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1.
Sci Total Environ ; 877: 162733, 2023 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-36924956

RESUMEN

This study focuses on the relevance of small watersheds in the macroplastic pollution of coastal environments. It aims to identify and quantify in terms of composition, number and mass, current riverine flows of floating macroplastics (>2.5 cm). Estimates are based on 66 visual monitoring of total litter over a 4-year-period (2016-2019) in a small coastal Mediterranean river, the Têt River (NW Mediterranean Sea). The plastic fraction represented 97 % of the observed litter, mainly cigarette butts (20.5 %), polystyrene fragments (18.8 %) and light packaging (16.3 %). The Tet River is characterized by frequent flash-flood events caused by heavy rain, that can induce a sudden rise of the water discharge. Such hydroclimatic forcing greatly influence macroplastic flows, both in terms of their average compositions and loads. We have estimated that 354,000 macroplastic items, corresponding to 0.65 tons, are discharged annually from the Tet River into the sea, and that 73 % of them are released during rain events (∼6 % of the year). The short observation distance from the water surface allowed to exhibit the great abundance of small litter (80 % of them were < 10 cm) and to evaluate to 1.8 g the average mass of floating plastics. Our results suggest that remediation actions must be taken on rainy days and target small litter in order to significantly limit macroplastic inputs from rivers to the sea. Moreover, the large share of cigarette butts in macrolitter inputs demonstrates that reducing ocean pollution cannot be achieved solely by improving waste management, but that changes in social behavior are also needed to stem waste production at the source.

2.
Anal Chem ; 94(7): 3135-3141, 2022 02 22.
Artículo en Inglés | MEDLINE | ID: mdl-35152703

RESUMEN

The analysis of 1D anti-diagonal spectra from the projections of 2D double-quantum filtered correlation spectroscopy NMR spectra is presented for the determination of the compositions of liquid mixtures of linear and branched alkanes confined within porous media. These projected spectra do not include the effects of line broadening and therefore retain high-resolution information even in the presence of inhomogeneous magnetic fields as are commonly found in porous media. A partial least-square regression analysis is used to characterize the mixture compositions. Two case studies are considered. First, mixtures of 2-methyl alkanes and n-alkanes are investigated. It is shown that estimation of the mol % of branched species present was achieved with a root-mean-square error of prediction (RMSEP) of 1.4 mol %. Second, the quantification of multicomponent mixtures consisting of linear alkanes and 2-, 3-, and 4-monomethyl alkanes was considered. Discrimination of 2-methyl and linear alkanes from other branched isomers in the mixture was achieved, although discrimination between 3- and 4- monomethyl alkanes was not possible. Compositions of the linear alkane, 2-methyl alkane, and the total composition of 3- and 4-methyl alkanes were estimated with a RMSEP <3 mol %. The approach was then used to estimate the composition of the mixtures in terms of submolecular groups of CH3CH2, (CH3)2CH, and CH2CH(CH3)CH2 present in the mixtures; a RMSEP <1 mol % was achieved for all groups. The ability to characterize the mixture compositions in terms of molecular subgroups allows the application of the method to characterize mixtures containing multimethyl alkanes. The motivation for this work is to develop a method for determining the mixture composition inside the catalyst pores during Fischer-Tropsch synthesis. However, the method reported is generic and can be applied to any system in which there is a need to characterize mixture compositions of linear and branched alkanes.


Asunto(s)
Alcanos , Hidrocarburos , Alcanos/análisis , Hidrocarburos/química , Isomerismo , Espectroscopía de Resonancia Magnética , Porosidad
3.
J Phys Chem B ; 124(48): 10971-10982, 2020 Dec 03.
Artículo en Inglés | MEDLINE | ID: mdl-33216551

RESUMEN

The ability to measure and predict molecular diffusion coefficients in multicomponent mixtures is not only of fundamental scientific interest but also of significant relevance in understanding how catalytic processes proceed. In the present work, the direct measurement of the molecular diffusion of H2 and CO gas-phase species diffusing in n-alkane mixtures using pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) methods is reported. The work is of direct relevance to Fischer-Tropsch (FT) catalysis, with the measurements being made of the gas-wax system with the wax in both the bulk liquid state and when confined within a titania catalyst support, at temperatures and pressures typical of low-temperature FT synthesis. Molecular diffusion coefficients of H2 and CO within wax-saturated porous titania in the range (1.00-2.43) × 10-8 and (6.44-8.50) × 10-9 m2 s-1, respectively, were measured in the temperature range of 140-240 and 200-240 °C for H2 and CO, respectively, at a pressure of 40 bar. The wax mixture was typical of a wax produced during FT catalysis and had a molar average carbon number of 36. It is shown that the hydrogen diffusion coefficient within this wax mixture is consistent, to within experimental error, with the hydrogen diffusion coefficient measured in pure single-component n-hexatriacontane (n-C36) wax; this result held with the waxes in the bulk liquid state and when confined within the porous titania. The tortuosity of the porous titania was also measured using PFG NMR and found to be 1.77; this value is independent of temperature. The ability of existing correlations to predict these experimentally determined data was then critically evaluated. Although the Wilke-Chang correlation was found to underestimate the molecular diffusion coefficients of both H2 and CO diffusing in the wax in both the bulk state and when confined within the porous titania, parameterized correlations based on the rough hard sphere model, having accounted for the experimentally determined tortuosity factor, predicted the H2 and CO diffusion within bulk and confined wax to within 3%.

4.
J Stomatol Oral Maxillofac Surg ; 121(1): 74-76, 2020 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-31476538

RESUMEN

Mandibular reconstruction using computer-aided design/computer-aided manufacturing cutting guides is currently a common procedure. However, inaccurate positioning of the cutting guide onto the fibular bone may result in osteosynthesis difficulties or imprecision in the reconstruction. A novel way to improve the stability of the cutting guides may be to add pillars in order for them to be suspended from the fibula, avoiding soft tissues interactions. We present the case of a 39-year-old male who needed mandibular reconstruction after a self-inflicted ballistic injury. We designed a customized cutting guide which included a set of 8 pillars allowing a suspension of the cutting guide 8 millimeters above the bone level. The pillars were perpendicular to one another, and allowed the operator to screw the cutting guide to the bone. The orthogonal position of the pillars enabled real stability during the osteotomies. In the operator experience, the length of the pillars was too important, and led to incomplete osteotomies, and the whole device was too bulky. However, with adaptations in the size of the pillars and the size of the whole device, this solution could be useful in cutting guide design to avoid impairments due to the soft tissues surrounding the fibula.


Asunto(s)
Colgajos Tisulares Libres , Reconstrucción Mandibular , Cirugía Asistida por Computador , Adulto , Diseño Asistido por Computadora , Peroné , Humanos , Masculino
5.
Talanta ; 174: 165-170, 2017 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-28738564

RESUMEN

Iodide in natural waters is an important nutrient to aquatic organisms and its determination is of relevance to marine aquaculture. For this reason it is of interest to have a simple analytical method for determination of iodide in water samples. Iodide in seawater can be determined electrochemically by cathodic stripping voltammetry (CSV) with a mercury drop electrode which has environmental drawbacks. In an attempt to minimise the use of mercury in voltammetry, a vibrating silver amalgam microwire electrode is used here for the determination by CSV of iodide speciation in natural waters including seawater. Microwire electrodes were made from silver wires (diameter: 12.5µm) and electrochemically coated with mercury. The electrode surface was stable for extended periods of analyses (at least one week) and was then replaced. The optimised conditions include a pH 8, a frequency of 500Hz and a deposition time of 60s, among others. The microwire was reactivated between scans using a conditioning potential at -3 V for 1s. The detection limit for iodide in seawater was found to be 0.7nM I- at a deposition time of 60s. The response increased linearly with the concentration of iodide in seawater up to 100nM I-. The method was successfully applied to various samples from the estuary of the river Mersey (Liverpool Bay). An existing procedure for iodine speciation was modified to enable determination of iodate and total iodine as well as iodide in estuarine waters.

6.
Artículo en Francés | MEDLINE | ID: mdl-27522243

RESUMEN

INTRODUCTION: Septic arthritis are serious infections rarely observed for the temporomandibular joint. They are mainly hematogenous or transmitted by contiguity. OBSERVATION: Our patient presents the case of an infection of the temporomandibular joint by maxillary sinusitis of dental origin further complicated by cerebral abscess and empyema. Initial treatment consisted of an endonasal and intraoral drainage, intravenous empirical antibiotic therapy, a close clinicoradiological monitoring, and rehabilitation following a long-term active physiotherapy. Furthermore, the patient reported the onset of a dental articulation disorder with a left side premature contact and right lateral open bite, corresponding to a significant left condylar resorption. DISCUSSION: This infectious disease is very rare for temporomandibular location; however, its general and functional outcome is determined by the precocity of the treatment. It is important to know the diagnosis and the associated symptoms even if they are not very specifically described. It is essential to consider the diagnosis when facing atypical pain of the temporomandibular joint associated with trismus.


Asunto(s)
Artritis Infecciosa/complicaciones , Resorción Ósea/etiología , Cóndilo Mandibular/patología , Trastornos de la Articulación Temporomandibular/complicaciones , Articulación Temporomandibular/microbiología , Anciano , Artritis Infecciosa/microbiología , Aspergilosis/complicaciones , Aspergilosis/microbiología , Aspergilosis/patología , Resorción Ósea/microbiología , Resorción Ósea/patología , Femenino , Humanos , Cóndilo Mandibular/microbiología , Articulación Temporomandibular/patología , Trastornos de la Articulación Temporomandibular/microbiología
8.
Phys Chem Chem Phys ; 16(2): 653-62, 2014 Jan 14.
Artículo en Inglés | MEDLINE | ID: mdl-24270575

RESUMEN

We discuss the relationship between the π-conjugation pattern, molecular length, and charge transport properties of molecular wires, both from an experimental and a theoretical viewpoint. Specifically, we focus on the role of quantum interference in the conductance properties of cross-conjugated molecules. For this, we compare experiments on two series of dithiolated wires. The first set we synthesized consists of three dithiolated oligo(phenylene ethynylene) (OPE) benchmark compounds with increasing length. The second series synthesized comprises three molecules with different π-conjugation patterns, but identical lengths, i.e. an anthracene (linear conjugation), an anthraquinone (cross-conjugation), and a dihydroanthracene (broken conjugation) derivative. To benchmark reliable trends, conductance experiments on these series have been performed by various techniques. Here, we compare data obtained by conductive-probe atomic force microscopy (CP-AFM) for self-assembled monolayers (SAMs) with single-molecule break junction and multi-molecule EGaIn data from other groups. For the benchmark OPE-series, we consistently find an exponential decay of the conductance with molecular length characterized by ß = 0.37 ± 0.03 Å(-1) (CP-AFM). Remarkably, for the second series, we do not only find that the linearly conjugated anthracene-containing wire is the most conductive, but also that the cross-conjugated anthraquinone-containing wire is less conductive than the broken-conjugated derivative. We attribute the low conductance values for the cross-conjugated species to quantum interference effects. Moreover, by theoretical modeling, we show that destructive quantum interference is a robust feature for cross-conjugated structures and that the energy at which complete destructive interference occurs can be tuned by the choice of side group. The latter provides an outlook for future devices in this fascinating field connecting chemistry and physics.

9.
Talanta ; 105: 287-91, 2013 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-23598021

RESUMEN

Chromium (Cr(VI)) in water can be determined by adsorptive catalytic cathodic stripping voltammetry in the presence of diethylenetriaminepentaacetic acid (DTPA) and nitrate on the hanging mercury drop electrode (HMDE). Predominately Cr(VI) is detected and the water is UV-digested to convert all Cr to Cr(VI) prior to analysis. We develop here an alternative to the HMDE by using a silver amalgam electrode based on a vibrating microwire. The microwire electrodes were 12.5 µm in diameter and electrochemically coated with mercury, and were stable for a week. Conditions were re-optimised, and we used a DTPA concentration of 5mM, 30 mM acetate pH buffer (pH 5.5 in seawater and pH 5.8 in pure water), and 1.5M nitrate solution. The microwire was reactivated prior to each scan by applying a negative potential (-3V) for 2s which removed all deposited Cr. The detection limit for chromium in pH buffer was found to be 0.2 nM Cr(VI) and in seawater 0.3 nM Cr(VI) at a deposition time of 30s. The response increased linearly with the concentration of Cr(VI) up to 60 nM Cr(VI) in seawater. The limit of detection is less good than using the HMDE, but the linear range is good and the microwire electrode could form the basis of apparatus for flow-analysis. The method was successfully tested on water samples from the estuary of the river Mersey (Liverpool Bay) giving chromium concentrations between 1.48 nM and 2.29 nM.

10.
Anal Chim Acta ; 769: 56-64, 2013 Mar 26.
Artículo en Inglés | MEDLINE | ID: mdl-23498121

RESUMEN

Silver amalgamated electrodes are a good substrate to determine lead (Pb) and cadmium (Cd) in seawater because they have properties similar to mercury but without the free mercury (Hg). Here a silver amalgamated microwire (SAM) electrode is optimised for the determination of Pb and Cd in coastal waters and uncontaminated ocean waters. The SAM was vibrated during the deposition step to increase the sensitivity, and electroanalytical parameters were optimised. The Hg coating required plating from a relatively concentrated (millimolar) solution, much greater (500×) than used for instance to coat glassy carbon electrodes. However, the coating on the ex situ amalgamated electrode was found to be stable and could be used for up to a week to determine trace levels of Pb in seawater of natural pH. The limit of detection square-wave ASV (50 Hz) using the pre-plated SAM electrode was 8 pM Pb using a 1-min plating time at pH 4.5. The limit of detection in pH 2 seawater was 4 pM using a 5-min plating time, and it was 12 pM using a 10-min plating time at natural pH in the presence of air, using a square-wave frequency of 700 Hz. The vibrating SAM electrode was tested on the determination of Pb in reference seawater samples from the open Atlantic (at the 20 pM level), Pacific, and used for a study of Pb in samples collected over 24 h in Liverpool Bay (Irish Sea).

11.
Anal Chim Acta ; 753: 42-7, 2012 Nov 13.
Artículo en Inglés | MEDLINE | ID: mdl-23107135

RESUMEN

A rapid electrochemical stripping chronopotentiometric procedure to determined sulfide in unaltered hydrothermal seawater samples is presented. Sulfide is deposited at -0.25 V (vs Ag/AgCl, KCl 3M) at a vibrating gold microwire and then stripped through the application of a reductive constant current (typically -2 µA). The hydrodynamic conditions are modulated by vibration allowing a short deposition step, which is shown here to be necessary to minimize H(2)S volatilization. The limit of detection (LOD) is 30 nM after a deposition step of 7s. This LOD is in the same range as the most sensitive cathodic voltammetric technique using a mercury drop electrode and is well below those reported previously for other electrodes capable of being implemented in situ.

12.
Anal Chim Acta ; 746: 53-62, 2012 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-22975180

RESUMEN

The oxidation potentials of As(0)/As(III) and Sb(0)/Sb(III) on the gold electrode are very close to each other due to their similar chemistry. Arsenic concentration in seawater is low (10-20 nM), Sb occurring at ~0.1 time that of As. Methods are shown here for the electroanalytical speciation of inorganic arsenic and inorganic antimony in seawater using a solid gold microwire electrode. Anodic stripping voltammetry (ASV) and chronopotentiometry (ASC) are used at pH ≤2 and pH 8, using a vibrating gold microwire electrode. Under vibrations, the diffusion layer size at a 5 µm diameter wire is 0.7 µm. The detection limits for the As(III) and Sb(III) are below 0.1 nM using 2 min and 10 min deposition times respectively. As(III) and Sb(III) can be determined in acidic conditions (after addition of hydrazine) or at neutral pH. In the latter case, oxidation of As(0) to As(III) was found to proceed through a transient As(III) species. Adsorption of this species on the gold electrode at potentials where Sb(III) diffused away is used for selective deposition of As(III). Addition of EDTA removes the interfering effect of manganese when analysing As(III). Imposition of a desorption step for Sb(III) analysis is required. Total inorganic arsenic (iAs=As(V)+As(III)) can be determined without interference from Sb nor mono-methyl arsenious acid (MMA) at 1.6

13.
J Environ Monit ; 14(10): 2793-802, 2012 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-22983404

RESUMEN

Apparatus is designed and tested to determine metals in situ in seawater. Voltammetry with a vibrating gold microwire electrode (VGME) is combined with a battery powered potentiostat and a processor board and is tested for in situ monitoring of copper (Cu) in coastal waters. The VGME was combined with solid state reference and counter electrodes to make a single vibrating probe which was rated up to a depth of 40 m. The measuring mode for Cu was square-wave anodic stripping voltammetry whilst dissolved oxygen (DO) was monitored by a linear sweep scan in a negative potential direction. The working electrode was reactivated between measurements using a suitable potential sequence. The novelties of this work are the field-testing of apparatus incorporating a VGME for copper monitoring, which eliminates the need for pumping and reagents, but has sufficient sensitivity for low ambient levels of copper, and the use of a novel potential sequence to stabilise the response over a long time period. The apparatus has a measuring time of about 6 weeks and a measuring frequency of 12 h(-1). Measurement is reagent-free and power use is low as no pump is required. Experiments are carried out to test the stability of response of the system at various temperatures and its robustness with respect to long-term copper monitoring. Preliminary data were obtained during autonomous deployment over several weeks on a buoy in the Irish Sea. Vertical movement of the buoy caused individual measurements to have a variability of about 15%. It was found that longer term variability of the electrode could be minimised by normalisation of the Cu response over that of DO as the response was related to diffusion through the electrode surface which was similarly affected. The detected fraction of Cu (labile Cu) amounted to 1.5-4 nM during different deployments at a total Cu concentration of ∼10 nM. The same ratio was found by voltammetry in samples taken to the laboratory. The new apparatus has demonstrated that metals in coastal waters can be monitored at trace level, much facilitating the monitoring of outfalls and local water contamination. Because of its sensitivity the apparatus would be of use in estuarine as well as coastal waters, with the aim of monitoring intermittent variability in the copper concentration.


Asunto(s)
Cobre/análisis , Monitoreo del Ambiente/instrumentación , Agua de Mar/química , Contaminantes Químicos del Agua/análisis , Electrodos , Monitoreo del Ambiente/métodos , Oro/química
14.
J Phys Chem A ; 116(25): 6609-20, 2012 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-22468628

RESUMEN

Copper (Cu) in seawater can be determined by anodic stripping voltammetry using a vibrating gold microwire electrode (VGME) with a much lower limit of detection than using a mercury electrode, enabling detection of labile Cu at trace level. The possibility of pseudopolarography of Cu using the VGME is investigated here and is calibrated against known chelating agents. The sensitivity much (15-fold) improved by application of a desorption step to remove adsorbed organic substances and excess anions. The notorious tendency of solid electrodes to be affected by memory effects was overcome by a conditioning interval between measurements that stabilized the electrode response. Model ligands, including EDTA, humic substances (HS), and glutathione (examples of natural ligands) were analyzed to calibrate the half-wave shift to complex stability. The half-wave shift on the VGME is much greater (~2×) than that on the mercury drop electrode which is attributed to several parameters including a much (5-fold) thinner diffusion layer on the VGME. Experiments showed that the same procedure is suitable for pseudopolarography of zinc. Application of the new method to samples from the Irish Sea showed Cu occurring in several complexes, all strongly bound, and some occurring in the electrochemically reversible region of the pseudopolarogram. The humic substance complex of Cu was also found to occur in the reversible region of the pseudopolarogram. The pseudopolarograms of Cu in seawater were unaffected by sample filtration and did not require purging to remove dissolved oxygen, suggesting that this method can be readily used as part of an in situ measuring system.


Asunto(s)
Cobre/análisis , Oro/química , Agua de Mar/química , Contaminantes Químicos del Agua/análisis , Electrodos
15.
Nat Nanotechnol ; 7(5): 305-9, 2012 Mar 25.
Artículo en Inglés | MEDLINE | ID: mdl-22447160

RESUMEN

As the dimensions of a conductor approach the nanoscale, quantum effects begin to dominate, and it becomes possible to control the conductance through direct manipulation of the electron wavefunction. Such control has been demonstrated in various mesoscopic devices at cryogenic temperatures, but it has proved to be difficult to exert control over the wavefunction at higher temperatures. Molecules have typical energy level spacings (∼eV) that are much larger than the thermal energy at 300 K (∼25 meV), and are therefore natural candidates for such experiments. Previously, phenomena such as giant magnetoresistance, Kondo effects and conductance switching have been observed in single molecules, and theorists have predicted that it should also be possible to observe quantum interference in molecular conductors, but until now all the evidence for such behaviour has been indirect. Here, we report the observation of destructive quantum interference in charge transport through two-terminal molecular junctions at room temperature. We studied five different rigid π-conjugated molecular wires, all of which form self-assembled monolayers on a gold surface, and find that the degree of interference can be controlled by simple chemical modifications of the molecular wire.

16.
Anal Chim Acta ; 710: 50-7, 2012 Jan 13.
Artículo en Inglés | MEDLINE | ID: mdl-22123111

RESUMEN

Direct electrochemical determination of arsenate (As(V)) in neutral pH waters is considered impossible due to electro-inactivity of As(V). As(III) on the other hand is readily plated as As(0) on a gold electrode and quantified by anodic stripping voltammetry (ASV). We found that the reduction of As(V) to As(III) was mediated by elemental Mn on the electrode surface in a novel redox couple in which 2 electrons are exchanged causing the Mn to be oxidised to Mn(II). Advantage is taken of this redox couple to enable for the first time the electrochemical determination of As(V) in natural waters of neutral pH including seawater by ASV using a manganese-coated gold microwire electrode. Thereto Mn is added to excess (~1 µM Mn) to the water leading to a Mn coating during the deposition of As on the electrode at a deposition potential of -1.3 V. Deposition of As(0) from dissolved As(V) caused elemental Mn to be re-oxidised to Mn(II) in a 1:1 molar ratio providing evidence for the reaction mechanism. The deposited As(V) is subsequently quantified using an ASV scan. As(III) interferes and should be quantified separately at a more positive deposition potential of -0.9 V. Combined inorganic As is quantified after oxidation of As(III) to As(V) using hypochlorite. The microwire electrode was vibrated during the deposition step to improve the sensitivity. The detection limit was 0.2 nM As(V) using a deposition time of 180 s.


Asunto(s)
Arseniatos/análisis , Técnicas Electroquímicas , Oro/química , Manganeso/química , Agua de Mar/química , Contaminantes Químicos del Agua/análisis , Electrodos , Concentración de Iones de Hidrógeno , Oxidación-Reducción , Salinidad
17.
Anal Chim Acta ; 703(1): 1-7, 2011 Oct 03.
Artículo en Inglés | MEDLINE | ID: mdl-21843669

RESUMEN

In this work, a simple, rapid, reliable and low cost method for simultaneous electrochemical determination of As, Cu, Hg and Pb ions, on a vibrating gold microwire electrode combined with stripping voltammetry, is described for the first time. The multi-element detection was performed in the presence of oxygen by differential pulse anodic stripping voltammetry (DPASV) in HCl 0.1 M with NaCl 0.5 M. This media was found optimum in terms of peak resolution, peak shape and sensitivities, and has a composition similar to seawater to which the method could potentially be applied. The gold microwire electrode presented well defined, undistorted, sharp and reproducible peaks for trace concentrations of Cu, Hg and Pb and As presented a reproducible peak with a small shoulder. Using a gold vibrating microwire electrode of 25 µm diameter and 30s deposition time, the detection limits of As, Cu, Hg and Pb were 0.07, 0.4, 0.07 and 0.2 µgL(-1), respectively. Possible effects of Al, Cd, Cr, Fe, Mn, Ni, Sb and Zn were investigated but did not cause any significant interferences. Finally, the method was applied for the simultaneous determination of these four metals in unpolluted river water samples and the results were validated by Atomic Absorption Spectroscopy with Electrothermal Atomization (AAS-EA) or by Inductively Coupled Plasma Mass Spectrometry (ICP-MS).

18.
Talanta ; 85(3): 1404-11, 2011 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-21807202

RESUMEN

Determination of the speciation of arsenic in groundwaters, using cathodic stripping voltammetry (CSV), is severely hampered by high levels of iron and manganese. Experiments showed that the interference is eliminated by addition of EDTA, making it possible to determine the arsenic speciation on-site by CSV. This work presents the CSV method to determine As(III) in high-iron or -manganese groundwaters in the field with only minor sample treatment. The method was field-tested in West-Bengal (India) on a series of groundwater samples. Total arsenic was subsequently determined after acidification to pH 1 by anodic stripping voltammetry (ASV). Comparative measurements by ICP-MS as reference method for total As, and by HPLC for its speciation, were used to corroborate the field data in stored samples. Most of the arsenic (78±0.02%) was found to occur as inorganic As(III) in the freshly collected waters, in accordance with previous studies. The data shows that the modified on-site CSV method for As(III) is a good measure of water contamination with As. The EDTA was also found to be effective in stabilising the arsenic speciation for longterm sample storage at room temperature. Without sample preservation, in water exposed to air and sunlight, the As(III) was found to become oxidised to As(V), and Fe(II) oxidised to Fe(III), removing the As(V) by adsorption on precipitating Fe(III)-hydroxides within a few hours.


Asunto(s)
Arsénico/análisis , Técnicas Electroquímicas/métodos , Hierro/análisis , Manganeso/análisis , Contaminantes Químicos del Agua/análisis , Arsénico/química , Cromatografía Líquida de Alta Presión , Ácido Edético/farmacología , Monitoreo del Ambiente/métodos , India , Hierro/química , Manganeso/química , Espectrometría de Masas/métodos , Oxidación-Reducción/efectos de los fármacos
19.
Anal Chem ; 83(10): 3848-56, 2011 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-21456613

RESUMEN

Stripping voltammetry is limited in acidic conditions to relatively high deposition potentials because of the interfering effects of the hydrogen produced at the working electrode. We report here a simple procedure to perform reliable and sensitive trace metal analysis in such conditions. Measurements are made at a gold microwire electrode. After applying a simple electrochemical conditioning procedure, hydrogen does not block the electrode, allowing reproducible analysis and smooth stripping signals to be obtained. Advantages of working inside the hydrogen wave are exemplified through the detection of the often considered electroinactive antimony(V). Sb(V) is detected in relatively low acidic conditions (pH ≤ 1) using low deposition potentials (≤-1.8 V). The detection limit is 5 pM (0.63 ppt), the lowest ever reported for an electroanalytical technique and one of the lowest analytical methods. The method is simple, robust, and free from the common arsenic interference due to selective electrochemical hydride generation of arsine over stibine during the deposition step. Analytical methods were optimized and tested on mineral, river, tap, and coastal seawater. Results favorably compare against Certified Reference Materials data (NASS-4 and SLRS-3) and ICPMS analysis. Deposition well below the hydrogen wave pushes the frontier of stripping voltammetry, and new analytical applications in this combined range of acidity and deposition potential are to be expected.

20.
Can J Occup Ther ; 77(2): 90-100, 2010 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-20464894

RESUMEN

BACKGROUND: Occupational therapists are frequently asked to document the interplay between individuals' neuropsychological deficits and the requirements of their daily lives. PURPOSE: The present study was designed to develop and validate a measure of independence in everyday functioning that considers recent advances in research regarding the ecological assessment of executive functions. METHOD: Experts (n=8) judged the IADL Profile's content validity and the tool was pilot tested with the target population (n=8). To document the tool's reliability, 30 patients aged 16 to 65 with moderate or severe TBI were recruited. A trained examiner administered the IADL Profile, and three trained judges rated video recordings on two occasions. RESULTS: An eight-task (29-item) test was developed. Comparing ratings of four raters, 95 percent of kappa coefficients indicated moderate to almost perfect agreement, and 94% showed almost perfect intrarater agreement. IMPLICATIONS: The IADL Profile provides occupational therapists with a set of measures of IADL independence with strong preliminary evidence of reliability.


Asunto(s)
Actividades Cotidianas , Lesiones Encefálicas/rehabilitación , Cognición , Enfermedad Aguda , Adolescente , Adulto , Lesiones Encefálicas/diagnóstico , Interpretación Estadística de Datos , Escala de Coma de Glasgow , Humanos , Persona de Mediana Edad , Proyectos Piloto , Psicometría , Reproducibilidad de los Resultados , Estudios de Validación como Asunto , Grabación en Video
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