Alberto de Diego

Use of Reflectance Infrared Spectroscopy for Monitoring the Metal Content of the Estuarine Sediments of the Nerbioi-Ibaizabal River (Metropolitan Bilbao, Bay of Biscay, Basque Country)

Multivariate partial least-squares (PLS) calibration models have been developed for the spatial and seasonal simultaneous monitoring of 14 trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V, and Zn) in sediments from 117 samples taken in the estuary of the Nerbioi-Ibaizabal River. Models were based on the chemometric treatment of diffuse reflectance near-infrared (NIR) and attenuated total reflectance (ATR) mid infrared (MIR) spectra, obtained from samples previously lyophilized and sieved with a particle size lower than 63 microm. Vibrational spectra were scanned in both, NIR and MIR regions. Developed PLS models, based on the interaction between trace elements and organic mater provide good screening tools for the prediction of trace elements concentration in sediments.

Risk assessment of trace elements in sediments: The case of the estuary of the Nerbioi–Ibaizabal River (Basque Country)

Long term (January 2005-January 2008) monitoring of sediments was used to investigate metal pollution in the estuary of the Nerbioi-Ibaizabal River (Bilbao, Basque Country). Sediments were collected from eight representative locations of the estuary approximately every three months. The concentration of fourteen elements was measured in sediment extracts. Different graphical representations of the data set, simple statistical methods and sediment quality guidelines were combined to investigate trends in space and time, identify pollution sources, and assess sediment quality from a toxicological point of view. In general terms, the main trend reveals a significant fall in metal concentration over the period investigated. There are still certain points of the estuary with relatively high concentration of toxic metals, but the toxicological approach suggests that the risk for living organisms is not important.

Interferences during mercury speciation determination by volatilization, cryofocusing, gas chromatography and atomic absorption spectroscopy: comparative study between hydride generation and ethylation techniques

The interfering effects of sodium chloride and a mixture of metal ions on the speciation determination of mercury by derivatization (hydride generation or ethylation), preconcentration by cryotrapping, gas chromatographic separation and detection by quartz furnace atomic absorption spectroscopy were investigated. The potential of the masking agent EDTA to overcome the interference was also studied. The experiments were arranged according to a 2n+1 factorial experimental design, so the possibility of synergistic effects among the variables considered was also taken into account. NaCl interferes in the determination of methylmercury (MeHg+) by ethylation, but causes fewer problems in the case of inorganic mercury (Hg2+) or if the analysis is carried out by hydride generation. The presence of metal ions strongly decreases the sensitivity in the determination of both compounds by hydride generation, but has no effect if ethylation is used as the derivatization technique. EDTA only partially eliminates the interfering effect of metals in the determination of MeHg+ by hydride generation. It also avoids decomposition of MeHg+ to Hg0 , promoted by NaCl, after derivatization of the compounds by hydride generation. The results obtained are discussed in terms of a comparison between the two derivatization techniques used, i.e., hydride generation and ethylation. Potential chemical pathways and reaction mechanisms for the observed interferences are also given.

Fate of hazardous elements in agricultural soils surrounding a coal power plant complex from Santa Catarina (Brazil)

Hazard element contamination coming from coal power plants is something obvious, but when this contamination is accompanied by other contamination sources, such as, urban, coal mining and farming activities the study gets complicated. This is the case of an area comprised in the southern part of Santa Catarina state (Brazil) with the largest private power plant generator. After the elemental analysis of 41 agricultural soils collected in an extensive area around the thermoelectric (from 0 to 47 km), the high presence of As, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sb, Sn, Tl, V and Zn was found in some specific areas around the power plant. Nevertheless, as the NWAC (Normalized-and-Weighted Average Concentration) confirmed, only soils from one site were classified as of very high concern due to the presence of potential toxic elements. This site was located within the sedimentation basin of the power plant. The spatial distribution obtained by kriging in combination with the analysis of the data by Principal Component Analysis (PCA) revealed three important hotspots in the area according to soil uses and geographic localization: the thermoelectric, its area of influence due to volatile compound deposition, and the area comprised between two urban areas. Farming practice turn out to be an important factor too for the quantity of hazard element stored in soils.

Ultrasound energy focused in a glass probe: an approach to the simultaneous and fast extraction of trace elements from sediments.

The 3051 USEPA method (or alternatively, the 3051A) can be considered nowadays as a reference method to extract metals from sediments. However, after microwave heating, the sample must be allowed to cool down, which results in a considerable lengthening of the whole analytical process. Microwave ovens and their maintenance are, in addition, expensive, and its use is relatively dangerous. The use of ultrasound focused energy to assist the extraction of chemicals from solid samples is a safe and relatively cheap technique. In this work we propose a new method to extract simultaneously several elements from sediments using ultrasound energy focused in a glass probe to accelerate the process, and check its possibilities to become an alternative to the EPA3051(A) approach. The optimised procedure allows extracting 13 elements in only 6 min, with similar recoveries and, in general, better repetitivities than the EPA3051. In addition, the suspension is only slightly heated during the leaching process.

Application of the electrical conductivity of concentrated electrolyte solutions to industrial process control and design: from experimental measurement towards prediction through modelling

Different aspects of the conductivity of concentrated electrolyte solutions and their application to design and control of chemical processes are discussed and reviewed, with particular focus on the work of our research group during the last few years. An automated system based on the electrodeless conductivity technique for the measurement of the electrical conductivity of solutions as the basis of a titration strategy is described. The inadequacy of classical calibration methods when high conductivities are to be measured is highlighted and an alternative methodology is proposed. Our measurements on specific concentrated systems of interest in industrial applications and the development of general methodologies to treat experimental conductivity data at constant or varying temperature in order to get comprehensive inter- and extrapolation mathematical models are summarised. Theoretical approaches to explain the variability of conductivity data of electrolyte solutions with the solute concentration as well as the deviations from ideality found at higher concentrations are reviewed and critically evaluated. Solutions of mixed electrolytes are treated in a similar fashion.

The mobilization of hazardous elements after a tropical storm event in a polluted estuary.

The Tubarão River (Santa Catarina, Brazil) is affected by hazardous elements (HEs) pollution from abandoned coal mines, agricultural activities, urban discharges, industrial and leisure zones, etc. In order to study the distribution and sources of HEs contamination in a polluted estuary after a tropical storm, waters and surface sediments were collected from 15 sampling sites along the Tubarão River. The concentration of 24 elements (Ag, Al, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ti, Tl, V, W, and Zn) were measured by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the mineralogical composition of the sediments by Raman spectroscopy and X-ray diffraction (XRD). The metal concentrations in water and sediment showed wide spatial variation due to the variability in water discharges and anthropogenic inputs after a storm. In general, higher metal concentration in water and lower in sediments were found upstream (closer to coal mining). Downstream sampling sites and the Oratorio River sampling site (one of the eight tributaries of the estuary) showed the highest values in sediment samples. Normalized and Weighed Average Concentrations (NWAC) were calculated, which allow us to identify, in a very simple way, the sampling sites of higher concern (hotspots of contamination) in the studied area. NWAC suggested that the strong rainfall events could affect to the metal distribution in sediments. The results of this study were compared with a previous study in the same area during dry season by Principal Component Analysis (PCA), showing changes in environmental pollution of the sediment after a strong storm event.

Methodology to assess the mobility of trace elements between water and contaminated estuarine sediments as a function of the site physico-chemical characteristics

This work presents an innovative methodology to have a rapid diagnosis about the mobility of selected trace elements of known toxicity and biological risk (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sn and Zn) present in contaminated sediments. The novel strategy presented in this work uses, therefore, the own estuarine water in contact with sediments as the extracting agent to perform the mobility tests, simulating the real situation of the estuary. This water suffers from different physico-chemical conditions (low and high tides) and gives consequently, rather better information than the one obtained by the routine sequential extraction procedures. The final step of this methodology was the use of spatial modelling by kriging method and multivariate chemometric analysis, both for a better interpretation of the results. To achieve this goal, sediment and water samples were strategically collected at eight different points (four in tributary rivers, one in a closed dock, two in the main channel and another one in the mouth) along the Nerbioi-Ibaizabal River estuary (Metropolitan Bilbao, Basque Country) approximately every three months (summer, autumn, winter and spring) during a whole year. Physico-chemical changes, such as pH, carbonate content and organic matter of the sediments, together with variations in water salinity appear to be responsible for metal mobility from the sediment to the water layer. The influence of these variables was higher in the sites located close to the sea. Moreover, the mobility of trace elements was even higher at high tide in sediments with lower metal content.

Use of portable devices and confocal Raman spectrometers at different wavelength to obtain the spectral information of the main organic components in tomato (Solanum lycopersicum) fruits

Tomato (Solanum lycopersicum) fruit samples, in two ripening stages, ripe (red) and unripe (green), collected from a cultivar in the North of Spain (Barrika, Basque Country), were analyzed directly, without any sample pretreatment, with two different Raman instruments (portable spectrometer coupled to a micro-videocamera and a confocal Raman microscope), using two different laser excitation wavelengths (514 and 785 nm, only for the confocal microscope). The combined use of these laser excitation wavelengths allows obtaining, in a short period of time, the maximum spectral information about the main organic compounds present in this fruit. The major identified components of unripe tomatoes were cutin and cuticular waxes. On the other hand, the main components on ripe tomatoes were carotenes, polyphenoles and polysaccharides. Among the carotenes, it was possible to distinguish the presence of lycopene from β-carotene with the help of both excitation wavelengths, but specially using the 514 nm one, which revealed specific overtones and combination tones of this type of carotene.

Partial least squares X-ray fluorescence determination of trace elements in sediments from the estuary of Nerbioi-Ibaizabal River.

The feasibility of partial least squares (PLS) regression modeling of X-ray fluorescence (XRF) spectra of estuarine sediments has been evaluated as a tool for rapid trace element content monitoring. Multivariate PLS calibration models were developed to predict the concentration of Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V and Zn in sediments collected from different locations across the estuary of the Nerbioi-Ibaizabal River (Metropolitan Bilbao, Bay of Biscay, Basque Country). The study was carried out on a set of 116 sediment samples, previously lyophilized and sieved with a particle size lower than 63 microm. Sample reference data were obtained by inductively coupled plasma mass spectrometry. 34 samples were selected for building PLS models through a hierarchical cluster analysis. The remaining 82 samples were used as a test set to validate the models. Results obtained in the present study involved relative root mean square errors of prediction varying from 21%, for the determination of Pb at hundreds microg g(-1) level, up to 87%, for Ni determination at little tens microg g(-1) level. An average prediction error of +/-37% for the 14 elements under study was obtained, being in all cases mean differences between predicted and reference results of the same order than the standard deviation of three replicates from a same sample. Residual predictive deviation values obtained ranged from 1.1 to 3.9.