RESUMEN
The local chemical structure of trace amounts of cadmium within microvolumes of highly inhomogeneous municipal solid waste fly ash particles was successfully monitored by means of micro-EXAFS. A new quantification procedure was developed for the evaluation of the micro-EXAFS data sets obtained from each individual particle based on a reverse Monte Carlo simulation. Evidence has been presented for the existence of cadmium silicate and cadmium chloride, with the cadmium silicate being the dominant form, and it has been demonstrated that the cadmium exists in both crystalline and amorphous states within the microspots analyzed.
Asunto(s)
Contaminantes Atmosféricos/análisis , Cadmio/análisis , Cadmio/química , Carbono/análisis , Espectrometría por Rayos X/métodos , Absorción , Carbono/química , Ceniza del Carbón , Monitoreo del Ambiente/instrumentación , Monitoreo del Ambiente/métodos , Material Particulado , Espectrometría por Rayos X/instrumentaciónRESUMEN
Four measurement campaigns were carried out to monitor total gaseous mercury (TGM) at one site in the Guiyang City, PR China in the following periods: April 19-30, 2000; February 26-March 14, 2001; June 26-July 20, 2001; and October 9-November 22, 2001, respectively. High temporal resolved data were obtained by using automated mercury analyzers Gardis 1A and Tekran 2537A. TGM data from all measurement periods followed the typical log normal distribution pattern. The geometric mean of TGM from different seasons were 8.56, 7.45, 5.20 and 8.33 ngm(-3) in spring 2000, winter 2001, summer 2001 and autumn 2001, respectively. The overall average TGM covering the sampling periods was 7.39 ngm(-3), which is significantly elevated comparing to global background of approximately 1.5-2.0 ngm(-3). The major anthropogenic atmospheric mercury emission sources differed significantly among seasons, which caused the seasonal variability of TGM level. Distinct daily variability of TGM was observed among seasons. The daytime TGM concentrations were larger than that of nighttime in spring and winter seasons, while in summer and autumn the opposite daily TGM distribution pattern was observed.
Asunto(s)
Contaminantes Atmosféricos/análisis , Mercurio/análisis , China , Monitoreo del Ambiente , Gases , Periodicidad , Estaciones del AñoRESUMEN
The mechanism and kinetics of the formation of methylmercury from an experimental solution containing divalent mercury and acetic acid has been investigated. The experiments were performed in a 2-dm(3) Teflon reactor. The organic mercury was measured with time resolutions varying between minutes and hours, after derivatisation, gas chromatography separation and Cold vapour atomic fluorescence detection. (GC)-CVAFS. CVAFS technique was used for determination of inorganic mercury in the aqueous phase using an automated mercury analyser. The experiments were carried out in concentrations relevant for natural waters. Our result shows that the reaction proceeds via mercury acetate complexes. A first order reaction coefficient has been calculated at various pH values, and was found to be (9.0+/-0.9) x 10(-7) s(-1) at pH 3.6-3.7. The rate was not found to be enhanced by UV-light when taking into account the photolytical degradation of methylmercury. The reaction rate at various pH values, the influences of some other relevant reaction parameters, and implications for atmospheric and terrestrial waters are discussed.
Asunto(s)
Contaminantes Ambientales/análisis , Mercurio/química , Compuestos de Metilmercurio/química , Cromatografía de Gases , Concentración de Iones de Hidrógeno , Cinética , Mercurio/análisis , Compuestos de Metilmercurio/análisis , Fotoquímica , Solubilidad , Volatilización , AguaRESUMEN
A comparison of manual procedures for measurements of dissolved gaseous mercury (DGM) in seawater was accomplished. The experiments were performed on board the Italian research vessel Urania during July 2000 as a subtask in the CNR "Med-Oceanor Project 2000". Water samples for DGM were collected by Go-Flo bottles and subsequently analysed for DGM on board the ship. Determinations of DGM were made in parallel by two groups using different analytical routines. The two sets of data obtained compare favourably. Based on the fieldwork and an additional laboratory study, analytical procedures are discussed and an optimised method to determine DGM is presented. In addition, a method for automated in situ measurements of DGM positioned in the water body was tested. This method has the potential to simplify studies of DGM dynamics, that is variation in concentration as a function of water temperature and solar radiation etc.
Asunto(s)
Mercurio/análisis , Agua de Mar/química , Contaminantes Químicos del Agua/análisis , Mar MediterráneoRESUMEN
Cadmium is a toxic metal that causes environmental concern in connection with utilization and land filling of ash from combustion of municipal solid waste (MSW). Collecting information about the chemical associations of Cd in ash is fundamental since this affects its solubility and leachability from the ash material. In the work presented here, the content, distribution, and chemical forms of toxic metals especially of Cd on/in individual Municipal Solid Waste (MSW) fly ash particles have been investigated in situ by synchrotron radiation induced mu-X-ray fluorescence and absorption spectrometry. The use of an excitation energy of 27 keV made it possible to detect trace metals, such as Cd, present at ppm levels routinely. Changing the excitation energy in the vicinity of the absorption edge of Cd (26.71 keV), the absorption spectra of this element were measured for the first time in this high energy range in micron-sized spots of individual fly ash particles. The measurements indicated Cd to be preferably concentrated in some small areas ("hot-spots") with high concentration (up to 200 ppm) rather than in a homogeneous distribution or as a thin coating on the whole particle surface, making the surface-reaction the most probable mechanism of Cd enrichment during MSW combustion processes. Comparisons of XAS spectra of fly ashes and reference compounds showed that in the particles studied Cd is present in the oxidation state +2. Analyses of linear combinations of standard spectra allowed estimating the Cd presence within fly ash particles as an admixture of primarily CdSO4, CdO, and CdCl2 as well as an unidentified compound not included as a standard.