César Oliveira

Fluorescence quenching of anthropogenic fulvic acids by Cu(II), Fe(III) and UO22+

The quenching of the fluorescence of three anthropogenic fulvic acids (FA) provoked by Cu(II) (pH 6.0), Fe(III) (pH 4.0) and UO(2)(2+) (pH 3.5), was analyzed by a non-linear method and by Stern-Volmer plots. The FA samples were extracted from composted sewage sludges (csFA), composted municipal wastes (mwFA) and composted livestock wastes (lsFA). Synchronous-scan fluorescence (SyF) spectra were collected as a function of metal ion concentration. Spectral data were treated by a self-modeling mixture analysis method (SIMPLISMA) to detect the SyF spectral band with the strongest quenching and to calculate the corresponding quenching profile. The analysis of these profiles by a non-linear method allowed the estimation of conditional stability constants (K) and of the percentage of non-complexing fluorophores. The same quantitative information was obtained by the modified Stern-Volmer equation taking into account the existence of fluorophores that do not participate in the complexation. Good agreement was found between the results of the two procedures. The logK calculated by the non-linear method were (standard deviation in parenthesis): csFA, Cu(II), 4.22 (5); Fe(III), 5.0 (1); UO(2)(2+), 5.2 (2); mwFA, Cu(II), 4.21 (3); Fe(III), 5.6 (2); UO(2)(2+), 4.7 (3); lsFA, Cu(II), 4.51 (8); Fe(III), 5.5 (2); UO(2)(2+), 3.6 (2).

Size distribution of polycyclic aromatic hydrocarbons in a roadway tunnel in Lisbon, Portugal

Atmospheric aerosols of four aerodynamic size ranges were collected using high volume cascade impactors in an extremely busy roadway tunnel in Lisbon (Portugal). Dust deposited on the tunnel walls and guardrails was also collected. Average particle mass concentrations in the tunnel atmosphere were more than 30times higher than in the outside urban background air, revealing its origins almost exclusively from fresh vehicle emissions. Most of the aerosol mass was concentrated in submicrometer fractions (65%), and polycyclic aromatic hydrocarbons (PAH) were even more concentrated in the finer particles with an average of 84% of total PAH present in sizes smaller than 0.49μm. The most abundant PAH were methylated phenanthrenes, fluoranthene and pyrene. About 46% of the total PAH mass was attributed to lower molecular weight compounds (two and three rings), suggesting a strong influence of diesel vehicle emissions on the production of local particulate PAH. The application of diagnostic ratios confirmed the relevance of this source of PAH in the tunnel ambient air. Deposited dust presented PAH profiles similar to the coarser aerosol size range, in agreement with the predominant origin of coarser aerosol particles from soil dust resuspension and vehicle wear products.

Metal ion complexation properties of fulvic acids extracted from composted sewage sludge as compared to a soil fulvic acid.

Complexation properties of an anthropogenic fulvic acid (FA) extracted from a composted sewage sludge (csFA) for Cu(II), Pb(II) and Cd(II) were studied at pH=6 and at a concentration of 25 mg L(-1). For the case of Cu(II), a particular analysis of the complexation phenomena was done at pH values of 3, 4, 5 and 6 and at aqueous FA concentrations of 25, 50 and 100 mg L(-1) by synchronous excitation molecular fluorescence spectroscopy (SyF). Potentiometric titrimetry with Cu(II), Pb(II), Cd(II) and H+ ion-selective electrodes and acid-base conductimetric titrations were used to obtain experimental information about the acid properties and complexation phenomena. A comparison of the results obtained for csFA with a natural soil FA (sFA) was made. Differences have been detected in the structural composition of the two samples and in the structure of the binding sites. In the csFA, binding site structures containing nitrogen probably play an important role in the complexation, besides oxygen containing structures. Complexation by sFA is mainly due to carboxylic and phenolic structures. Nevertheless, this work shows that csFA have macroscopic complexation properties (magnitude of the conditional stability constant and binding sites concentration) somewhat similar to the natural sFA samples.

Parafac decomposition of three-way kinetic-spectrophotometric spectral matrices corresponding to mixtures of heavy metal ions

Binary and ternary mixtures of some of the following heavy metal ions Zn(II), Ni(II), Pb(II), Co(II) and Cd(II) were analyzed by a ligand substitution kinetic method. Three-way data matrices were generated by acquisition of UV-Vis spectra (332-580 nm) as a function of the time of a substitution reaction observed between the complex of the heavy metal ions with the non selective metallochromic indicator 4-(2-pyridylazo) resorcinol (PAR) and EDTA, and of different relative concentration of the metal ions (1-6 mM). The PARAFAC trilinear model, without restrictions, was used in the data analysis. A full decomposition of the data matrices was obtained (spectra, concentration and time profiles). It was shown that ligand substitution kinetic methods coupled to three-way chemometric analytical methods can be used for the development of robust sensors for the analysis of binary [Zn(II)+Ni(II), Pb(II)+Cd(II), Zn(II)+Pb(II)] or ternary [Zn(II)+Pb(II)+Co(II)] mixtures of metal ions in the micromolar concentration range.

Study of the interaction of a soil fulvic acid with UO22+ by self-modelling mixture analysis of synchronous molecular fluorescence spectra

The interactions between UO22+ and fulvic acids (FUA) were studied by a methodology that involves synchronous molecular fluorescence spectroscopy, to monitor the quenching of the intrinsic fluorescence of FUA by UO22+, and a self-modelling mixture analysis method (SIMPLISMA), to treat spectroscopic data. This methodology was applied to the analysis of the interaction of UO22+ with salicylic acid at pH 3.5 and with a soil FUA at pH 3.5 and 7.0, in this case in the presence of various concentrations of carbonate ion (10–5, 10–4 and 10–3 mol l–1). From the calculated quenching fluorescence intensity profiles, using either the Stern–Volmer relationship or a non-linear least-squares method, mean conditional stability constants (log values with standard deviations in parentheses) were estimated for salicylic acid [respectively 2.72(4) and 2.77(6)], for FUA at pH 3.5 [3.93(2) and 4.4(1)] and pH 7.0 [4.06 and 4.1 (average values for the various concentrations of carbonate ion)]. The non-linear least-squares method also allowed the estimation of the number of binding sites that exist in FUA (0.11 and 0.24 mol g–1 at pH 3.5 and 7.0, respectively).

Variations in wood burning organic marker concentrations in the atmospheres of four European cities

The particulate emissions from biomass burning are a growing concern due to the recent evidence of their ubiquitous and important contribution to the ambient aerosol load. A possible strategy to apportion the biomass burning share of particulate matter is the use of organic molecular tracers. Anhydrosugars (levoglucosan, mannosan and galactosan), together with two organic acids (dehydroabietic and pimaric acids), were previously reported as organic markers for particulate wood burning emissions. These five compounds were studied in four European cities (Helsinki, Copenhagen, Birmingham and Oporto), at both a Roadside and an Urban Background station, during a summer and a winter campaign in the fine (PM(2.5)) and the coarse (PM(10-2.5)) size-fractions of the ambient aerosol. Levoglucosan concentrations were highest in the city of Oporto. In winter, levoglucosan was more present in the fine fraction but in summer, concentrations were similar in both size fractions. Levoglucosan concentrations in the fine size fraction were higher in winter, but no seasonal differences were observed for the coarse size fraction. The lack of difference between the Roadside and Urban Background levoglucosan concentrations points towards a regional nature of this type of pollution. Wood burning was estimated to contribute to about 3.1% of the winter PM(10) mass in Oporto, and to 3.7% in Copenhagen. Mannosan followed the trends exhibited by levoglucosan. The ratio between the levoglucosan and mannosan concentrations allowed determination of a preference for softwood over hardwood in all four cities. Galactosan, pimaric acid and dehydroabietic acid were found to be minor compounds.

Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40°C during 18h in water bath with mechanical stirring or 1h in ultrasonic bath followed by 6h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24h to 7h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization.

Study of the interaction of Al(III) with a soil fulvic acid in the acid pH range by self-modeling mixture analysis of synchronous fluorescence spectral data

The association of Al(III) with a soil fulvic acid (fua) was monitored in the pH range of 2.5–5.0 by synchronous fluorescence (SyF) spectroscopy. Sets of spectra of 100 mg/l fua solutions obtained at increasing Al(III) concentration (up to about 0.7 mM) at each pH (2.5, 3.0, 3.5, 4.0, 4.5 and 5.0) were preprocessed by the self-modeling mixture analysis method SIMPLISMA, with inverted second derivative spectra in the pure variable selection step, to determine the number and to calculate the spectra and concentration profiles of the components. This procedure detected two major components at all pH values: 1. (i) one shows an increase of fluorescence which corresponds to a fluorescent complex formed between Al(III) and one of the binding sites of the fua; 2. (ii) the other shows a decrease of fluorescence probably due to the decrease of the free concentration of a fluorescent binding site that complexes Al(III) forming a complex that does not show fluorescence. Considering the component that shows increase of fluorescence, conditional stability constants [log(K) with standard deviation in parenthesis] were estimated: pH=2.5, 4.5(3); pH=3.0, 4.6(3); pH=3.5, 4.8(2); pH = 4.0, 5.2(1); pH = 4.5, 6.1(2); and pH = 5.0, 6.2(3). These results show that the stability of the complexes between fua and Al(III) decreases markedly for pH < 4.5. This behavior may have an important influence on the changes of the environmental speciation of Al(III) upon acidification.

Monitoring of molecular transformations in acid-base reactions by evolving factor analysis of Fourier transform infrared spectral data

An evolving factor analysis procedure with concentration constraints (gradient concentration window) was applied to the analysis of data sets of aqueous Fourier transform infrared (FT-IR) spectra of carboxylic acids (acetic, malonic and succinic acids) collected in experiments with varying pH. Besides the calculation of the number of acid-base systems, this procedure allowed the calculation of the FT-IR spectra of the acid-base species present in equilibrium as well as the corresponding pK(a) values.

Aerosol particle size distributions at a traffic exposed site and an urban background location in Oporto, Portugal

Aerosol size distributions from 6 to 700 nm were measured simultaneously at an urban background site and a roadside station in Oporto. The particle number concentration was higher at the traffic exposed site, where up to 90% of the size spectrum was dominated by the nucleation mode. Larger aerosol mode diameters were observed in the urban background site possibly due to the coagulation processes or uptake of gases during transport. Factor analysis has shown that road traffic and the neighbour stationary sources localised upwind affect the urban area thought intra-regional pollutant transport.