mássica reconstituída se observou que as fontes naturais, representadas pelo aporte do solo e do sal marinho contribuem com cerca do 50 porcento dos aerossóis nas duas frações, apresentando maiores porcentagens no MP10, enquanto que, os aerossóis secundários predominam no MP2,5. / [en] During the period between June and December of 2014, was collected samples of PM2.5 and PM10 along the seafront of Rio de Janeiro, in order to chemically characterize the species present, identify the possible sources and evaluate the influence of the ocean in the samples. The samples were collected for a 24 h period using Hi-Vol and quartz and glass fiber filters. The particulate material (PM) mass was determined by gravimetry. The filters with PM were extracted with water and/or HNO3. The acid extract was analyzed by Inductively Coupled Plasma Mass Spectrometry for the determination of eleven elements. The aqueous extract was analyzed by Ionic Chromatography and Total Organic Carbon, for the determination of inorganic ions and organic acids and organic carbon. The highest inorganic ions concentrations were obtained for SO42->Na+>NO3->Cl-->C2O42- in most of the monitored stations. In PM2,5 correlations were observed above 0,7 between the ions NO3- and SO42-, furthermore, this anions also showed significant correlation coefficients with NH4+, suggesting anthropogenic sources and the formation of secondary aerossols. On the other hand, in PM10 was possible to observed the marine contribution in the samples, through the strong correlations, between o Na+, major tracer of seawater, with Cl-, Mg2+ e Ca2+. Finally, through the reconstituted mass fraction it was observed that the natural sources, represented by land and sea salt contributes about 50 percent of the aerossol in the two fractions, showing higher percentages in the PM10, while, the secondary aerossol prevail in the PM2,5.