E. Barrado

TEMPORAL EVOLUTION OF GROUNDWATER COMPOSITION IN AN ALLUVIAL AQUIFER (PISUERGA RIVER, SPAIN) BY PRINCIPAL COMPONENT ANALYSIS

Abstract A set of quantitative analytical data from the alluvial aquifer of the Pisuerga river, located at the north-east of Valladolid (Spain), has been processed by multivariate statistical techniques in order to investigate the evolution of the groundwater composition between two surveys. The original matrix consisted of 16 physico-chemical variables, determined in 32 groundwater samples collected in 32 sampling sites of the aquifer. The surveys were carried out in October 1994, at the end of the irrigation and low water period just before autumn rains, and in April–May 1995 at the beginning of the irrigation and high water period and after the recharge of aquifer. The experimental 64×16 matrix was analysed by Principal Component Analysis (PCA), and the resulting Principal Components (PCs) and Varimax rotated PCs (VFs) analysed by means of box and bivariate plots. The exploration of the correlation matrix allowed to uncover strong associations between some variables (sulphate, chloride, hydrogencarbonate, sodium, potassium, magnesium, calcium and electrical conductivity) as well as a lack of association between the others (pH, nitrate, and trace metals). PCA showed the existence of up to five significant PCs which account for 71.39% of the variance. Two of them can be initially assigned to ‘mineralization’ whereas the other PCs are built from variables indicative of pollution. Box and bivariate plots of the two first PCs showed that ‘mineralization’ is maintained through surveys and that trace elements increase from the first to the second survey in all zones, as a possible consequence of soil leaching caused by the rise of the groundwater level. Varimax rotation allowed to ‘break up’ the ‘mineralization’ PC into two VFs, assigned respectively to ‘natural’ mineralization and to ‘saline’ man-made contamination (sodium and chloride). Box and bivariate plots of VFs confirmed the existence of a differential ‘natural’ mineralization pattern, now ascribed exclusively to dissolution of geological materials, as well as the presence of a zone with unusually high levels of ‘saline’ contamination attributed to leakages from sanitary systems. The plot of VFs also allowed to visualise seasonal variations, identifying a process of dilution of the ‘natural’ mineralization during the recharge of the aquifer, and an increase of the ‘saline’ contamination, assigned to a variety of non-natural causes.

Magnetic solids in analytical chemistry: A review

Magnetic solids are widely used in detection and analytical systems because of the performance advantages they offer compared to similar solids that lack magnetic properties. These solids can be used to pre-concentrate analytes and for the magnetic separation and molecular identification of biomolecules, and organic and inorganic species. Magnetic solid separation techniques also offer benefits over centrifugation, filtration, and solid-phase extraction. In this review, we describe the synthesis, characterization and applications of a series of solids including silica supports, carbon nanotubes, alumina, organic polymers and other materials, mostly containing magnetite or paramagnetic metals. Also addressed are the future perspectives of magnetic solid applications.

Determination and speciation of heavy metals in sediments of the Pisuerga river

Abstract We have analysed the contents and speciation of Zn, Cd, Pb, Cu, Ni and Co in sediments taken in the Pisuerga river, that flows through the town of Valladolid and is polluted by industrial and municipal effluents. All heavy metals were determined by voltammetric methods, and their mean total contents were (in μgg−1): Zn, 245.49; Cd, 1.05; Pb, 18.77; Cu, 66.53; Ni, 46.51; and Co, 11.41. We also determined the % H2O, % loss at 800°C, % CaCO3, % organic matter and % organic N for each sediment. All the data were examinated by principal components analysis in order to explain the behaviour of each metal and sampling point. The speciation was carried out by Tessiers method to find five metal categories: (a) adsorptive and exchangeable, (b) bound to carbonates, (c) bound to reducible phases, (d) bound to organic matter and sulphides and (e) residual metals. Cd and Pb, and to a lesser degree Zn, appeared in fractions (a), (b) and (c), whereas Cu, Ni and Co were mainly found in fractions (c) and (d). The residual metal fractions, taken as a guide for pollution, were found to be similar to the ones obtained in rivers belonging to our same European zone.

Magnetic solid phase extraction based on phenyl silica adsorbent for the determination of tetracyclines in milk samples by capillary electrophoresis

A magnetic solid phase extraction method coupled to capillary electrophoresis is proposed for the determination of tetracycline, oxytetracycline, chlortetracycline and doxycycline in milk samples. Five different magnetic phenyl silica adsorbents covered with magnetite were synthesized by varying the molar ratio of phenyltrimethylsilane and tetramethylorthosilicate; these adsorbents were evaluated in terms of their pH and degree of hydrophobicity for tetracycline retention. The optimal, selected combination of conditions was a pH of 10.0 and a magnetic sorbent ratio of 4:1; under these conditions, the retention capacity ranged from 99.7% to 101.2% for the four tetracyclines analyzed. The elution conditions and initial sample volume of the proposed extraction method were also optimized, and the best results were obtained with 1×10(-3) M acetic acid in methanol as eluent and a 200 ml of sample volume. Under optimal conditions, average recoveries ranged from 94.2% to 99.8% and the limits of detection ranged from 2 to 9 μg l(-1) for the four tetracyclines. After the proposed method was optimized and validated, 25 milk samples of different brands were analyzed, oxytetracycline residues were detected in five samples, in concentrations ranging from 98 to 213 μg l(-1). Subsequent analysis of positive samples by SPE-CE and magnetic solid phase extraction-HPLC revealed than no significant differences were found from results obtained by the proposed methodology. Thus, the developed magnetic extraction is a robust pre-concentration technique that can be coupled to other analytical methods for the quantitative determination of tetracyclines.

Voltammetric determination of food colorants using a polyallylamine modified tubular electrode in a multicommutated flow system

This work describes the construction of a polyallylamine modified tubular glassy carbon electrode and its application in the electroreduction of food azo colorants (tartrazine, sunset yellow and allura red) by square wave voltammetry. The electrode modification prevented the surface fouling and, simultaneously, enhanced the analytical signal intensity. The developed unit was coupled to a multicommutated flow system which, given the complexity of samples, was designed to allow the implementation of the standard additions method in an automatic way, using only one standard solution. The described method presented a linear range up to about 2.0x10(-4)moll(-1) for the referred colorants, with a detection limit of 1.8x10(-6)moll(-1) for tartrazine, 3.5x10(-6)moll(-1) for sunset yellow and 1.4x10(-6)moll(-1) for allura red. The method was applied in the analysis of these colorants in several food samples, and no statistically significant difference between the results obtained by the proposed and the comparative method (HPLC) was found, at a 95% confidence level. Repeatability in the analysis of samples (expressed in R.S.D.) was about 3% (n=10).

Determination of non-steroidal anti-inflammatory drugs in wastewaters by magnetic matrix solid phase dispersion–HPLC

A series of supports functionalized with different alkyl chains and covered with magnetite were synthesized, characterized and applied in the sample pre-concentration of four non-steroidal anti-inflammatory drugs (acetaminophen, naproxen, diclofenac and ibuprofen) contained in wastewater samples. The general methodology involved magnetic solid phase dispersion followed by the analysis by high-performance liquid chromatography with ultraviolet detection. The magnetic supports were initially dispersed in the samples with the aid of Triton X-100, then supports were magnetically isolated and the analytes were eluted with methanol. Finally the extract was injected into the HPLC system. The highest recovery percentage (>90%) was obtained with the support containing octyl chains (C8) at pH 3. The lowest limits of detection achieved ranged within 1-2microgL(-1) with repeatability (expressed as RSD) below 5% in all cases. The method was applied in the analysis of wastewater samples.

Trace elements in human milk: Correlation with blood levels, inter-element correlations and changes in concentration during the first month of lactation

Using inductively coupled plasma mass spectrometry (ICP-MS) based analytical procedures, the concentration of several trace elements (Mn, As, Pb, Co, Ni, Cu, Zn and Se) was determined in human milk samples collected from a group of healthy lactating Portuguese women (n=44), both on the 2nd day postpartum (i.e., colostrum; n=34) and at 1 month postpartum (i.e., mature milk; n=19). Blood samples (n=44), collected on the 2nd day after parturition, were also analyzed for the same trace elements. No major correlations were observed between the levels of the analyzed trace elements in blood and colostrum samples. All the studied elements, except for Co, Pb and Ni, showed a significant trend for a decrease in concentration in milk during the first month of lactation. This trend was more pronounced for Zn and Se, whose levels decreased to approximately 23% and 44% of their initial mean concentration, respectively. With the exception of Co (r=0.607) and Zn (r=0.487), no significant correlations were observed when comparing the levels of each trace element between samples of colostrum and mature milk. Several inter-element correlations were found within each type of milk sample. The most significant were: (i) Se vs Cu (r=0.828) and Se vs Co (r=0.605) in colostrum samples and (ii) Ni vs Pb (r=0.756), Ni vs Mn (r=0.743) and Se vs Co (r=0.714) in mature milk samples. An inverse correlation between Zn and Se was also found in both types of milk sample; however, it only reached statistical significance for mature milk (r=-0.624).

A Case of Hydrochemical Characterization of an Alluvial Aquifer Influenced by Human Activities

Abstract21 physico-chemical parameters have been determined in 47 groundwater samples collected in October 1994 from the alluvial aquifer of the Pisuerga river, located at the north-east of Valladolid (north-western Spain). Conventional hydrochemical methods and multivariate statistical analysis have been used to discriminate natural phenomena and pollution processes in the area. It has been demonstrated the existence of a heterogeneity in groundwater mineral contents related to anthropic actions such as irrigation, source of irrigation water and location of polluting sources. This study demonstrates the existence of two sub-units in the alluvial aquifer (left and right river banks) with different hydrochemical characteristics, and identifies three different singular areas in the left bank. Groundwater from this bank showed higher levels of dissolved ions caused by concentration processes derived from the predominant use of groundwater for crop irrigation, whilst in the right bank of the aquifer less saline water from canals is used. Degradation of groundwater quality has been observed in some areas of the left aquifer sub-unit (north, Santovenia and south-central sites) where anomalous high concentrations of sulphate, sodium, chloride and nitrate were measured, and can be related to the presence of potentially polluting sources such as leachates from industrial waste disposals, sewage effluents and use of organic and inorganic fertilizers.

Characterisation of solid residues obtained on removal of Cr from waste water

Abstract This investigation was designed to characterise the solid residues obtained when waste water heavily contaminated with Cr 3+ is purified by the ‘ferrite precipitation method’ and to evaluate the efficiency of the process using different starting Fe 2+ /Cr 3+ ratios. In the case of Cr(VI) contamination, to avoid altering the proportions, the Cr 6+ was reduced to Cr 3+ in a preliminary step, and the same procedure applied. The solid compounds obtained were subjected to X-ray fluorescence and chemical analysis (inductively coupled plasma and potentiometric titrations). Findings suggest Cr x Fe 2+ Fe 3+ 2− x O 4 as the most probable stoichiometry of the products, where 0.09≤ x ≤0.59. X-ray diffractometry, differential scanning calorimetry and Fourier transform infrared patterns indicated a ‘normal spinel’ structure corresponding to ‘chromite-type’ chromium iron oxides. This structure differs considerably from that of divalent metal-bearing ferrites (‘inverse spinel’) and constitutes a new hydrothermal pathway for the generation of ‘non-stoichiometric chromites’. The following is proposed as the general oxide formation reaction: a Fe 2+ + x Cr 3+ + b OH − + c O 2 →Cr x Fe 3− x O 4 +Fe 2 O 3 . n H 2 O

Study of the Contents and Speciation of Heavy Metals in River sediments By Factor Analysis

Abstract Heavy metals Zn, Cd, Pb, Cu, Ni and Co from two spanish river sediments have been determined by voltammetric techniques, along with % CaCO3 and % organic matter, and the whole data set examined by means of Factor Analysis, finding a different behaviour of the metals in each river. Heavy metal speciation in the sediments was carried out by using the Tessiers scheme: Zn and Pb were mainly associated to ‘reducible phases’, Cd and Cu bound to ‘organic matter and sulphides’, and Ni and Co were distributed between the above fractions. The ‘residual’ metals were used as pollution indicators from the rivers, finding a similar behaviour to other industrialized river systems.