RESUMEN
The monitoring of Advanced Oxidation/Reduction Processes (AO/RPs) for the evaluation of the yield and mechanisms of decomposition of perfluorinated compounds (PFCs) is often a more difficult task than their determination in the environmental, biological or food samples with complex matrices. This is mostly due to the formation of hundreds, or even thousands, of both intermediate and final products. The considered AO/RPs, involving free radical reactions, include photolytic and photocatalytic processes, Fenton reactions, sonolysis, ozonation, application of ionizing radiation and several wet oxidation processes. The main attention is paid to the most commonly occurring PFCs in the environment, namely PFOA and PFOS. The most powerful and widely exploited method for this purpose is without a doubt LC/MS/MS, which allows the identification and trace quantitation of all species with detectability and resolution power depending on the particular instrumental configurations. The GC/MS is often employed for the monitoring of volatile fluorocarbons, confirming the formation of radicals in the processes of CâC and CâS bonds cleavage. For the direct monitoring of radicals participating in the reactions of PFCs decomposition, the molecular spectrophotometry is employed, especially electron paramagnetic resonance (EPR). The UV/Vis spectrophotometry as a detection method is of special importance in the evaluation of kinetics of radical reactions with the use of pulse radiolysis methods. The most commonly employed for the determination of the yield of mineralization of PFCs is ion-chromatography, but there is also potentiometry with ion-selective electrode and the measurements of general parameters such as Total Organic Carbon and Total Organic Fluoride. The presented review is based on about 100 original papers published in both analytical and environmental journals.
Asunto(s)
Técnicas de Química Analítica/métodos , Contaminantes Ambientales/análisis , Contaminantes Ambientales/química , Fluorocarburos/análisis , Fluorocarburos/química , Radicales Libres/química , Humanos , Oxidación-Reducción , VolatilizaciónRESUMEN
Separation of Y from other rare earth elements (REE) is difficult because of similarity of its ionic radius to ionic radii of Tb, Dy and Ho. In the new RP-HPLC system with C18 column, tetra-n-butyl ammonium hydroxide (TBAOH) as an ion interaction reagent (IIR), nitrilotriacetic acid (NTA) as a complexing agent at pH=2.8-3.5, and post column derivatization with Arsenazo III, yttrium is eluted in the region of light REE, between Nd and Sm and is base line separated from Nd and Sm and even from promethium. Simple model employing literature data on complex formation of REE with NTA and based on anion exchange mechanism was developed to foresee the order of elution of individual REE. The model correctly predicted that lanthanides up to Tb will be eluted in the order of increasing Atomic Number (At.No.) but all heavier REE will show smaller retention factors than Tb. Concurrent UV/VIS detection at 658nm and the use of radioactive tracers together with γ-ray spectrometric measurements made possible to establish an unique elution order of elution of REE: La, Ce, Pr, Nd, Pm, Y, Sm, Er, Ho, Tm, Yb, Eu, Lu, Dy+Gd, Tb, Sc. The real place of Y however, in this elution series differs from that predicted by the model (Y between Sm and Eu). The method described in this work enables selective separation of Y from La, Ce, Pr, Nd, Pm, Sm and all heavier REE treated as a group.
Asunto(s)
Cromatografía Líquida de Alta Presión , Cromatografía de Fase Inversa , Complejos de Coordinación/química , Metales de Tierras Raras/química , Ácido Nitrilotriacético/química , Itrio/aislamiento & purificación , Aniones/química , Complejos de Coordinación/aislamiento & purificación , Concentración de Iones de Hidrógeno , Elementos de la Serie de los Lantanoides/química , Elementos de la Serie de los Lantanoides/aislamiento & purificación , Itrio/químicaRESUMEN
Analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for determination of lanthanides in plant materials was investigated and compared with neutron activation analysis (NAA) as well as ion chromatography (IC) with UV-VIS detection. Two sample preparation protocols were tested: (i) microwave assisted digestion by concentrated nitric acid; (ii) microwave digestion involving silica and fluoride removal, followed by the selective and quantitative lanthanides group separation from the plant matrix. Several Certified Reference Materials (CRM) of plant origin were used for the evaluation of the accuracy of the applied analytical procedures. The consistency of results, obtained by various methods, enabled to establish the tentative recommended values (TRV) for several missing elements in one of CRMs. The ICP-MS, due to its very high sensitivity, has the potential to contribute to this aim. The discrepancy of the results obtained by various methods was discussed in a view of possible matrix effects related to the composition of investigated materials.
Asunto(s)
Elementos de la Serie de los Lantanoides/análisis , Espectrometría de Masas/métodos , Neutrones , Plantas/química , Espectrofotometría Ultravioleta/métodos , Límite de Detección , Espectrometría de Masas/normas , Estándares de Referencia , Espectrofotometría Ultravioleta/normasRESUMEN
The preparation, certification, and characterization of two new biological certified reference materials for inorganic trace analysis have been presented. They are based on two different varieties of tobacco leaves, namely, Oriental Basma Tobacco Leaves (INCT-OBTL-5), grown in Greece, and Polish Virginia Tobacco Leaves (INCT-PVTL-6), grown in Poland. Certification of the materials was based on the statistical evaluation of results obtained in a worldwide interlaboratory comparison, in which 87 laboratories from 18 countries participated, providing 2568 laboratory averages on nearly 80 elements. It was possible to establish the certified values of concentration for many elements in the new materials, that is, 37 in INCT-OBTL-5 and 36 in INCT-PVTL-6, including several toxic ones like As, Cd, Hg, Pb, and so forth. The share and the role of instrumental analytical techniques used in the process of certification of the new CRMs are discussed.
Asunto(s)
Nicotiana/química , Hojas de la Planta/química , Oligoelementos/análisis , Laboratorios , Tamaño de la Partícula , Hojas de la Planta/toxicidad , Estándares de ReferenciaRESUMEN
Lanthanides represent an interesting group of elements which are steadily gaining importance in science and in industry. Literature data suggest that they may have a role in regulating cellular processes and also in agriculture enhancing plant growth. Only few instrumental methods like NAA, ICP-OES and ICP-MS have potential for the determination of low levels of all lanthanides, but in practice they often have to be combined with suitable separation/preconcentration methods to achieve maximum number of elements being determined and to assure good accuracy and precision. In this work an attempt has been made to compare the performance of both variants of NAA: purely instrumental activation analysis (INAA) and radiochemical mode (RNAA) with pre- and post-irradiation group separation for the determination of individual lanthanides with the special emphasis on rarely determined elements (Gd, Ho, Er, Tm, Lu). This has been done by the analysis of two reference materials with different matrices viz. biological (CTA-OTL-1) and mineral (CTA-FFA-1). The results are compared with those obtained by ion chromatography (IC) employing the same lanthanide group preseparation scheme as in the case of RNAA.
Asunto(s)
Análisis por Activación/métodos , Elementos de la Serie de los Lantanoides/análisis , Elementos de la Serie de los Lantanoides/aislamiento & purificación , Cromatografía , Plantas/químicaRESUMEN
The optimization of experimental conditions for radiolytic removal of organic pollutants from water and waste with the use of ionizing radiation via controlling the concentration of target compound(s) requires also monitoring the toxicity changes during the process. Commonly used herbicides 2,4-D and dicamba were shown to increase toxicity measured with the Microtox test at low irradiation doses resulting from formation of more toxic transient products, which can be decomposed at larger doses. The changes of toxicity were examined with respect to dose magnitude and the presence of commonly occurring scavengers of radiation.