Orientador: Matthieu Tubino / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-19T12:43:39Z (GMT). No. of bitstreams: 1 Caland_LiliaBasiliode_D.pdf: 2271472 bytes, checksum: b5d42f422be0f6983fc7ae4d28db0182 (MD5) Previous issue date: 2011 / Resumo: O trabalho reportou dois métodos alternativos para determinação de íons metálicos (Na, K, Ca e Mg) em amostras de biodiesel. Tais métodos foram aplicados em amostras de biodiesel sintetisados a partir de diferentes óleos vegetais e, também, de gordura animal. Os métodos propostos utilizam, no tratamento da amostra, extração líquido-líquido em meio aquoso ácido, com aquecimento e extração assistida por ultrassom. A quantificação dos íons metálicos é feita por cromatografia de íons (Na, K, Ca e Mg) e por fotometria de chama (Na, K). Uma melhor separação cromatográfica dos íons Na, K, Ca e Mg foi obtida quando se empregou como eluente uma solução mista de ácido dipicolínico 1,7 mmol L com HNO3 2,5 mmol L. Para o método empregando cromatografia de íons, os limites de detecção (LD) e os limites de quantificação (LQ) foram respectivamente: 0,28 e 0,83 mg kg (Na); 0,38 e 1,13 mg kg (K); 0,41 e 1,22 mg kg (Ca); 0,29 e 0,86 mg kg (Mg). Os desvios padrão relativos dos valores encontrados foram menores do que 18,6 %. A exatidão do método foi avaliada através de teste de recuperação, com resultados entre 88,45 e 109,8 %, e por comparação dos dados obtidos por ICP OES. O teste t-Student e o teste¿F mostraram que ambos os métodos apresentaram resultados equivalentes em termos de exatidão e precisão. Na fotometria de chama, os valores de LD e LQ, foram respectivamente: 0,6 e 1,8 mg kg (Na); 0,4 e 1,4 mg kg (K). A recuperação obtida foi de 92,1 % para Na e de 103,6 % para K. Na comparação dos teores dos íons Na e K fornecidos pelo procedimento que usa fotometria de chama com aqueles provindos da cromatografia de íons, não foi observada diferença significativa entre os resultados, ao nível de confiança de 95%, tanto no que se refere à exatidão como à precisão. A simplicidade, exatidão, precisão e custo relativamente baixo dos métodos propostos sugerem que podem ser boas alternativas para a determinação dos íons metálicos (Na, K, Mg e Ca) em amostras de biodiesel / Abstract: In this work reports two alternative methods for the quantitation of metallic ions (Na, K, Mg e Ca) in biodiesel samples. The proposed methods were applied to biodiesel that were synthesized from different vegetable oils and also animal fat. The proposed method uses water extraction, heating and ultrasound. The quantitation of the ions was performed using ion chromatography (Na, K, Mg e Ca) and flame photometry (Na, K).The best chromatographic separation of the cations (Na, K, Ca e Mg) was observed when a solution containing dipicolinic acid (1.7 mmol L) plus nitric acid was used (2.5 mmol L). For the method with ion chromatography, the limits of detection (LOD) and of quantitation (LOQ) were respectively: 0.28 and 0.83 mg kg (Na); 0.38 and 1.13 mg kg (K); 0.41 and 1.22 mg kg (Ca); 0.29 and 0.86 mg kg (Mg). The relative standard deviations of the obtained values were smaller than 18.6 %. The accuracy was determined through recovery procedures, with presented results between 88.45 and 109.8 %, and also by comparison with the data obtained from ICP-OES. The Student.s t-test and the F-test showed that both methods presented equivalent results in with respect to accuracy and precision. In the case of flame photometry the LD and LQ values were respectively: 0.6 and 1.8 mg kg (Na); 0.4 and 1.4 mg kg (K). The observed recoveries were 92.1 % for Na and 103.6 % for K. In the comparison between the set containing the results obtained for Na and K with flame photometry with that came from ion chromatography, it was not observed significant difference at the 95% confidence level, both with respect to accuracy as well to precision. The simplicity, accuracy, precision and relative low cost of the proposed methods suggest that they are interesting alternatives for the quantitation of metallic ions (Na, K, Mg and Ca) in biodiesel samples / Doutorado / Quimica Analitica / Doutor em Ciências

Orientador: Matthieu Tubino / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:33:03Z (GMT). No. of bitstreams: 1 Silveira_EvaLuciaCardoso_D.pdf: 1544784 bytes, checksum: 21e0e9cae43209115424068ca5568476 (MD5) Previous issue date: 2012 / Resumo: Um método de baixo custo é proposto neste trabalho para a análise quantitativa do álcool residual em biodiesel através da determinação do ponto de fulgor. Foram analisados ésteres metílicos obtidos de óleos de soja, milho, girassol e de sebo bovino. Os ésteres etílicos foram obtidos de óleo de soja. Em todos os casos ficou evidente que há uma correlação entre o ponto de fulgor e o teor de álcool residual no biodiesel. Assim, o parâmetro ponto de fulgor pode ser usado diretamente para determinar o teor de álcool residual do biodiesel. Foi proposto também um método para a determinação de fósforo em biodiesel por espectrofotometria de absorção molecular UV-Vis. As amostras de biodiesel são mineralizadas por calcinação a 550 °C seguindo dissolução do resíduo em H2SO4 1,0 mol L. O procedimento analítico é baseado na formação do complexo azul de molibdênio. Empregou-se o ácido 1-amino-2-naftol-4-sulfônico como agente redutor. O método foi aplicado para amostras de biodiesel de soja, canola, girassol e de sebo bovino. Os limites de detecção e quantificação obtidos para fósforo foram de 0,57 mg kg e 1,71 mg kg, respectivamente. O desvio padrão relativo médio obtido foi cerca de 5 %. A simplicidade do procedimento adicionado à precisão, exatidão e o baixo custo indicam que é uma excelente opção para a determinação de fósforo em biodiesel. Um terceiro método, neste caso, para a determinação de ânions em biodiesel baseado na extração com água assistida por ultrassom também foi desenvolvido neste trabalho. Os extratos obtidos das amostras de biodiesel foram analisados por cromatografia de íons. Os limites de quantificação foram 0,97; 4,10; 0,30; 2,47 e 0,26 mg kg para acetato, formiato, cloreto, fosfato e sulfato, respectivamente. A técnica de cromatografia de íons mostrou-se viável para a separação e quantificação de ânions orgânicos e inorgânicos em biodiesel simultaneamente diminuindo assim o tempo de análise / Abstract: A low cost method is proposed in this work for the quantitative analysis of residual alcohol in biodiesel through determination of the flash point. We analyzed methyl esters obtained from oils such as soy, corn, sunflower and of bovine fat. The ethyl esters were obtained from soy oil. In all cases it became very evident that there is a correlation between the flash point and the residual alcohol content in the biodiesel. Therefore the parameter flash point can be used to directly determine the residual alcohol content of biodiesel. A method has been proposed for the determination of phosphorus in biodiesel by UV-vis molecular absorption spectrophotometry. The biodiesel samples are mineralized using an ashing procedure at 550 °C following dissolution of the residue in 1.0 mol L H2SO4. The analytical procedure is based on the formation of a blue molybdenum complex. 1-amino-2naphthol-4-sulfonic acid is used as reducing agent. The method was applied to biodiesel samples of soy, canola and sunflower oils and of bovine fat. The limits of detection and quantification are 0.57 mg kg and 1.71 mg kg, respectively. The average standard deviation obtained was about 5 %. The simplicity of the procedure added to its precision, accuracy and low cost indicate that it is an excellent option for the determination of phosphorus in biodiesel. A third method, in this case, for the determination of anions in biodiesel based on extraction with ultrasound assisted water has also been developed in this study. The extracts of biodiesel samples were analyzed by ion chromatography. The limits of quantification obtained were 0.97, 4.10, 0.30, 2.47 and 0.26 mg kg for acetate, formate, chloride, phosphate and sulfate, respectively. The technique of ion chromatography proved to be feasible for the simultaneously separation and quantification of organic anions in biodiesel, thereby reducing analysis time / Doutorado / Quimica Analitica / Doutora em Ciências

[pt] De acordo com a legislação federal no Brasil (CONAMA: Res. 20/86, Art. 21), a concentração total máxima de selênio permissível em efluentes de fontes poluidoras deve ser tão baixa quanto 0,05 mg L-1. Em refinarias de óleo, nas quais óleo cru proveniente de xisto marinho selenífero é processado, os efluentes podem conter concentrações muito mais altas, exigindo a remoção deste elemento por processos de coagulação/precipitação. O comportamento de selênio nestes processos depende, criticamente, de sua forma química; selenocianato não é eficientemente removido por tratamentos convencionais de precipitação com uso de Fe(OH)3. O conhecimento sobre especiação de selênio no rejeito hídrico é portanto importante para o desenvolvimento de adequadas estratégias de tratamento. Neste trabalho, um novo método para análise de especiação de selenito (Se-IV), selenato (Se-VI) e selenocianato (SeCN-) é descrito, e são apresentados os primeiros resultados sobre a distribuição destas espécies em rejeitos hídricos oriundos de uma planta de refino de óleo brasileira. O método é baseado em separação das espécies por cromatografia de íons seguida por detecção em linha de 77Se, 78Se e 82Se usando ICPMS. O sistema cromatográfico empregado consiste de uma bomba HPLC equipada com válvula injetora manual e uma coluna de troca aniônica (Metrosep A Supp1); esta última interfaceada com o detector (ICPMS) utilizando nebulizador concêntrico-câmara ciclônica como sistema de introdução de amostra. Detecção condutimétrica e amperométrica das espécies de selênio foram também avaliadas, usando-se um cromatógrafo comercial de íons. Vários eluentes, já descritos na literatura para análise de especiação de selênio inorgânico, foram testados (carbonato/bicarbonato, tampão ftalato, ácido p-hidroxibenzóico, etc.) e permitiram, na maioria dos casos, uma boa separação entre Se(IV) e Se(VI), no entanto, resultaram todos em tempos de retenção muito longos e como conseqüência, alargamento do pico para o íon SeCN-1. Esta desvantagem foi eficientemente eliminada usando-se uma solução de ácido cianúrico (0,003 mol L-1), modificado com acetonitrila (2% v/v) e perclorato (0,002 mol/L) como fase móvel. Típicos tempos de retenção (s) para os três analitos aqui estudados foram: selenito (210), < selenato (250) e selenocianato (450). Repetitividades em posição de picos foram melhores que 1%, e na avaliação de área de pico melhores que 3 %. Limites de detecção (em ng) para as espécies usando o instrumento ELAN 5000 e uma alça de amostragem de 500-uL foram 0,04, 0,05 e 0,09, respectivamente. Não se dispunha de materiais de referência certificados para este estudo, contudo, resultados em efluentes de complexa composição e fortificados com os íons de interesse, mostraram aceitáveis recuperações (85% - 115%) e repetitividades (RSD < 5%), validando este método para o propósito previsto. Uma vez otimizado, o método foi aplicado a efluentes hídricos de uma refinaria de óleo. Em todas as amostras analisadas, selenocianato foi de longe a espécie mais abundante, atingindo concentrações de até 90 ug L-1, seguida por selenito. As concentrações de selenato estavam abaixo do limite de detecção em todas as amostras, explicável pelas características redutoras destas águas. As concentrações totais de selênio em todas as amostras, avaliadas por geração de hidretos (HG-ICPMS) e, alternativamente, por ICPOES, excederam aquelas obtidas pela análise de especiação, indicando a presença de outras espécies de selênio, não observadas pela metodologia aqui usada. Trabalhos estão em progresso para identificar e quantificar estas espécies. / [en] According to federal laws in Brazil (CONAMA: Res. 20/86, Art. 21), the maximum permissible total concentration of selenium in effluents from polluting sources must be as low as 0,05 mg L-1. In oil refineries, in which crude oil from seleniferous marine shales are processed, wastewater may contain much higher concentrations, thus requiring removal of this element by coprecipitation/ coagulation procedures. The behavior of selenium in such processes depends critically on its chemical form; e.g. selenocyanate is not efficiently removed by the conventional treatment using Fe(OH)3 precipitation. Knowledge on the speciation of selenium in wastewater is therefore important for the development of adequate treatment strategies. In this work, a new method for the speciation analysis of selenite (Se-IV), selenate (Se-VI) e selenocyanate (SeCN-) is described and first results are presented on the distribution of these species in wastewater samples from a Brazilian oil refinery plant. The method is based on their ion chromatographic separation followed by on-line detection of 77Se, 78Se and 82Se using ICPMS. The chromatographic system employed consisted of HPLC pump equipped with a manual syringe loading injector, and an anion exchange column (Metrosep A Supp1, Metrohm); the latter interfaced with the ICPMS detector via a concentric nebulizer/cyclonic spray chamber sample introduction device. Suppressed conductivity detection and constant potential amperometric detection of these selenium species were also evaluated using a commercial IC-system. Several eluants, already described in the literature for the speciation analysis of inorganic selenium, were tested (e.g. carbonatehidrogencarbonate and phthalate buffer, p-hydroxy benzoic acid, etc) permitting in most cases a good separation of Se(IV) and Se(VI), however resulting all in very long residence times (>20min) and associated peak broadening for the polarizable SeCN - ion. This drawback could be effectively avoided using a solution of cyanuric acid (0.003 mol L-1), modified with acetonitrile (2% v/v) and perclorate (0.002 mol L-1), as the mobile phase. Typical residence times for the three analyte species here studied were: selenite (210 s) < selenate (250 s) < selenocyanate (450 s), with repeatabilities in peak position better than 1% and peak area evaluation better than 3 %. Limits of detection (in ng) for these species using an ELAN 5000 instrument and a 500-uL sample injection loop are 0.04, 0.05 and 0.09, respectively. No certified reference materials were available for this study, however, results on spiked effluent samples of complex composition showed acceptable recoveries (85% - 115%) and repeatibilities (RSD < 5 %), thus validating this method for its intended purpose. Once optimized, the method was applied to wastewater samples from a Brazilian oil refinery plant. In all samples so far analyzed, selenocyanate was by far the most abundant selenium species reaching concentrations of up to 90 uL-1, followed by selenite. Selenate concentrations were below the quantification limit in all samples, explainable by the reducing character of these waters. Total concentrations of selenium in most samples, assessed by hydride generation ICPMS and alternatively by ICPOES, exceeded those obtained from speciation analysis, indicating the presence of other selenium species, not observed by the here used methodology. Work is in progress to identify and quantify these species.

The foremost aim for performing this study was to focus on the electrodeposition of mixed hydrogen molybdenum tungsten bronze films, which have the potential for e– transfer interactions carrying out the reduction of carbon dioxide. A yellow peroxymolybdic tungstate solution was prepared and used for the electrodeposition of hydrogen molybdenum tungsten bronze films on conductive carbon paper. Electrodeposition was carried out at -2.0 V from 20 - 120 minutes to determine the effect of deposition time on film thickness and CO2 reduction. These films were characterized by X-ray photoelectron spectroscopy. The deposited films served as a working electrode for CO2 electrochemical reduction utilizing 0.8 M NaHCO3 as the electrolyte. Carbon dioxide gas was bubbled into the cathode solution for an hour while bulk electrolysis was carried out at different applied potentials. Products were identified and evaluated using ion chromatography.

This Master’s thesis deals with the determination of selected micro and macro elements in bottled water purchased in retail chains Czech Republic. There are described macro elements and micro elements that occur in the waters, bottled waters legislation and the most frequent used instrumental methods for elemental analysis. In this work for the analysis of bottled water were used methods optical emission spectrometry with inductively coupled plasma (ICP-OES) and ion chromatography (IC). Elemental composition of bottled water after analysis corresponded to the composition indicated on the labels, there were recorded only minor deviations from the reported concentrations. All bottled water meets the conditions of the legislation of the Czech Republic. The measured data were statistically processed in the XL Stat program and by multivariate data analysis was examined whether it is possible to individual bottled water from each other based on the analyzes differentiate, which can help in verifying the authenticity of bottled water and in the detection of adulteration of bottled water for profit.

Separation of 225Ra (t1/2 = 15 d) from its daughter isotope 225Ac (t1/2 = 10 d) is necessary to obtain pure 225Ac for cancer alpha-therapy. In this study, microscale separation of 225Ra from its daughter 225Ac using BioRad AG50X4 cation exchange resin was achieved with good reproducibility across microdevices, and ≥90% purity was achieved for 225Ac, which is comparable to conventional chromatography. These results indicate the potential for greater use of microfluidics for biomedical radiochemistry. The modularity of the system and its compatibility with different resins allows for quick and easy adaptation to the various needs of a separation campaign.

Resorcinarenes are cyclic tetramers that are synthesized by the condensation of resorcinol and various aldehydes. The upper and lower rims can be modified with substituents that provide specific selectivity and other chemical features. In this work, resorcinarene-based macrocyclic ligands with specific selectivities have been designed, synthesized and applied to chiral amine discrimination and transition metal ion separations.These resorcinarenes fall into two categories. In the first type, the upper rims of resorcinarenes were modified with amino acid groups, including chiral alanine groups. The lower rims were modified with --CH3, or --C11H23 groups. The structures were studied by nuclear magnetic resonance (NMR), mass spectrometry (MS), dynamic light scattering (DLS), and sustained off-resonance irradiation collision induced dissociation (SORI-CID) techniques in Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The binding strength between the resorcinarenes with amines was studied by 1H NMR titration. Among these new resorcinarenes, the chiral alanine undecyl resorcinarenes acid (AUA) showed chiral discrimination among chiral secondary amines. The AUA ligands were adsorbed onto 55% cross-linked styrene-divinylbenzene resin and used as cation-exchangers in ion chromatography (IC) for transition metal ion separations. The AUA IC column showed selectivity for Cu2+ when no chelating eluent was used in the eluent, a selectivity which was not observed with a commercial column containing standard cation-exchangers. Six metal ions (Cu2+, Mn2+, Co2+, Ni2+, Cd2+, and Zn2+) were separated on the AUA column within a reasonable time with a simple oxalic acid gradient eluent. The second type of resorcinarene-based ligand, cyclenbowl, contains four cyclen units on the upper rim and four --C11H23 chains on the lower rim. The column packed with cyclenbowl adsorbed onto polystyrene showed selectivity for Cu2+ over five other transition metal ions including Mn2+, Co2+, Ni2+, Cd2+, and Zn2+ ions. The preconcentration of Cu2+ at the parts per billion level from a high concentration matrix of Mn2+, Co2+, Ni2+, Cd2+, and Zn2+ ions was achieved using HNO3 eluent. Recovery of Cu2+ was greater than 98%. Furthermore, the other five transition metal ions were well separated on the cyclenbowl column with an oxalic acid eluent gradient.

Bottled drinking water is a common form of water consumption that has grown in popularity and dependency. With countless types and brands available, there are factors to consider regarding the variations in mineral content and microbiological quality, and environmental consequences associated with importing natural bottled waters. Saudi Arabia is the largest desalinated water producer, and although there are scarce natural water resources, consuming locally produced water can alleviate environmental pressures, so long as local bottled water is of good quality and provides the basic function of drinking water. The objective of this study is to scrutinize the variations in bottled waters available in the Saudi market and compare local and imported waters regarding water quality and compliance with health regulations. Surveying local bottled waters revealed that over 60% were imported, adding to the environmental significance. Results from inductively coupled plasma-atomic emission spectroscopy, ion chromatography, and pH meters indicate most bottled waters were compliant with health standards. Flow Cytometry (FCM) was used to determine microbial cell densities. Purified waters, on average, contained significantly lower concentrations than other water types, while mineral waters contained the most cells per milliliter. Microbiological stability was examined through incubating samples at 30°C to promote microbial growth, and results were analyzed using an online FCM system. Purified waters had the least amount of growth and to a lesser degree than mineral and sparkling, which varied in microbial growth responses. DNA extractions and microbial community analyses were performed on select mineral waters before and after incubation. Results showed microbial genera found were similar between samples from the same country and some were unique. All samples exhibited some change in microbial community composition after incubation, signifying that certain communities thrived more than others. Proteobacteria was the most common abundant phylum among samples. Although analysis was restricted to the genera level, there were no health concern associated with types of bacteria discovered. In conclusion, local purified waters had greater microbiological quality and stability than imported waters, and mineral compositions were within the healthy range. Reducing reliance on foreign natural waters may help alleviate environmental consequences and improve local economy

Waste-to-energy has become an attractive alternative to landfills. One concern in this development is the release of pollutants in the combustion process. The binder enhanced d-RDF pellets satisfy the requirements of environmental acceptance, chemical/biological stability, and being storeable. The acid gas emissions of combusting d-RDF pellets with sulfur-rich coal were analyzed by ion chromatography and decreased when d-RDF pellets were utilized. The results imply the possibility of using d-RDF pellets to substitute for sulfur-rich coal as fuel, and also substantiate the effectiveness of a binder, calcium hydroxide, in decreasing emissions of SOx. In order to perform the analysis of the combustion sample, sampling and sample pretreatment methods prior to the IC analysis and the first derivative detection mode in IC are investigated as well. At least two trapping reagents are necessary for collecting acid gases: one for hydrogen halides, and the other for NOx and SOx. Factors affecting the absorption of acid gases are studied, and the strength of an oxidizing agent is the main factor affecting the collection of NOx and SOx. The absorption preference series of acid gases are determined and the absorption models of acid gases in trapping reagents are derived from the analytical results. To prevent the back-flushing of trapping reagents between impingers when leak-checking, a design for the sampling train is suggested, which can be adopted in sample collections. Several reducing agents are studied for pretreating the sample collected in alkali-permanganate media. Besides the recommendation of the hydrogen peroxide solution in EPA method, methanol and formic acid are worth considering as alternate reducing agents in the pretreatment of alkaline-permanganate media prior to IC analysis. The first derivative conductivity detection mode is developed and used in IC system. It is efficient for the detection and quantification of overlapping peaks as well as being applicable for non-overlapping peaks.

Esta dissertação investiga o registro de conteúdo iônico do testemunho de gelo monte Johns (79°55'28"S; 94°23'18"O) obtido na Antártica Ocidental, contribuindo para o adensamento espacial de informações glacioquímicas empregadas em estudos paleoclimáticos. As concentrações de Na+ (16,6 ± 28,2 μg L-1), K+ (1,3 ± 3,7 μg L-1), Mg2+ (3,7 ± 3,7 μg L-1), Ca2+ (5,4 ± 3,4 μg L-1), Cl- (33,3 ± 43,7 μg L-1), SO42- (25,9 ± 17,7 μg L-1), NO3- (50,8 ± 18,5 μg L-1) e H3CSO3- (7,1 ± 5,4 μg L-1) foram determinadas por cromatografia iônica em 2.164 amostras para o período 1882–2008. A variabilidade sazonal de NO3- e, especialmente do nssSO42-, em antifase com Na+, possibilitou a datação pela contagem de ciclos anuais ao longo do período estudado. A identificação dos sinais vulcânicos do Krakatoa (1883), Agung (1963) e Pinatubo/Hudson (1991) foi usada para determinar horizontes de referência (datação absoluta). Eventos de aporte significativo de aerossóis foram identificados e agrupados considerando o conteúdo iônico, proveniência e estação do ano. A avaliação da proveniência dos íons e do balanço iônico mostra a origem da carga iônica: 36% é oriunda de aerossóis de sal marinho, 13% de poeira mineral, 17% de atividade biogênica marinha e 34% de produtos da reatividade química na atmosfera. É observada uma leve redução nas concentrações de Mg2+ (-0,04 μg L-1 ano-1) e K+ (-0,01 μg L-1 ano-1), e mais forte para NO3- (-0,17 μg L-1 ano-1), no período 1909–2008. A média anual da acumulação líquida de neve foi 0,21 ± 0,04 m eq. H2O no período 1882–2008 sem apresentar tendência significante. A acumulação mostra alta correspondência com dados anuais de reanálise climática, com coeficiente de correlação cruzada de +0,42 (α < 0,05) para o período 1979–2008. / This dissertation investigates the ionic content record of the mount Johns ice core (79°55'28"S; 94°23'18"W) recovered from the West Antarctica, contributing to the spatial densification of glaciochemical information used in paleoclimatic studies. The concentrations of Na+ (16.6 ± 28.2 μg L-1), K+ (1.3 ± 3.7 μg L-1), Mg2+ (3.7 ± 3.7 μg L-1), Ca2+ (5.4 ± 3.4 μg L-1), Cl- (33.3 ± 43.7 μg L-1), SO42- (25.9 ± 17.7 μg L-1), NO3- (50.8 ± 18.5 μg L-1) e H3CSO3- (7.1 ± 5.4 μg L-1) were determined by ion chromatography on 2,164 samples for the period 1882–2008. The NO3- seasonal variability and, especially, of the nssSO42- in antiphase with the Na+, allowed the counting of annual cycles over the studied period. The identification of Krakatau (1883), Agung (1963) and Pinatubo / Hudson (1991) volcanic signals was used to determine reference horizons (absolute dating). Significant aerosols events were identified and grouped considering the ionic content, provenance and season of the year. The evaluation of the ions provenance and of the ionic balance points to ionic content origin: 36% come from sea salt aerosols, 13% from mineral dust, 17% originate from marine biogenic activity and 34% are chemical reactivity products in the atmosphere. It is observed a slight reduction in the Mg2+ (-0.04 μg L-1 y-1) and K+ (-0.01 μg L-1 y-1) concentrations, and stronger in the NO3- (-0.17 μg L-1 y-1), during the 1909–2008 period. The annual mean net accumulation rate averaged 0.21 ± 0.04 m w.e. y-1 in the period 1882–2008 did not show any significant trend and shows high correspondence with climatic reanalysis data in years with data overlap, with a cross-correlation coefficient of +0.42 (α < 0.05) for the period 1979–2008.