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1.
PLoS One ; 15(12): e0243492, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-33320863

RESUMEN

Total reflection X-ray fluorescence analysis (TXRF) was used to determine chromium, selenium and bromine concentrations in blood serum samples of 50 patients with parenteral nutrition treatment. The concentrations were measured two times, namely in the first day (I measurement) of the treatment and the seventh day (II measurement) after the chromium and selenium supplementation. For comparison purposes also serum samples of 50 patients without nutritional disorders, admitted to a planned surgical procedure to remove the gall bladder (cholecystectomy), were analyzed and treated as the control group. Descriptive statistics of measured concentrations of Cr, Se and Br both for the studied and control groups was determined. In order to check the effectiveness of Cr and Se supplementation, the results of the first and seventh day measurements for studied group were statistically compared with each other, with literature reference values and with the results of the control group (two-group comparison). These comparisons indicate the effectiveness of selenium supplementation in the applied treatment procedure. In the case of Cr and Br concentrations no statistically significant differences were observed. We conclude that monitoring of the concentration of the important trace elements in human serum should be standard procedure in parenteral nutrition treatment. In this monitoring the TXRF technique can be successfully used.


Asunto(s)
Bromo/sangre , Cromo/sangre , Nutrición Parenteral , Selenio/sangre , Adulto , Anciano , Anciano de 80 o más Años , Bromo/normas , Estudios de Casos y Controles , Cromo/normas , Femenino , Humanos , Masculino , Persona de Mediana Edad , Valores de Referencia , Selenio/normas , Espectrometría por Rayos X/normas
2.
Radiat Prot Dosimetry ; 186(2-3): 268-273, 2019 Dec 31.
Artículo en Inglés | MEDLINE | ID: mdl-31845991

RESUMEN

Confocal micro-beam X-ray fluorescence analysis (confocal micro-XRF) is a non-destructive analytical tool for investigation of sample composition that enables acquiring three-dimensionally resolved information. This work describes a calibration procedure of a laboratory confocal micro-XRF setup, which leads to determination of its characteristic parameters. The calibration is performed using a tabletop confocal micro-XRF spectrometer designed recently at the Czech Technical University in Prague. The calibration procedure performed within this work comprises the essential steps of the setup characterization: excitation spectrum calculation, experimental determination of energy-dependent confocal volume size and integral sensitivity and calculation of the spectrometer sensitivity function. The results of the setup calibration will be used for development of a procedure enabling quantitative evaluation of the measured depth profiles.


Asunto(s)
Fluorescencia , Espectrometría por Rayos X/instrumentación , Espectrometría por Rayos X/normas , Algoritmos , Calibración , Humanos , Espectrometría por Rayos X/métodos , Rayos X
3.
Ultrastruct Pathol ; 43(6): 248-260, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-31736386

RESUMEN

Talc may lodge in human tissues through various routes, and has been associated with the development of ovarian carcinoma in case control epidemiologic studies. Talc is detected in tissues with scanning electron microscopy and energy dispersive X-ray analysis (SEM/EDS), with expected magnesium (Mg) and silicon (Si) peaks. The theoretical atomic weight % Mg/Si ratio for talc is 0.649, and for diagnostic purposes, a range of ± 5% (~0.617 to 0.681) is often used as a standard. Our goal was to establish empirically the quantitative range for talc identification by SEM/EDS using two source materials: a Johnson's Baby PowderTM (cosmetic-grade) consumer sample, and talc from Sigma-Aldrich (particle-grade material intended for scientific use). We examined 401 Mg-Si particles with SEM/EDS across the two samples, using two different SEM microscopes. Overall, we found a mean Mg/Si atomic weight % ratio of 0.645, with minimal differences between study subsets. The standard deviation was 0.025; (± 1σ = 0.620-0.670). The currently used ± 5% diagnostic range (Mg/Si 0.617-0.681) is thus reasonably close to this study's ± 1σ range, and well within a ± 2 σ confidence interval span (Mg/Si 0.595-0.695). The ± 5% range is thus an appropriately conservative standard whose continued use seems justified.


Asunto(s)
Microscopía Electrónica de Rastreo/normas , Espectrometría por Rayos X/normas , Talco/análisis , Humanos
4.
Rev. chil. radiol ; 25(3): 94-102, oct. 2019. tab, ilus
Artículo en Español | LILACS | ID: biblio-1058206

RESUMEN

Resumen: Se presenta una aplicación basada en Microsoft Excel llamada Xpektrin para el cálculo de dosis en radiología general. La aplicación permite simular espectros de rayos X en radiología general utilizando el modelo TASMICS a partir de mediciones del kerma en aire (Kair) y de la capa Hemirreductora (HVL). Tiene implementado el cálculo de magnitudes radiométricas y dosimétricas, como el kerma en aire en la superficie de entrada (Ke) y la dosis en piel (Dskin), en función de la elección arbitraria de los factores de exposición, el tipo y grosor de filtro, la distancia foco-piel y el tamaño de campo. Xpektrin fue validado con la herramienta computacional SPEKTR 3.0, utilizando mediciones de dosis y de HVL de tubos de rayos X de tres recintos hospitalarios. Se encontró buena correlación en ambas aplicaciones entre las mediciones experimentales y los valores calculados de HVL y con coeficientes de Pearson R² ≥ 0.99 en todos los casos. Sin embargo, se obtuvo mejor concordancia con los valores experimentales de HVL con Xpektrin (mediana de diferencias -0.43%, -0.04% y 0.01%) que con SPEKTR 3.0 (mediana de diferencias -3.31%, 0.10% y -7.85%), en particular para el tubo con mayor filtración. Xpektrin está optimizada para ser utilizada en los departamentos de radiología para la determinación de dosis de pacientes individuales en función de los parámetros utilizados durante la exposición, por lo que puede ser utilizada como parte de un sistema de registro dosimétrico o como apoyo para el establecimiento de niveles de referencia para diagnóstico (NRD), siendo particularmente útil en servicios con equipos sin registros automáticos de dosis. Además, debido a sus características de simulador, puede ser útil como herramienta pedagógica. El uso de Excel permite que sea altamente distribuible y fácil de usar, sin necesidad de conocimientos de programación.


Abstract: Xpektrin, an easy to use and highly distributable X-Ray Spectra Simulator in General Radiography. An application based on Microsoft Excel called Xpektrin is presented for dose calculation in general radiology. The application was developed to simulate X-ray spectra in general radiography using the TASMICS model. Using as inputs air kerma (Kair) and Half-value layer (HVL) measurements, Xpektrin allows the calculation of several radiometric and dosimetric quantities, such as the entrance surface air kerma (Ke) and the skin dose (Dskin), depending on the exposure factors, filter material type, filter thickness, focus-skin distance and field size. Xpektrin was validated against the Matlab toolkit SPEKTR 3.0, using dose and HVL measurements of X-ray tubes from three different hospitals. It was found good correlation in both applications between the experimental measurements and the calculated HVL and Kair values with Pearson coefficients R² ≥ 0.99 in all cases. However, experimental and calculated HVL have better agreement with Xpektrin (median percent difference -0.43%, -0.04% and 0.01%) than SPEKTR 3.0 (median percent difference -3.31%, 0.10% and -7.85%), particularly for the tube with greater filtration thickness. Xpektrin is optimized to be used in radiology departments for patient dose determination depending on the exposure parameters and may be used as part of a dosimetric record system or as a support for the determination of Diagnostic Reference Levels, which may be useful when no automatic dose records are available. In addition, due to its simulator characteristics, it can be useful as a pedagogical tool. Using Excel allows Xpektrin to be highly distributable and easy to use, without the need for programming skills.


Asunto(s)
Humanos , Radiología/métodos , Espectrometría por Rayos X/métodos , Simulación por Computador , Espectrometría por Rayos X/normas , Programas Informáticos , Método de Montecarlo , Niveles de Referencia para Diagnóstico
5.
IEEE Trans Med Imaging ; 38(4): 968-978, 2019 04.
Artículo en Inglés | MEDLINE | ID: mdl-30346280

RESUMEN

This paper describes the implementation of a novel and robust threshold energy calibration method for photon counting detectors using polychromatic X-ray tubes. Methods often used for such energy calibration may require re-orientation of the detector or introduce calibration errors that are flux and acquisition time-dependent. Our newly proposed "differential intensity ratios" (DIR) method offers a practical and robust alternative to existing methods. We demonstrate this robustness against photon flux used in calibration, spectral errors such as pulse pile-up as well as the detector's inherent spectral resolution limits. The demonstrated significant insensitivity of the proposed DIR signature to detector spectral distortions and energy resolution is a key finding. The proposed DIR calibration method is demonstrated using Medipix3RX detectors with a CdTe sensor under varying flux conditions. A per pixel calibration using the DIR method has also been implemented to demonstrate an improvement over the global energy resolution of the PCD.


Asunto(s)
Espectrometría por Rayos X/métodos , Espectrometría por Rayos X/normas , Calibración , Fotones
6.
J Anal Toxicol ; 42(6): 409-416, 2018 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-29566234

RESUMEN

The aim of this research is to develop a fast analytical method for multielemental analysis of the tobacco plant Virginia tobacco (cultivated in Poland) and tobacco products (cigarettes, cigars, cigarillos, snuff and two kinds of properly crafted tobacco such as a shisha and cigarette tobacco) distributed in Polish markets by means of a low-power benchtop total reflection X-ray fluorescence (TXRF) system. For this purpose, a set of certified tobacco materials and real samples was employed. In leaves and stalks of V. tobacco and tobacco products, a concentration of 18 elements (P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, Rb, Sr and Pb) was determined. Analyzing elemental composition of tobacco plants, one can see that concentrations of S, Ca, Ti, Mn, Zn, Sr and Pb are higher in leaves, whereas the concentrations of P, Cl, K, Fe Cu and Br are higher in stalks; the levels of Cr, Ni, As and Rb are comparable in both these parts of the tobacco plant. All of the parameters affecting sample preparation and TXRF measurements conditions were carefully evaluated. The accuracy and precision of the TXRF measurements were verified using an internal standardization approach for quantification.


Asunto(s)
Metales/análisis , Nicotiana/química , Extractos Vegetales/análisis , Espectrometría por Rayos X , Productos de Tabaco/análisis , Calibración , Metales/efectos adversos , Extractos Vegetales/efectos adversos , Extractos Vegetales/aislamiento & purificación , Hojas de la Planta/química , Tallos de la Planta/química , Polonia , Estándares de Referencia , Reproducibilidad de los Resultados , Espectrometría por Rayos X/normas , Nicotiana/efectos adversos , Nicotiana/crecimiento & desarrollo , Productos de Tabaco/efectos adversos
7.
Appl Radiat Isot ; 136: 21-26, 2018 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-29453080

RESUMEN

In this paper, effective energy of pulsed X-Ray emitted from a Mather-type plasma focus device in stored energy of 2.5 kJ with six different anode's insert materials was measured using radiographic method with attenuation filters. Since intensity and energy of X-ray beam were considerably changed with changing the insert material, the method was improved by using different filters simultaneously in all the experiments and selection of the best filter in each experiment according to the appropriate criteria. Effective energy of pulsed X-ray beam was measured 16, 28, 50, 51, 34 and 44 keV when aluminum, copper, zinc, tin, tungsten and lead were used as insert materials, and aluminum, copper, silver, silver, copper and lead were used as filters, respectively.


Asunto(s)
Electrodos , Gases em Plasma , Radiografía/métodos , Espectrometría por Rayos X/métodos , Metales Pesados/química , Modelos Teóricos , Espectrometría por Rayos X/normas
8.
J Pharm Biomed Anal ; 150: 308-317, 2018 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-29272815

RESUMEN

There is a strong need in the medical device industry to decrease failure rates of biomedical devices by reducing the incidence of defect structures and contaminants during the production process. The detection and identification of defect structures and contaminants is crucial for many industrial applications. The present study exploits reference-free X-ray fluorescence (XRF) analysis as an analytical tool for the traceable characterization of surface contaminants of medical devices, in particular N,N'-ethylene-bis (stearamide), an ubiquitous compound used in many industrial applications as a release agent or friction reduction additive. Reference-free XRF analysis as primary method has been proven to be capable of underpinning all other applied methods since it yields the absolute mass deposition of the selected N,N'-ethylene-bis (stearamide) contaminant whilst X-ray absorption fine structure analysis determines the chemical species. Ambient vibrational spectroscopy and mass spectroscopy methodologies such as Fourier transform infrared, Raman, and secondary ion mass spectroscopy have been used in this systematic procedure providing an extensive range of complementary analyses. The calibration procedure described in this paper was developed using specially designed and fabricated model systems varying in thickness and substrate material. Furthermore, typical real medical devices such as both a polyethylene hip liner and a silver-coated wound dressing have been contaminated and investigated by these diverse methods, enabling testing of this developed procedure. These well-characterized samples may be used as calibration standards for bench top instrumentation from the perspective of providing traceable analysis of biomaterials and surface treatments. These findings demonstrate the potential importance and usefulness of combining complementary methods for a better understanding of the relevant organic materials.


Asunto(s)
Contaminación de Equipos , Equipos y Suministros , Espectrometría por Rayos X/normas , Ácidos Esteáricos/análisis , Calibración , Estándares de Referencia , Reproducibilidad de los Resultados , Espectrometría de Masa de Ion Secundario , Espectroscopía Infrarroja por Transformada de Fourier , Espectrometría Raman
9.
Appl Radiat Isot ; 129: 49-56, 2017 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-28806597

RESUMEN

Compton scatter-modulated fluorescence and multivariate chemometric (artificial neural network (ANN) and principal component regression (PCR)) calibration strategy was explored for direct rapid trace biometals (Mn, Fe, Cu, Zn, Se) analysis in "complex" matrices (model soft tissues). This involved spectral feature selection (multiple fluorescence signatures) normalized to or in conjunction with Compton scatter. ANN model resulted in more accurate trace biometal determination (R2>0.9) compared to PCR. Hybrid nested (ANN and PCR) approach led to optimized accurate biometals' concentrations in Oyster tissue (≤ ± 10%).


Asunto(s)
Espectrometría por Rayos X/métodos , Oligoelementos/análisis , Algoritmos , Animales , Calibración , Análisis Multivariante , Redes Neurales de la Computación , Ostreidae/química , Análisis de Componente Principal , Estándares de Referencia , Dispersión de Radiación , Espectrometría por Rayos X/normas , Espectrometría por Rayos X/estadística & datos numéricos , Distribución Tisular , Oligoelementos/normas
10.
Talanta ; 174: 274-278, 2017 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-28738578

RESUMEN

A method of direct analysis for quantification of 15 inorganic elements (P, S, Cl, K, Ca, Mn, Fe, Ni, Cu, Zn, Br, As, Rb, Sr and Pb) in beers by Total Reflection X-Ray Fluorescence (TXRF) was developed. The experimental conditions were optimized. Direct analysis was compared with the acid digestion procedure to evaluate the effect matrix and the results were satisfactory. The evaluation of the accuracy and precision was realized by analysis of two certified reference materials of natural and waste water. For the majority of the elements, good agreement was achieved between the certified value and the value measured in the CRM´s. Low detection limits were obtained and it was adequate to determine trace elements in beers and to quality control Pb and As, whose maximum limits are 200 and 100µgL-1, respectively. The relative standard deviation (RSD%) ranged from 2.4% to 10%. The method was applied to 30 beer samples collected in several regions of Brazil. The concentration ranges (mgL-1) for the studied analytes were: P: (37.40-140.85); S (10.32-50.73); Cl (82.74-281.7); K (183.8-418.5); Ca (9.82-96.0); Mn (0.06-1.42); Fe (0.07-1.57); Ni (< LLD-1.13); Cu (< LLD-0.32); Zn (0.02-1.98); As (< LLD-0.10); Br (0.01-2.04); Rb (< LLD-0.52); Sr (< LLD-0.41) and Pb (< LLD-0.18). Some beer samples showed As and Pb concentrations above the levels established by Brazilian legislation. The developed method is simple, fast, consumes low amounts of reagents and allows the determination of a large number of analytes simultaneously. TXRF proved to be attractive and useful for routine analysis.


Asunto(s)
Cerveza/análisis , Espectrometría por Rayos X/métodos , Industrias , Estándares de Referencia , Espectrometría por Rayos X/normas , Factores de Tiempo
11.
Appl Radiat Isot ; 121: 91-95, 2017 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-28040603

RESUMEN

Assessment of chromium content in human nail or nail clippings could serve as an effective biomarker of chromium status. The feasibility of a new portable x-ray fluorescence (XRF) approach to chromium measurement was investigated through analysis of nail and nail clipping phantoms. Five measurements of 180s (real time) duration were first performed on six whole nail phantoms having chromium concentrations of 0, 2, 5, 10, 15, and 20µg/g. Using nail clippers, these phantoms were then converted to nail clippings, and assembled into different mass groups of 20, 40, 60, 80, and 100mg for additional measurements. The amplitude of the chromium Kα characteristic x-ray energy peak was examined as a function of phantom concentration for all measurement conditions to create a series of calibration lines. The minimum detection limit (MDL) for chromium was also calculated for each case. The chromium MDL determined from the whole nail intact phantoms was 0.88±0.03µg/g. For the clipping phantoms, the MDL ranged from 1.2 to 3.3µg/g, depending on the mass group analyzed. For the 40mg clipping group, the MDL was 1.2±0.1µg/g, and higher mass collections did not improve upon this result. This MDL is comparable to chromium concentration levels seen in various studies involving human nail clippings. Further improvements to the portable XRF technique would be required to detect chromium levels expected from the lower end of a typical population.


Asunto(s)
Cromo/análisis , Uñas/química , Espectrometría por Rayos X/métodos , Biomarcadores/análisis , Calibración , Estudios de Factibilidad , Humanos , Límite de Detección , Fantasmas de Imagen , Espectrometría por Rayos X/instrumentación , Espectrometría por Rayos X/normas , Oligoelementos/análisis
12.
IEEE Trans Med Imaging ; 34(3): 697-706, 2015 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-25051546

RESUMEN

The energy information acquired using spectral X-ray detectors allows noninvasive identification and characterization of chemical components of a material. To achieve this, it is important that the energy response of the detector is calibrated. The established techniques for energy calibration are not practical for routine use in pre-clinical or clinical research environment. This is due to the requirements of using monochromatic radiation sources such as synchrotron, radio-isotopes, and prohibitively long time needed to set up the equipment and make measurements. To address these limitations, we have developed an automated technique for calibrating the energy response of the pixels in a spectral X-ray detector that runs with minimal user intervention. This technique uses the X-ray tube voltage (kVp) as a reference energy, which is stepped through an energy range of interest. This technique locates the energy threshold where a pixel transitions from not-counting (off) to counting (on). Similarly, we have developed a technique for calibrating the energy response of individual pixels using X-ray fluorescence generated by metallic targets directly irradiated with polychromatic X-rays, and additionally γ-rays from (241)Am. This technique was used to measure the energy response of individual pixels in CdTe-Medipix3RX by characterizing noise performance, threshold dispersion, gain variation and spectral resolution. The comparison of these two techniques shows the energy difference of 1 keV at 59.5 keV which is less than the spectral resolution of the detector (full-width at half-maximum of 8 keV at 59.5 keV). Both techniques can be used as quality control tools in a pre-clinical multi-energy CT scanner using spectral X-ray detectors.


Asunto(s)
Espectrometría por Rayos X/normas , Tomografía Computarizada por Rayos X/métodos , Fenómenos Biofísicos , Calibración , Diseño de Equipo , Fluorescencia , Humanos , Fotones , Espectrometría por Rayos X/instrumentación
13.
Phys Med Biol ; 59(23): 7211-27, 2014 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-25369288

RESUMEN

Accurate energy calibration is critical for the application of energy-resolved photon-counting detectors in spectral imaging. The aim of this study is to investigate the feasibility of energy response calibration and characterization of a photon-counting detector using x-ray fluorescence. A comprehensive Monte Carlo simulation study was performed using Geant4 Application for Tomographic Emission (GATE) to investigate the optimal technique for x-ray fluorescence calibration. Simulations were conducted using a 100 kVp tungsten-anode spectra with 2.7 mm Al filter for a single pixel cadmium telluride (CdTe) detector with 3 × 3 mm(2) in detection area. The angular dependence of x-ray fluorescence and scatter background was investigated by varying the detection angle from 20° to 170° with respect to the beam direction. The effects of the detector material, shape, and size on the recorded x-ray fluorescence were investigated. The fluorescent material size effect was considered with and without the container for the fluorescent material. In order to provide validation for the simulation result, the angular dependence of x-ray fluorescence from five fluorescent materials was experimentally measured using a spectrometer. Finally, eleven of the fluorescent materials were used for energy calibration of a CZT-based photon-counting detector. The optimal detection angle was determined to be approximately at 120° with respect to the beam direction, which showed the highest fluorescence to scatter ratio (FSR) with a weak dependence on the fluorescent material size. The feasibility of x-ray fluorescence for energy calibration of photon-counting detectors in the diagnostic x-ray energy range was verified by successfully calibrating the energy response of a CZT-based photon-counting detector. The results of this study can be used as a guideline to implement the x-ray fluorescence calibration method for photon-counting detectors in a typical imaging laboratory.


Asunto(s)
Algoritmos , Fotones , Espectrometría por Rayos X/normas , Calibración , Estudios de Factibilidad , Espectrometría por Rayos X/instrumentación
14.
Environ Int ; 66: 38-43, 2014 May.
Artículo en Inglés | MEDLINE | ID: mdl-24518434

RESUMEN

Extensive evidence of the adverse impacts of polychlorinated biphenyls (PCBs) to wildlife, domestic animals, and humans has now been documented for over 40 years. Despite the ban on production and new use of PCBs in the United States in 1979, a number of fish consumption advisories remain in effect, and there remains considerable uncertainty regarding ongoing environmental sources and management alternatives. Using a blind sampling approach, 25 caulk samples were collected from the exterior of ten buildings in the San Francisco Bay Area and analyzed for PCBs using congener-specific gas chromatography-mass spectrometry (GC-MS) and chlorine using portable X-ray fluorescence (XRF). PCBs were detected in 88% of the caulk samples collected from the study area buildings, with 40% exceeding 50 ppm. Detectable PCB concentrations ranged from 1 to 220,000 ppm. These data are consistent with previous studies in other cities that have identified relatively high concentrations of PCBs in concrete and masonry buildings built between 1950 and 1980. Portable XRF was not a good predictor of the PCB content in caulk and the results indicate that portable XRF analysis may only be useful for identifying caulk that contains low concentrations of Cl (≤ 10,000 ppm) and by extension low or no PCBs. A geographic information system-based approach was used to estimate that 10,500 kg of PCBs remain in interior and exterior caulk in buildings located in the study area, which equates to an average of 4.7 kg PCBs per building. The presence of high concentrations in the exterior caulk of currently standing buildings suggests that building caulk may be an ongoing source of PCBs to the San Francisco Bay Area environment. Further studies to expand the currently small international dataset on PCBs in caulking materials in buildings of countries that produced or imported PCBs appear justified in the context of both human health and possible ongoing environmental release.


Asunto(s)
Materiales de Construcción/análisis , Monitoreo del Ambiente , Contaminantes Ambientales/análisis , Bifenilos Policlorados/análisis , Bahías , California , Espectrometría por Rayos X/normas
15.
Analyst ; 138(16): 4649-55, 2013 Aug 21.
Artículo en Inglés | MEDLINE | ID: mdl-23775063

RESUMEN

Imaging and analyzing gunshot residue (GSR) particles using the scanning electron microscope equipped with an energy dispersive X-ray spectrometer (SEM-EDS) is a standard technique that can provide important forensic evidence, but the discrimination power of this technique is limited due to low sensitivity to trace elements and difficulties in obtaining quantitative results from small particles. A new, faster method using a scanning proton microbeam and Particle Induced X-ray Emission (µ-PIXE), together with Elastic Backscattering Spectrometry (EBS) is presented for the non-destructive, quantitative analysis of the elemental composition of single GSR particles. In this study, the GSR particles were all Pb, Ba, Sb. The precision of the method is assessed. The grouping behaviour of different makes of ammunition is determined using multivariate analysis. The protocol correctly groups the cartridges studied here, with a confidence >99%, irrespective of the firearm or population of particles selected.


Asunto(s)
Armas de Fuego , Medicina Legal/métodos , Espectrometría por Rayos X/métodos , Heridas por Arma de Fuego , Medicina Legal/normas , Humanos , Microscopía Electrónica de Rastreo/métodos , Microscopía Electrónica de Rastreo/normas , Espectrometría por Rayos X/normas
16.
Anal Chim Acta ; 786: 8-15, 2013 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-23790285

RESUMEN

In the present study, and taking into account the microanalytical capability of total reflection X-ray spectrometry (TXRF), we explored the possibilities of hollow fibre liquid-phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME) combined with TXRF for the determination of low amounts of inorganic Sb species in waters. For each of the LPME configurations aforementioned, experimental parameters affecting Sb extraction but specially the proper sample preparation process (deposition volume on the reflective carrier and drying mode) and measurement conditions for subsequent TXRF analysis have been carefully evaluated. The best analytical strategy for the determination of Sb(III) and Sb(V) in the low µg L(-1) range was found to be the application of the DLLME mode before TXRF analysis. The developed methodology was successfully applied to the determination of inorganic Sb speciation in different types of spiked water samples.


Asunto(s)
Antimonio/análisis , Microextracción en Fase Líquida/métodos , Espectrometría por Rayos X/métodos , Contaminantes Químicos del Agua/análisis , Agua/análisis , Microextracción en Fase Líquida/normas , Espectrometría por Rayos X/normas
17.
Biometals ; 26(1): 179-87, 2013 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-23334711

RESUMEN

In manganese-enhanced magnetic resonance imaging (MEMRI), the paramagnetic divalent ion of manganese (Mn(2+)) is injected into animals to generate tissue contrast, typically at much higher exposures than have been previously used in studies of Mn toxicity. Here we investigate the effect of these injections on the homeostasis of the transition metals iron and copper in mice to see if there are disruptions which should be considered in MEMRI studies. Manganese shares transport proteins with other transition metals including iron and copper, so it is possible that changes in manganese levels in tissue following injections of the metal may affect other metal levels too. This in turn may affect MRI contrast or the investigation of disease processes in the animal models being imaged. In this study, we measured manganese, iron, and copper concentrations in the blood, kidney, liver and in brain regions in mice treated with four injections of 30 mg/kg MnCl(2) 4H(2)O (dry chemical weight/body weight)-a common dose used in MEMRI. In addition to the expected increases in manganese in tissues, we noted a statistically significant reduction in copper in the kidney and liver. Also, we noted a statistically significant decrease in concentration of iron in the thalamus of the brain. These findings suggest that the high doses of manganese injected in MEMRI studies can disrupt the homeostasis of other transition metals in mice.


Asunto(s)
Medios de Contraste/administración & dosificación , Cobre/metabolismo , Homeostasis , Hierro/metabolismo , Manganeso/administración & dosificación , Animales , Encéfalo/metabolismo , Medios de Contraste/farmacocinética , Riñón/metabolismo , Hígado/metabolismo , Imagen por Resonancia Magnética , Masculino , Manganeso/farmacocinética , Ratones , Ratones Endogámicos C57BL , Estándares de Referencia , Espectrometría por Rayos X/normas , Elementos de Transición/metabolismo
18.
J Pharm Biomed Anal ; 70: 713-7, 2012 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-22883603

RESUMEN

Total reflection X-ray spectrometry is an instrumental technique based on X-ray fluorescence, which offers detection limits low enough to quantify trace element concentrations with negligible interference from matrix components. The technique is well established in material sciences and now reaches out to extended applications in life sciences and pharmaceutical quality control. In our study we focused on possible applications for the quantification of gold and platinum containing active ingredients in trace concentrations (ppb range) in a matrix of biological origin (cell suspensions). General aspects of sample preparation as well as selected important method performance parameters (precision, recovery rates) were investigated. Overall, TXRF represents an useful option to quantify metals in ppb concentrations with acceptable precision and recovery.


Asunto(s)
Antineoplásicos/análisis , Antirreumáticos/análisis , Auranofina/análisis , Cisplatino/análisis , Espectrometría por Rayos X , Antineoplásicos/metabolismo , Antirreumáticos/metabolismo , Auranofina/metabolismo , Calibración , Extractos Celulares/química , Cisplatino/metabolismo , Células HT29 , Humanos , Límite de Detección , Proyectos Piloto , Estándares de Referencia , Reproducibilidad de los Resultados , Espectrometría por Rayos X/normas
19.
J Pharm Biomed Anal ; 63: 151-9, 2012 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-22349883

RESUMEN

Palladium (Pd) is extensively used in pharmaceutical small molecule drug substance processes, however it must be removed prior to release of the active pharmaceutical ingredient (API). Evaluation of four TXRF instruments and configurations were compared to ICP-MS instrumentation for trace metal analysis, most importantly for Pd. Standards and six pharmaceutical drug substances, triprolidine HCl, diphenhydramine HCl, chlorpheniramine maleate, pseudoephedrine HCl, ephedrine sulfate, and scopolamine HBr, were analyzed to determine linearity, sensitivity, accuracy, and precision for Pd plus Cr, Fe, Cu, Rh, and Pt versus interferences, particularly from Cl, S, and Ar, on the various X-ray fluorescence lines. Irrespective of instrument platform, in general X-ray sources capable of accessing Pd-K lines were found to be most effective in determination of Pd in APIs.


Asunto(s)
Contaminación de Medicamentos , Paladio/análisis , Preparaciones Farmacéuticas/química , Espectrometría por Rayos X , Tecnología Farmacéutica/métodos , Calibración , Catálisis , Química Farmacéutica , Clorfeniramina/química , Difenhidramina/química , Efedrina/química , Seudoefedrina/química , Escopolamina/química , Espectrometría por Rayos X/normas , Tecnología Farmacéutica/normas , Triprolidina/química
20.
Environ Res ; 111(1): 17-20, 2011 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-21092947

RESUMEN

In-vivo measurement of bone lead by means of K-X-ray fluorescence (KXRF) is the preferred biological marker of chronic exposure to lead. Unfortunately, considerable measurement error associated with KXRF estimations can introduce bias in estimates of the effect of bone lead when this variable is included as the exposure in a regression model. Estimates of uncertainty reported by the KXRF instrument reflect the variance of the measurement error and, although they can be used to correct the measurement error bias, they are seldom used in epidemiological statistical analyzes. Errors-in-variables regression (EIV) allows for correction of bias caused by measurement error in predictor variables, based on the knowledge of the reliability of such variables. The authors propose a way to obtain reliability coefficients for bone lead measurements from uncertainty data reported by the KXRF instrument and compare, by the use of Monte Carlo simulations, results obtained using EIV regression models vs. those obtained by the standard procedures. Results of the simulations show that Ordinary Least Square (OLS) regression models provide severely biased estimates of effect, and that EIV provides nearly unbiased estimates. Although EIV effect estimates are more imprecise, their mean squared error is much smaller than that of OLS estimates. In conclusion, EIV is a better alternative than OLS to estimate the effect of bone lead when measured by KXRF.


Asunto(s)
Huesos/química , Plomo/análisis , Espectrometría por Rayos X/métodos , Sesgo , Simulación por Computador , Humanos , Análisis de Regresión , Espectrometría por Rayos X/normas
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