Fluorescence quenching of anthropogenic fulvic acids by Cu(II), Fe(III) and UO(2)(2+)

The quenching of the fluorescence of three anthropogenic fulvic acids (FA) provoked by Cu(II) (pH 6.0), Fe(III) (pH 4.0) and UO₂²⁺ (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 log K calculated by the non-linear method were (standard deviation in parenthesis): csFA, Cu(II), 4.22 (5); Fe(III), 5.0 (1); UO₂²⁺, 5.2 (2); mwFA, Cu(II), 4.21 (3); Fe(III), 5.6 (2); UO₂²⁺, 4.7 (3); lsFA, Cu(II), 4.51 (8); Fe(III), 5.5 (2); UO₂²⁺, 3.6 (2).     

Thermal lens spectrometric determination of hexavalent chromium

The applicability of thermal lens spectrometry (TLS) for quantification and routine determination of hexavalent chromium was investigated by using a collinear dual beam thermal lens spectrometer. In aqueous solutions the LOD of 0.1 μg l⁻¹ was obtained for Cr(VI) by using 160 mW laser power. The performance of the technique was verified by the determination of hexavalent chromium in standard reference water samples (NIST SRM 1643a and NIST SRM 1643c) and comparing the results for Cr(VI) in CCA (Cr, Cu, As)-treated timber extracts to concentrations obtained by atomic absorption spectrometry (AAS). Good agreement between the TLS results and reported values for Cr(VI) in SRMs as well as AAS results for Cr(VI) in CCA-treated timbers confirmed that TLS is a reliable and accurate analytical technique applicable for the determination of Cr(VI) in aqueous solutions at concentration levels 0.5–100 μg l⁻¹.     

Transport properties of alkyltrimethylammonium bromide surfactants in aqueous solutions

Differential mutual diffusion coefficients of n-alkyltrimethylammonium bromides [CH₃(CH₂)_n–1N(CH₃)₃Br, C_nTAB] (n=10, 12, 14, 16) have been measured in aqueous solutions at 298.15 K using a conductimetric cell and an automatic apparatus to follow diffusion. The cell is based on an open-ended capillary, and the technique follows the diffusion process by measuring the resistance of a solution inside the capillaries at various times. The electrical conductances of those solutions have also been measured to calculate the critical micellar concentration (cmc). Thermodynamic analysis of the data suggests that the free ion concentration decreases at concentrations above the cmc, in agreement with theoretical predictions. The obtained values of the micellization parameters were used to model the mutual diffusion coefficients of C_nTAB aqueous solutions.     

Thermochemical studies of phthalimide and two N-alkylsubstituted phthalimides (ALKYL=ETHYL AND n-PROPYL)

The standard (p⁰=0.1 MPa) molar enthalpies of formation, Δ_fH_m⁰, for crystalline phthalimides: phthalimide, N-ethylphthalimide and N-propylphthalimide were derived from the standard molar enthalpies of combustion, in oxygen, at the temperature 298.15 K, measured by static bomb-combustion calorimetry, as, respectively, – (318.0±1.7), – (350.1±2.7) and – (377.3±2.2) kJ mol^–1. The standard molar enthalpies of sublimation, Δ_cr^gH_m⁰, at T=298.15 K were derived by the Clausius-Clapeyron equation, from the temperature dependence of the vapour pressures for phthalimide, as (106.9±1.2) kJ mol^–1 and from high temperature Calvet microcalorimetry for phthalimide, N-ethylphthalimide and N-propylphthalimide as, respectively, (106.3±1.3), (91.0±1.2) and (98.2±1.4) kJ mol^–1. The derived standard molar enthalpies of formation, in the gaseous state, are analysed in terms of enthalpic increments and interpreted in terms of molecular structure.     

Estimation of precision and efficiency mass transfer steps for the determination of pesticides in vegetables aiming at the expression of results with reliable uncertainty

A 'bottom-up' approach for the expression of results obtained from analytical methods that include analytical steps with recovery inherently different from 100% [mass transfer steps (MTS): extraction, evaporation, clean-up procedures, digestion, etc.] is presented. The estimation of the combination of all MTS uncertainty involves the comparison of the experimental dispersion of replicated analyses of spiked samples with the estimation of the uncertainty obtained for the combination of all uncertainty sources except MTS ones ('incomplete' estimation). The estimation of MTS uncertainty by difference is performed after evaluating the statistical difference between the 'incomplete' estimation and the experimental dispersion (F-test). When the two estimations are statistically equivalent, the MTS uncertainty is considered to be negligible in relation to the other sources budget. The assumption of constancy of MTS performance within the analytical range is tested through single analyses at several concentration levels and is evaluated by the inclusion of the expected values at the intervals resulting from the combination of the MTS uncertainty estimation performed at one concentration level and the 'incomplete' estimation. The developed methodology can also be useful for method optimisation and validation and for the detection of small trends in results. The determination of pesticides in sweet peppers by GC-NPD was used to explore the above concepts.     

Chemometric interpretation of pesticide occurence in soil samples from an intensive horticulture area in north Portugal

An extensive monitoring programme of pesticides was carried out in soil samples from an intensive horticulture area in north of Portugal, putting into practice the needs for increased control of soil quality as far as organic pollution is concerned. The area under investigation was additionally defined as vulnerable to nitrates due to local soil and aquifer characteristics, which might be extended to pesticides contamination. Five sampling sites were selected and soils analysed at three depths in eight sampling campaigns, for the period of 2 years. A stepwise multivariate statistical approach was selected to uncover most relevant patterns inside a complex environmental data matrix. Cluster analysis was applied both to group pesticides and samples, giving a primary and unsupervised overlook of privileged relationships. Clusters of persistent pesticides and selected herbicides were identified, whereas sample classes were also formed and disposed geographically. Thirty eight percent of analysed soils samples fell into one class characterized by low contamination (class 1 in cluster analysis), which is entirely representative of the sampling site no. 1. Afterwards, linear discriminant analysis was applied to identify those pesticides, which had a higher impact in the definition of classes. Finally, factor analysis using a five component model was implemented in order to bring to light the constitution and data variance explained by each of the five main principal components, as well as, their relation to pest management practices. A factor was identified (PC1 – 22% variance) composed of chlorinated pesticides, which was representative of one of the investigated sites indicating its high contamination status. Qualitative main findings and class average concentration values were obtained through this multivariate statistical approach.     

Determination of lead in the urine of exposed and unexposed adults by extraction and flow-injection/atomic absorption spectrometry

Lead is extracted from urine with ammonium pyrrolidien dithiocrbamate into methyl isobutyl ketone, and 20 μl of the extract is injected into a water carrier stream in a flow-injection/atomic absorption system. The procedure is simple, quick, accurate and reproducible. Recoveries are 96–105%. The mean urine lead contents of 20 unexposed and 20 printing-press lead exposed workers was found to be 39.0 ± 8.3 and 71.7 ± 26.3 μg Pb l^?1, respectively.     

A more convenient and general procedure for O-monobenzylation of diols via stannylenes: a critical reevaluation of the Bu2SnO method

A more consistent, straightforward, and economical protocol for generation of stannylene species and their reaction with BnBr leading to products of O-monobenzylation of diols has been set. It has shown to be specially indicated for substrates bearing vicinal trans 1,2-diol moieties on cyclohexane backbones, which are more resistant to these transformations. Such protocol has been successfully applied to myo-inositol derivatives and acyclic diols.     

A new production method for carrier-free201Tl using IEN'S cyclotron in Rio De Janeiro

A new and simplified method was developed for the separation of thallium 201 which will allow the shipment of a “one shot generator” to distant places and easy elution at the destination. Thallium is produced as usually, through the reaction $${}^{nat}Tl/p,xn/^{201} pb\xrightarrow{{\beta ^ + }}{}^{201}Tl$$ with 24-MeV protons from IEN'S CV-28 cyclotron. The separation is based on the properties of a chelating carboxylic acid cation exchange resin column which at pH 4.5 retains lead while thallim is easily eluted. This column can also be used as a regular generator to produced greater quantities of²⁰¹Tl but at the expense of more elutions.     

Synthesis of a Naphthalimide Functionalized Calix[4]arene; A Host Type Fluorophore for Inclusion Compounds in Organic Medium

This article reports the synthesis and the properties of 5,11,17,23-tetra(t-butyl)-25,27-bis-(ethoxy-1,8-naphthalimide)-26,28-hidroxy-calix[4]arene and the formation of an inclusion compound in organic medium. This functionalized calix[4]arene was conceived as the association of a potential host species with a good fluorophore for optical sensoring purposes. Calix[4]-NI as we will call it, maintains its ‘cone-pinched’ configuration and exhibits typical naphthalimide fluorescence bands in non-polar solvents. Its ability to interact with guest species via hydrogen bonding in its endo-hydrophilic cavity to form inclusion compounds was verified with absorption and fluorescence measurements using N-ethanol-1,8-naphthalimide as guest species, which was projected to fit exactly the host cavity and to interact with its naphthalimide π electrons. For this reason, it was possible to follow the formation of the inclusion compound with electronic spectroscopy.