Characterization of humic-rich hydrocolloids and their metal species by means of competing ligand and metal exchange - an on-site approach

An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators ( diethylenetetraaminepentaacetic acid ( DTPA), ethylendiaminetetraacetic acid ( EDTA)) and metal exchange with strongly competitive cations (Cu(II)) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake ( Venner Moor, Munsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC ( dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES ( inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species ( Fe, Mn, Zn) could be characterized. Conditional exchange constants K ex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn >> Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu( II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.

Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal - humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile. (C) 2007 Elsevier B.V. All rights reserved.

Aquatic humus from an unpolluted Brazilian dark-brown stream: general characterization and size fractionation of bound heavy metals

The main pool of dissolved organic carbon in tropical aquatic environments, notably in dark-coloured streams, is concentrated in humic substances (HS). Aquatic HS are large organic molecules formed by micro-biotic degradation of biopolymers and polymerization of smaller organic molecules. From an environmental point of view, the study of metal-humic interactions is often aimed at predicting the effect of aquatic HS on the bioavailability of heavy metal ions in the environment. In the present work the aquatic humic substances (HS) isolated from a dark-brown stream (located in an environmental protection area near Cubatao city in São Paulo-State, Brazil) by means of the collector XAD-8 were investigated. FTIR studies showed that the carboxylic carbons are probably the most important binding sites for Hg(II) ions within humic molecules. C-13-NMR and H-1-NMR studies of aquatic HS showed the presence of constituents with a high degree of aromaticity (40% of carbons) and small substitution. A special five-stage tangential-flow ultrafiltration device (UF) was used for size fractionation of the aquatic HS under study and for their metal species in the molecular size range 1-100 kDa (six fractions). The fractionation patterns showed that metal traces remaining in aquatic HS after their XAD-8 isolation have different distributions. Generally, the major percentage of traces of Mn, Cd and Ni (determined by ICP-AES) was preferably complexed by molecules with relatively high molecular size. Cu was bound by fractions with low molecular size and Co showed no preferential binding site in the various humic fractions. Moreover, the species formed between aquatic HS and Hg(II), prepared by spiking (determined by CVAAS), appeared to be concentrated in the relatively high molecular size fraction F-1 (> 100 kDa).

Photoelectrocatalytic oxidation of remazol turquoise blue and toxicological assessment of its oxidation products

The ability of photoelectrocatalytic oxidation to degrade the commercially important copper-plitalocyanine dye, remazol turquoise blue 15 (RTB) was investigated. The best experimental condition was optimized, evaluating the performance of Ti/TiO2 thin-film electrodes prepared by sol-gel method in the decolourization of 32 mg L-1 RTB dye in 0.5 mol L-1 Na2SO4 pH 8 and applied potential of +1.5 V versus SCE under UV irradiation. Spectrophotometric measurements, high performance liquid chromatography, dissolved organic carbon (TOC) evaluation and stripping analysis of yielding solution obtained after 3 h of photoelectrolysis leads to 100% of absorbance removal from wavelength of 250-800 nm, 79.6% of TOC reduction and the releasing of up to 54.6% dye-bound copper (0.85 mg L-1) into the solution. Both, original and oxidized dye solution did not presented mutagenic activity with the strains TA98 and WOO of Salmonella in the presence and absence of S9 mix at the tested doses. Nevertheless, the yielding photoelectrocatalytic oxidized solution showed an increase in the acute toxicity for Vibrio fischeri bacteria, explained by copper liberation during treatment. (c) 2006 Elsevier B.V. All rights reserved.

Environmental implications of soil remediation using the Fenton process

This work evaluates some collateral effects caused by the application of the Fenton process to 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) and diesel degradation in soil. While about 80% of the diesel and 75% of the DDT present in the soil were degraded in a slurry system, the dissolved organic carbon (DOC) in the slurry filtrate increased from 80 to 880 mg l(-1) after 64 h of reaction and the DDT concentration increased from 12 to 50 mu g l(-1). Experiments of diesel degradation conducted on silica evidenced that soluble compounds were also formed during diesel oxidation. Furthermore, significant increase in metal concentrations was also observed in the slurry filtrate after the Fenton treatment when compared to the control experiment leading to excessive concentrations of Cr, Ni, Cu and Mn according to the limits imposed for water. Moreover, 80% of the organic matter naturally present in the soil was degraded and a drastic volatilization of DDT and 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene was observed. Despite the high percentages of diesel and DDT degradation in soil, the potential overall benefits of its application must be evaluated beforehand taking into account the metal and target compounds dissolution and the volatilization of contaminants when the process is applied. (c) 2007 Elsevier Ltd. All rights reserved.

Aerosol and precipitation chemistry measurements in a remote site in Central Amazonia: the role of biogenic contribution

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

Carbono orgânico em função do uso do solo

Pós-graduação em Agronomia (Ciência do Solo) - FCAV

Determinação de acetaldeído e formaldeído em água de chuva e suas correlações com carbono orgânico dissolvido em uma região canavieira: Daniely de Godoy Silva. -

Pós-graduação em Química - IQ

Dinâmica do carbono dissolvido no Rio Acre: variações espaciais e sazonais

Este trabalho teve como principal objetivo estudar a dinâmica do carbono dissolvido ao longo de um trecho do rio Acre, avaliando a influência da área urbana da cidade de Rio Branco, e da descarga de três de seus tributários (Riozinho do Rola, igarapé Judia, igarapé São Francisco), bem como a influência das mudanças hidrológicas sazonais. Foram realizadas campanhas de campo mensais, entre dezembro de 2006 e setembro de 2007, em cinco sítios no rio Acre e um sítio na foz de cada um dos três tributários. A cada amostragem 1 litro de amostra de água era submetida a filtração e dividida em alíquotas para as análises de carbono orgânico dissolvido (COO), carbono inorgânico dissolvido (CIO) e íons maiores (Ca² + , Mg² + , K + , Na + , NH 4 + , HCO 3 -, Cl¯, SO 4 ²¯, NO 3 - , NO 2 - , e PO 4 3-) . Além das coletas foram medidos in situ os parâmetros físico-químicos pH, condutividade elétrica, oxigênio dissolvido e temperatura da água. O pH médio anual no rio Acre variou de 6,46 a 6,54 entre os sítios e a condutividade elétrica apresentou valores médios anuais entre os sítios que variam de 69,93 a 77,84 µS cm¯¹. Nos tributários, os valores médios anuais de pH variaram de 6,10 a 6,51 e a condutividade elétrica apresentou valores médios anuais que variaram entre 54,08 e 153,03 S cm¯¹. Os cátions predominantes no rio Acre e nos tributários foram o Na + e o Ca 2+ e os ânions foram o cr e o sol-. A concentração média anual de COD no rio Acre variou de 4,62 a 5,17 mg l¯¹, sem diferenças significativas entre os sítios de amostragem. Nos tributários as médias anuais, de COD variaram de 3,55 a 6,55 mg r1. As concentrações foram, significativamente maiores no período de cheia, com médias que variaram de 6,26 a 6,39 mg l¯¹ nos sítios do rio Acre. O igarapé São Francisco foi o único tributário que não apresentou diferenças entre os períodos sazonais. O CID teve uma concentração média anual no rio Acre que variou de 527,91 a 598,18 µM, sem diferenças significativas entre os sítios de amostragem. As maiores concentrações foram observada na seca, quando as concentrações médias variaram de 816,31 a 998,52 µM. Nos tributários as concentrações médias anuais de CID variaram de 248,54 a 986,50 µM.Quanto a pressão parcial do CO2 (pCO 2 ) , os sítios no rio Acre apresentam valores médios anuais variando entre 3559 e 4059 ppm, sem diferenças entre os sítios e com os maiores valores ocorrendo no período de cheia. Com base nos resultados, pode-se concluir que a dinâmica do carbono dissolvido no rio Acre não apresenta variações significativas decorrentes das descargas dos tributários nem do lançamento de esgotos. Por outro lado, as mudanças hidrológicas sazonais são os maiores responsáveis pelas alterações nesta dinâmica.

Dinâmica do carbono em pequenas bacias de drenagem sob uso de agricultura familiar na Amazônia Oriental

O presente estudo teve como objetivo avaliar a dinâmica do carbono em uma região da Amazônia Oriental, cujo uso da terra predominante é a agricultura familiar; a unidade espacial adotada neste estudo foram três pequenas bacias de drenagem. A dinâmica do carbono foi avaliada a partir de medidas hidrológicas e biogeoquímicas em águas dos igarapés Cumaru, Pachibá e São João entre junho de 2006 a maio de 2007. O ambiente aquático e a hidrogeoquímica fluvial foram caracterizados a partir de medidas in situ da condutividade elétrica, temperatura, pH e concentração de oxigênio dissolvido. Amostras de água foram coletadas e analisadas para determinação do carbono orgânico dissolvido (COD) e pressão parcial do dióxido de carbono (pCO 2 ). A partir dos valores de pCO 2 , foram calculadas as concentrações de carbono inorgânico dissolvido (CID). Já os fluxos de C02 foram medidos in situ e também calculados a partir do pC0 2 . Utilizando-se medidas de vazão instantânea a cada campanha mensal de campo, calcularam-se fluxos anuais de COD. A caracterização dos solos e do uso da terra nas porções estudadas das bacias, assim como os índices pluviométricos e fluviométricos, foram considerados na interpretação dos resultados. Podem-se enumerar como principais resultados o seguinte: 1) As características físico-químicas das águas fluviais das bacias estudadas retrataram seus solos ácidos, a vegetação ripária, e processos hidrológicos biogeoquímicos no ambiente aquático e terrestre, e com certa variabilidade sazonal; 2)0 pH e o oxigênio dissolvido se correlacionaram positivamente com o carbono dissolvido na coluna d'água; 3) O transporte de COD por unidade de área foi elevado quando comparado com outras bacias amazônicas, e mais intenso em períodos chuvosos; 4) O transporte de COD e a evasão de C0 2 pareceram responder positivamente à presença de vegetação secundária e floresta densa, e negativamente às atividades agropecuárias; e 5) As taxas de evasão de C0 2 foram elevadas comparando-as a outros rios amazônicos, e corroboram a hipótese de que pequenas bacias são importante fontes de C0 2 para atmosfera na região.

Influência da bacia hidrográfica e características espaço-temporais de variáveis limnológicas sobre reservatórios no Rio Jacuí - RS

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Redução de mercúrio iônico por substâncias húmicas aquáticas

Pós-graduação em Química - IQ

Carotenogênese em células de Haematococcus pluvialis induzidas pelos estresses luminoso e nutricional

The objective of this work was to evaluate the responses of Haematococcus pluvialis cells to the carotenogenesis induction process, under light and nutrition stress. Cells were acclimated during 15 days in WC medium, with aeration with synthetic, filtered atmospheric air and flow rate of 100 mL min-1, light intensity of 50 µmol photons m-2 s-1, photoperiod of 12 hours, and temperature of 23ºC. The following two treatments were compared: cultivation under the described conditions, but with increase of light intensity up to 350 µmol photons m-2 s-1 ; and cultivation under the same conditions as the previous treatment, but with aeration containing 4% CO2. The treatments were done in triplicate, during ten days. With the addition of CO2 and the increment in lighting, an increase was observed in the carotenoids/chlorophyll ratio and cell biomass. Cells stopped dividing on the second day of stress, when nitrate became limiting, and significantly increased their biovolume. The excretion of organic carbon and the concentration of astaxanthin increase in response to the addition of CO2. Stress by light intensity combined with CO2 addition optimizes carotenogenesis in H. pluvialis and increases astaxanthin production.

Interações entre espécies de arsênio e matéria orgânica natural: Lílian Karla de Oliveira. -

Pós-graduação em Química - IQ

Zero-valent iron mediated degradation of ciprofloxacin - Assessment of adsorption, operational parameters and degradation products

The zero-valent iron (ZVI) mediated degradation of the antibiotic ciprofloxacin (CIP) was studied under oxic condition. Operational parameters such as ZVI concentration and initial pH value were evaluated. Increase of the ZVI concentration from 1 to 5 g L−1 resulted in a sharp increase of the observed pseudo-first order rate constant of CIP degradation, reaching a plateau at around 10 g L−1. The contribution of adsorption to the overall removal of CIP and dissolved organic carbon (DOC) was evaluated after a procedure of acidification to pH 2.5 with sulfuric acid and sonication for 2 min. Adsorption increased as pH increased, while degradation decreased, showing that adsorption is not important for degradation. Contribution of adsorption was much more important for DOC removal than for CIP. Degradation of CIP resulted in partial defluorination since the fluoride measured corresponded to 34% of the theoretical value after 120 min of reaction. Analysis by liquid chromatography coupled to mass spectrometry showed the presence of products of hydroxylation on both piperazine and quinolonic rings generating fluorinated and defluorinated compounds as well as a product of the piperazine ring cleavage.