Juan C. Raposo

MultiSimplex optimisation of the solid-phase microextraction-gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and phthalates from water samples

Solid-phase microextraction coupled to GC-MS was optimised for the determination of polycyclic aromatic hydrocarbons (PAHs), phthalate esters and polychlorinated biphenyls (PCBs) in water samples. A 30-microm polydimethylsiloxane fiber was immersed in a 30-ml water sample that contained the analytes of interest (PAHs, PCBs and phthalate esters) and the variables studied were extraction time (15-60 min), extraction temperature (30-90 degrees C), desorption time (1-5 min), desorption temperature (220-270 degrees C) and the addition of sodium chloride (0-9 g). The MultiSimplex programme based on the simplex algorithm was used to establish the optimal conditions. MultiSimplex allowed the simultaneous study of the variables mentioned above and considered the answers of all types of compounds studied in this work. Thus, the optimal conditions obtained allowed the simultaneous determination of PAHs, phthalate esters and PCBs. Furthermore, the accuracy and repeatability of the developed method were calculated from water samples spiked at known concentrations of the analytes. Finally, the optimised method was used to analyse water samples from different sampling points of the Urdaibai and Nerbioi-Ibaizabal estuaries (Biscay, Spain).

Development of a Modified Bromley's Methodology for the estimation of ionic media effects on solution equilibria: Part 3. Application to the construction of thermodynamic models

Abstract The development of the Modified Bromleys Methodology (MBM) is extended for the estimation of the activity coefficients of individual species in aqueous solution at 25°C in single and mixed ionic media. The estimation is compared with literature data of activity coefficients of mixtures of electrolytes in water and applied to (a) the prediction of the ionic product of water in aqueous solutions containing different salts which are commonly used as background electrolytes (NaCl, KNO3 and NaClO4) and (b) the equilibrium constants of the Cr(VI)–H2O system.

The thermodynamic model of inorganic arsenic species in aqueous solutions Potentiometric study of the hydrolitic equilibrium of arsenic acid.

Protonation constants of arsenic acid were determined at different ionic strengths in NaClO(4) (0.1, 0.5, 1.0, 3.0 mol dm(-3)), NaCl (0.5 and 1.0 mol dm(-3)) and KCl (0.5, 1.0 and 3.0 mol dm(-3)) ionic media by means of a potentiometric study. The distribution of arsenate species was defined depending on two important variables in natural environments: pH and composition. All the experimentation was performed at 25 degrees C. The differences found in the protonation constants for different medium compositions, were explained by the different behaviour of the interaction parameters of the species considered in the different media and ionic strengths. These parameters were reported for all hydrolitic As(V) species and were calculated using the Modified Bromleys Methodology (MBM). The corresponding thermodynamic stepwise formation constants were also determined (log degrees K(1)=11.58+/-0.01, log degrees K(2)=7.06+/-0.01, log degrees K(3)=2.25+/-0.01). All the results obtained showed not only the importance of the ionic strength but also of the composition of the ionic medium on the distribution of the acid-base species of As(V) as a function of pH in natural waters.

Optimisation of flow-injection-hydride generation inductively coupled plasma spectrometric determination of selenium in electrolytic manganese.

Flow-injection-hydride generation procedure for Se in electrolytic manganese was optimized by means of the experimental design approach. Instrumental variables like power supplied (P), sample (F) and argon (G) flow rates together with chemical variables like NaBH(4) and HCl concentrations were studied. In case of the chemical variables, it was concluded that sodium tetrahydridoborate concentrations higher than 1.0% extinguished the plasma while HCl concentration should always be higher than 0.6moldm(-3). The analysis of effects suggested that all the instrumental variables are significant factors, and the optimum conditions were P=1550W, F=4.75mLmin(-1) and G=0.6mLmin(-1). The influence of Mn was specially studied and it was concluded that the interferences were negligible if Mn is below 2.0gL(-1). In the same sense, the interferences of antimony(III), arsenic(V) and mercury(II) were also considered negligible. Finally, a detection limit of 0.0005% (w/w) was obtained (a repeatability R.S.D. <2.0% for all Se concentrations tried). Some manganese samples were also spiked with different concentrations of Se(IV) and the results demonstrated to be in good statistical agreement with expected values.

Preparation of a reference mussel tissue material for polycyclic aromatic hydrocarbons and trace metals determination

Due to high cost of certified reference materials (CRMs), reference materials (RMs) are preferred to check the method performance in environmental analysis. In this work, a laboratory reference material (LRM) was prepared and characterised to carry out the quality control in monitoring analysis of eight polycyclic aromatic hydrocarbons (PAHs) and nine trace metals in mussel tissue. Mussels were collected in a naturally polluted area. Before the reference material was bottled, the mussel tissue was stabilised by freeze-drying, ground and sieved. For the material characterisation, several statistical tests were applied to check the homogeneity of the analytes in the tissue, and a stability test was performed to study the effect of the storage temperature in the analyte concentration. Other characteristics such as specific density, moisture and lipid contents as well as particle size distribution of the material were determined. Although the LRM had a homogeneous distribution for all PAHs and almost all metals, the stability study showed different results at both storage temperatures studied. For both PAHs and trace metals, the material was suitable to assure the quality control of the analysis.

Validation of chemical speciation model of inorganic arsenic in river waters with mobilisation processes

Abstract The thermodynamic model of inorganic arsenic (acid–base, complexation, precipitation and redox equilibria) was validated with results obtained in arsenic mobilisation processes taking place in several river sediment samples of the Basque Country (North of Spain). Natural waters in contact with the sediment were collected at each sampling point, together with the sediment samples. These waters were analysed and then used as the extractant in the mobilisation studies. Considering pH, redox potential and total concentration values of the main cations and anions, the stoichiometric equilibrium constant were computed for each river water situation. The activity coefficient values of the inorganic arsenic species were estimated by means of the Modified Bromley Methodology (MBM). Both water and sediment for each sampling site were used in the mobility experiments, and the results were compared with the theoretical predictions of the thermodynamic model extrapolated to the chemical conditions of the sampling point. Moreover, a correlation analysis was also performed taking into account all the data and sampling sites; these results were also discussed and compared with the theoretical speciation obtained from the basic model of inorganic arsenic.

Validation of total inorganic element determination in wastewater samples by on-line isotope dilution inductively coupled plasma mass spectrometry

Current interest in analytical chemistry concerns the traceability of analytical measurements to the International System of Units (SI) and estimation of their uncertainties. Primary methods of measurement achieve traceability directly without intermediate reference standards or materials and without significant empirical correction factors. In this work, isotope dilution mass spectrometry was regarded as such a primary method and wastewater as a matrix of significant ecological and toxicological relevance. In that sense, a validation study was performed for total (dissolved + particulate) element determination (Cd, Cr, Fe, Ni, Pb and Zn) in acidified (pH < 2) wastewater samples by using on-line isotope dilution mass spectrometry with inductively coupled plasma (OID-ICP-MS) after acid extraction in a microwave system. Emphasis was placed on the OID-ICP-MS method and its validation by comparison against direct external calibration mass spectrometry with inductively coupled plasma analysis (ICP-MS), including differences in calibration strategies. Good agreement (trueness) between the two analysis methods was achieved for all trace metals involved. However, OID-ICP-MS offers more accurate and precise results with smaller measurement uncertainties, when properly applied, compared to external calibration. Thus, OID-ICP-MS proved to be an ideal solution for routine wastewater analysis, increasing the sample throughput without any previous sample handling and improving the quality and reliability of the analytical results.