Modelling spatial and temporal variations in the water quality of an artificial water reservoir in the semiarid midwest of Argentina

Temporal and spatial patterns of water quality of an important artificial water reservoir located in the semiarid Midwest of Argentina were investigated using chemometric techniques. Surface water samples were collected at 38 points of the water reservoir during eleven sampling campaigns between October 1998 and June 2000, covering the warm wet season and the cold dry season, and analyzed for dissolved oxygen (DO), conductivity, pH, ammonium, nitrate, nitrite, total dissolved solids (TDS), alkalinity, hardness, bicarbonate, chloride, sulfate, calcium, magnesium, fluoride, sodium, potassium, iron, aluminum, silica, phosphate, sulfide, arsenic, chromium, lead, cadmium, chemical oxygen demand (COD), biochemical oxygen demand (BOD), viable aerobic bacteria (VAB) and total coliform bacteria (TC). Concentrations of lead, ammonium, nitrite and coliforms were higher than the maximum allowable limits for drinking water in a large proportion of the water samples. To obtain a general representation of the spatial and temporal trends of the water quality parameters at the reservoir, the three-dimensional dataset (sampling sites×parameters×sampling campaigns) has been analyzed by matrix augmentation principal component analysis (MA-PCA) and N-way principal component analysis (N-PCA) using Tucker3 and PARAFAC (Parallel Factor Analysis) models. MA-PCA produced a component accounting for the general behavior of parameters associated with organic pollution. The Tucker3 models were not appropriate for modelling the water quality dataset. The two-factor PARAFAC model provided the best picture to understand the spatial and temporal variation of the water quality parameters of the reservoir. The first PARAFAC factor contains useful information regarding the relation of organic pollution with seasonality, whereas the second factor also encloses information concerning lead pollution. The most polluted areas in the reservoir and the polluting sources were identified by plotting PARAFAC loadings as a function of the UTM (Universal Transverse Mercator) coordinates.     

A Dynamic Nuclear Polarization spectrometer at 95 GHz/144 MHz with EPR and NMR excitation and detection capabilities

A spectrometer specifically designed for systematic studies of the spin dynamics underlying Dynamic Nuclear Polarization (DNP) in solids at low temperatures is described. The spectrometer functions as a fully operational NMR spectrometer (144 MHz) and pulse EPR spectrometer (95 GHz) with a microwave (MW) power of up to 300 mW at the sample position, generating a MW B(1) field as high as 800 KHz. The combined NMR/EPR probe comprises of an open-structure horn-reflector configuration that functions as a low Q EPR cavity and an RF coil that can accommodate a 30-50 μl sample tube. The performance of the spectrometer is demonstrated through some basic pulsed EPR experiments, such as echo-detected EPR, saturation recovery and nutation measurements, that enable quantification of the actual intensity of MW irradiation at the position of the sample. In addition, DNP enhanced NMR signals of samples containing TEMPO and trityl are followed as a function of the MW frequency. Buildup curves of the nuclear polarization are recorded as a function of the microwave irradiation time period at different temperatures and for different MW powers.     

Tetrathiafulvalene‐Based Mixed‐Valence Acceptor–Donor–Acceptor Triads: A Joint Theoretical and Experimental Approach

This work presents a joint theoretical and experimental characterisation of the structural and electronic properties of two tetrathiafulvalene (TTF)‐based acceptor–donor–acceptor triads (BQ–TTF–BQ and BTCNQ–TTF—BTCNQ; BQ is naphthoquinone and BTCNQ is benzotetracyano‐p‐quinodimethane) in their neutral and reduced states. The study is performed with the use of electrochemical, electron paramagnetic resonance (EPR), and UV/Vis/NIR spectroelectrochemical techniques guided by quantum‐chemical calculations. Emphasis is placed on the mixed‐valence properties of both triads in their radical anion states. The electrochemical and EPR results reveal that both BQ–TTF–BQ and BTCNQ–TTF–BTCNQ triads in their radical anion states behave as class‐II mixed‐valence compounds with significant electronic communication between the acceptor moieties. Density functional theory calculations (BLYP35/cc‐pVTZ), taking into account the solvent effects, predict charge‐localised species (BQ ^{. ?}–TTF–BQ and BTCNQ ^{. ?}–TTF–BTCNQ) as the most stable structures for the radical anion states of both triads. A stronger localisation is found both experimentally and theoretically for the BTCNQ–TTF–BTCNQ anion, in accordance with the more electron‐withdrawing character of the BTCNQ acceptor. CASSCF/CASPT2 calculations suggest that the low‐energy, broad absorption bands observed experimentally for the BQ–TTF–BQ and BTCNQ–TTF–BTCNQ radical anions are associated with the intervalence charge transfer (IV‐CT) electronic transition and two nearby donor‐to‐acceptor CT excitations. The study highlights the molecular efficiency of the electron‐donor TTF unit as a molecular wire connecting two acceptor redox centres.     

Electrochemical detection of phenolic estrogenic compounds at carbon nanotube-modified electrodes

The use of a carbon nanotube-modified glassy carbon electrode (CNT-GCE) for the LC-EC detection of phenolic compounds with estrogenic activity is reported. Cyclic voltammograms for phenolic endocrine disruptors and estrogenic hormones showed, in general, an enhancement of their electrochemical oxidation responses at CNT-GCE attributable to the electrocatalytic effect caused by CNTs. Hydrodynamic voltammograms obtained under flow injection conditions lead to the selection of +700 mV as the potential value to be applied for the amperometric detection of the phenolic estrogenic compounds, this value being remarkably less positive than those reported in the literature using other electrode materials. Successive injections of these compounds demonstrated that no electrode surface fouling occurred. A mobile phase consisting of a 50:50 (v/v) acetonitrile:0.05 mol l⁻¹ phosphate buffer of pH 7.0 was selected for the chromatographic separation of mixtures of these compounds, with detection limits ranging between 98 and 340 nmol l⁻¹. Good recoveries were obtained in the analysis of underground well water and tap water samples spiked with some phenolic estrogenic compounds at a 14 nmol l⁻¹ concentration level.     

Competitive sorption and desorption of heavy metals in mine soils: influence of mine soil characteristics

Many mine soils are chemically, physically, and biologically unstable and deficient. They are sometimes amended with sewage sludge and ashes but often contain heavy metals that increase the already high mine soils' heavy metal contents. Cd, Cr, Cu, Ni, Pb, and Zn in mutual competition were added to five mine soils (Galicia, Spain). Soil capacities for heavy metal sorption and retention were determined by means of distribution coefficients and selectivity sequences among metals. Influence of soil characteristics on sorption and retention was also examined. Retention selectivity sequences indicate that, in most of the soils, Pb is the preferred retained metal, followed by Cr. The last metals in these sequences are Ni, Cd, and Zn. Soil organic matter content plays a fundamental role in control of Pb sorption. Gibbsite, goethite, and mica influence Cr retention. Soil organic matter, oxides, and chlorite contents are correlated with K(d sigma sp medium). Heavy metals are weakly adsorbed by soils and then desorbed in high amounts. To recover these soils it is necessary to avoid the use of residues or ashes that contain heavy metals due to their low heavy metal retention capacity.     

Liquid–liquid equilibrium of (1H,1H,7H-perfluoroheptan-1-ol + perfluoroalkane) binary mixtures

This work presents new liquid–liquid equilibrium data for mixtures of 1H,1H,7H-perfluoroheptan-1-ol and linear perfluoroalkanes from C₆ to C₉. Data were measured at atmospheric pressure by turbidimetry and at pressures up to 5 MPa using a laser light scattering technique. The coexistence curves have been fitted to renormalization group extended-scaling expressions with the critical temperature and molar fraction obtained from the fit.     

Copper(II) complexes with new polypodal ligands presenting axial-equatorial phenoxo bridges {2-[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenol, 2-[(bis(2-pyridylmethyl)amino)methyl]-4-methyl-6-(methylthio)phenol}: examples of ferromagnetically coupled bi- and trinuclear copper(II) complexes

Two new ligands, 2-[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenol (HL) and 2-[(bis(2-pyridylmethyl)amino)methyl]-4-methyl-6-(methylthio)phenol (HSL), were synthesized and were used to prepare the trinuclear copper(II) complex {[CuSL(Cl)]2Cu}(PF6)2.H2O (1) and the corresponding binuclear complexes [Cu2(SL)2](PF6)2 (2) and [Cu2L2](PF6)2 (3). The crystal structure of 1 shows two different coordination environments: two square base pyramidal centers (Cu1 and Cu1a, related by a C2 axes), acting as ligands of a distorted square planar copper center (Cu2) by means of the sulfur atom of the SCH3 substituent and the bridging phenoxo oxygen atom of the ligand (Cu2-S = 2.294 A). Compounds 2 and 3 show two equivalent distorted square base pyramidal copper(II) centers, bridged in an axial-equatorial fashion by two phenoxo groups, thus defining an asymmetric Cu2O2 core. A long copper-sulfur distance measured in 2 (2.9261(18) A) suggests a weak bonding interaction. This interaction induces a torsion angle between the methylthio group and the phenoxo plane resulting in a dihedral angle of 41.4(5) degrees. A still larger distortion is observed in 1 with a dihedral angle of 74.0(6) degrees. DFT calculations for 1 gave a ferromagnetic exchange between first neighbors interaction, the calculated J value for this interaction being +11.7 cm-1. In addition, an antiferromagnetic exchange for 1 was obtained for the second neighbor interaction with a J value of -0.05 cm-1. The Bleaney-Bowers equation was used to fit the experimental magnetic susceptibility data for 2 and 3; the best fit was obtained with J values of +3.4 and -16.7 cm-1, respectively. DFT calculations for 2 and 3 confirm the nature and the values of the J constants obtained by the fit of the experimental data. ESR and magnetic studies on the reported compounds show a weak exchange interaction between the copper(II) centers. The low values obtained for the coupling constants can be explained in terms of a poor overlap between the magnetic orbitals, due to the axial-equatorial phenoxo bridging mode observed in these complexes.     

Hamiltonian theory for vibrational line shapes of atoms adsorbed on surfaces

The vibrational motions of atomic adsorbates on surfaces can be probed by helium atom scattering. The experimental observable is the dynamic structure factor, which shows an inelastic peak around the vibrational frequency of the isolated adsorbates known as the frustrated translational or T-mode peak. In this paper we develop a theory for the line shape of this peak, as well as for its temperature-dependent shift and broadening, based on a Hamiltonian equivalent of the generalized Langevin equation. The theory can be used to infer physical parameters of the adatom-surface interaction, such as the friction coefficient, the barrier height to diffusion, and the anharmonicity parameter. Numerical simulations are used to ascertain the range of validity of the theory, which is also generalized to describe multidimensional systems and to include quantum corrections. We compare the theoretical predictions for the shift and broadening with experimental results for the Na/Cu(001) system, showing quantitative agreement within experimental resolution.