Iron-oxide aerogel and xerogel catalyst formulations: characterization by 57Fe Mössbauer and XAFS spectroscopies.

Iron in various iron-oxide aerogel and xerogel catalyst formulations (> or =85% Fe(2)O(3); < or =10% K, Co, Cu, or Pd) developed for possible use in Fischer-Tropsch synthesis (FTS) or the water-gas-shift (WGS) reaction has been examined by (57)Fe Mössbauer spectroscopy. The seventeen samples consisted of both as-prepared and calcined aerogels and xerogels and their products after use as catalysts for FTS or the WGS reaction. Complementary XAFS spectra were obtained on the occurrence of the secondary elements in some of the same materials. A broad, slightly asymmetric, two-peak Mössbauer spectrum was obtained from the different as-prepared and calcined catalyst formulations in the majority of cases. Such spectra could only be satisfactorily fit with three quadrupole doublet components, but no systematic trends in the isomer shift and quadrupole splitting parameters and area ratios of the individual components could be discerned that reflected variations in the composition or preparation of the aerogel or xerogel materials. However, significant reductions were noted in the Mössbauer effective thickness (recoilless absorption effect per unit mass of iron) parameter, chi(eff)/g, determined at room temperature, for aerogels and xerogels compared to bulk iron oxides, reflecting the openness and lack of rigidity of the aerogel and xerogel structures. Mössbauer measurements for two aerogels over the range from 15 to 292K confirmed the greatly diminished nature of this parameter at room temperature. Major increases in the effective thickness parameter were observed when the open structure of the aerogel or xerogel collapsed during calcination resulting in the formation of iron oxides (hematite, spinel ferrite). Similar structural changes were indicated by increases in this parameter after use of iron-oxide aerogels as catalysts for FTS or the WGS reaction, during which the iron-oxide aerogel was converted to a mixture of nonstoichiometric magnetite and the Hägg carbide, chi-Fe(5)C(2), or nonstoichiometric magnetite, respectively.

Selenium and arsenic speciation in fly ash from full-scale coal-burning utility plants.

X-ray absorption fine structure spectroscopy has been used to determine directly the oxidation states and speciation of selenium and arsenic in 10 fly ash samples collected from full-scale utility plants. Such information is needed to assess the health risk posed by these elements in fly ash and to understand their behavior during combustion and in fly ash disposal options, such as sequestration in tailings ponds. Selenium is found predominantly as Se(IV) in selenite (SeO3(2-)) species, whereas arsenic is found predominantly as As(V) in arsenate (AsO4(3-)) species. Two distinct types of selenite and arsenate spectra were observed depending upon whether the fly ash was derived from eastern U.S. bituminous (Fe-rich) coals or from western subbituminous or lignite (Ca-rich) coals. Similar spectral details were observed for both arsenic and selenium in the two different types of fly ash, suggesting that the postcombustion behavior and capture of both of these elements are likely controlled by the same dominant element or phase in each type of fly ash.