| The distribution and association of trace elements in the bitumen, kerogen and pyrolysates from New Albany oil shale were investigated using instrumental neutron activation analysis (INAA), x-ray diffraction (XRD), electron microprobe x-ray fluorescence (EMP-XRF), liquid chromatography, ultra-violet spectroscopy and mass spectrometry.; Kerogen which was isolated from the New Albany shale was found to contain several HCl/HF resistant minerals (determined by XRD), including pyrite, marcasite, chalcopyrite, rutile, and anatase, and the neoformed mineral ralstonite. Kerogens (prepared at UNOCAL, CA) which were fractionated in an aqueous ZnBr{dollar}sb2{dollar} solution were found to contain {dollar}sim{dollar}20% less acid-resistant minerals than "traditional" HCl/HF isolated kerogens and were contaminated with Zn and Br. Kerogens (prepared at the University of Munich) treated with SnCl{dollar}sb2{dollar}/H{dollar}sb3{dollar}PO{dollar}sb4{dollar} at 150-270{dollar}spcirc{dollar}C (Kiba) and/or SnCl{dollar}sb2{dollar}/HCl at 110{dollar}spcirc{dollar}C were found to contain {dollar}<{dollar}10% of their original pyrite/marcasite (FeS{dollar}sb2{dollar}), but were contaminated with large amounts of Sn. The Kiba treatment also appeared to demetallate Ni(II) and VO(II) porphyrins.; The inorganic and organic associations of trace elements in New Albany kerogen were studied by analysis of kerogen fractions and a mineral residue ({dollar}sim{dollar}85% FeS{dollar}sb2{dollar}) obtained through density separations. The degree of association of several elements (As, Co, Mn, Mo, Ni, Sb, and Se) with FeS{dollar}sb2{dollar} was determined through the analysis of individual mineral grains by EMP-XRF and by analysis of the mineral residue treated with dilute HNO{dollar}sb3{dollar} to remove FeS{dollar}sb2{dollar}. These studies indicate that essentially all of the V and {dollar}sim{dollar}95% of the Ni present in New Albany kerogen is organically associated. Methods which are designed to account for the inorganic associations of trace elements in kerogens, including methods based on physical methods of separation, chemical removal of FeS{dollar}sb2{dollar}, EMP-XRF and low temperature ashing, are compared.; The bitumen-free New Albany shale was pyrolyzed under different conditions (hydrous, anhydrous or "dry", toluene, toluene/methanol, and sequential pyrolysis in toluene) and the trace element distributions of the respective pyrolysates were compared with those of the bitumen-I and kerogen. The Ni/V ratios of the pyrolysates resembled that of the kerogen (1.91), except for the first toluene pyrolysate which was similar to the bitumen-I (0.95). Bitumen and pyrolysate samples were separated into chromatographic fractions and the resultant yields and trace elements distributions compared. |
