[en] Chemical ionization-proton exchange mass spectrometry (CIPE) allows the number of unsubstituted aromatic carbons in alkylbenzene isomers to be determined. Only the aromatic hydrogens undergo exchange with deuterium when deuterated water, methanol, or ethanol is used as the reagent gas. Chemical ionization with deuterated methanol gives an acceptable mass spectral background and allows the determination of the number of unsubstituted positions on the benzene ring yielding structural information often unavailable from conventional electron impact spectra. Structural isomers such as propyl-, methylethyl-, and trimethylbenzene can easily be identified. The comparison of CIPE spectra from standard compounds, which are often unavailable, is not required to determine the number of unsubstituted aromatic carbons in alkylbenzene isomers. The method also allows ortho and para to be distinguished from meta disubstituted alkylbenzenes. Deuteriomethanol chemical ionization is used to characterize alkylbenzenes in a complex and relatively well studied sample, diesel exhaust. 14 references, 3 figures, 3 tables

[en] The objective of the Environmental Management program at the Energy and Environmental Research Center (EERC) is to develop, demonstrate, and commercialize technologies that address the environmental management needs of contaminated sites, including characterization, sensors, and monitoring; low-level mixed waste processing; material disposition technology; improved waste forms; in situ containment and remediation; and efficient separation technologies for radioactive wastes. Task 2 is the extraction and analysis of pollutant organics from contaminated solids using off-line supercritical fluid extraction (SFE) and on-line SFE-infrared spectroscopy. Task 3, pyrolysis of plastics, has as its objectives to develop a commercial process to significantly reduce the volume of mixed-plastics-paper-resin waste contaminated with low-level radioactive material; concentrate contaminants in a collectible form; and determine the distribution and form of contaminants after pyrolysis of the mixed waste. Task 4, stabilization of vitrified wastes, has as its objectives to (1) demonstrate a waste vitrification procedure for enhanced stabilization of waste materials and (2) develop a testing protocol to understand the long-term leaching behavior of the stabilized waste form. The primary objective of Task 8, Management and reporting, is coordination of this project with other programs and opportunities. In addition, management oversight will be maintained to ensure that tasks are completed and coordinated as planned and that deliverables are submitted in a timely manner. Accomplishments to date is each task are described. 62 refs

[en] Deuterium-labled compounds are useful as internal standards for quantitative analyses using gas chromatography coupled with mass spectrometry (GC/MS), and also as indicators in determining the fate of organic compounds in complex systems such as the environment, biological systems, and fuels processing reactions. Unfortunately, the lack of availability and high cost of many deuterium-labeled species limits their practical utility. A method requiring a minimum of equipment, supplies, and expertise was developed which enables the substitution of deuterium for aromatic hydrogen on several classes of compounds, including polycyclic aromatic hydrocarbons, phenols, aromatic N-, S-, and O-containing heterocyclic compounds, and chlorinated aromatic compounds. This method for deuterium substitution can also be used with complex mixtures as demonstrated by the deuteration of aromatic species in a coal-derived anthracene oil and a mixture of polychlorinated biphenyls (Arclor 1254). The reaction utilizes a solution containing 10 mg/mL chromium metal dissolved in 4 wt% deuterium chloride (DCl) in deuterium oxide (D₂O). Approximately 100 Mg substrate was weighed into a glass tube, one end of which had been sealed with a propane flame. A predetermined amount of DCl/D₂O solution was pipetted into the tube to give a 20:1 molar ratio of reagent deuterium to exchangeable hydrogen. The mixture was frozen in liquid nitrogen, a vacuum was applied, and the tube was sealed with a propane flame. The sealed tube was then placed in a pressure vessel and heated at 200⁰-300⁰C for an appropriate time period, usually 2 or 15 hours

[en] In order to better understand the reactions of heteroatom-containing organics which occur during liquefaction of subbituminous coal, it is necessary to distinguish between coal-derived and solvent-derived species. A coal-derived liquefaction solvent, AO/sub 4/, was deuterium-labeled by a method developed at the University of North Dakota Energy and Minerals Research Center and found to be stable under liquefaction conditions. The deuterium-labeled AO4 was reacted in the presence of unconverted coal (tetraydrofuran-insoluble material from a previous autoclave liquefaction test), water, carbon monoxide, and hydrogen sulfide at 350⁰C and 1000 psia for 30 minutes. No significant degradation in isotopic purity was observed in the mass spectra of the individual deuterated species comprising approximately 95 wt% of the deuterated solvent. Tests were also conducted with raw coal under similar liquefaction conditions to determine the amounts of coal-derived compounds evolved, and whether these compounds will undergo deuterium exchange with the deuterated solvent. Distillable products are being analyzed using GC/MS, and soluble and insoluble products are being analyzed using liquid proton and solid state C-13 NMR. The deuterium-labeling method has also been used to synthesize 16 model compounds including O-, S-, and N-containing aromatics to be used in future liquefaction tests. Analytical results including product component identification, coal conversion as determined by tetraydrofuran solubility, and changes observed in NMR spectra will be presented

[en] A simple and reliable system for determining the solubility and partitioning behavior of liquid fuel components in liquid water up to 250 C has been developed. The system shows good agreement with literature values at ambient temperature for the solubility of toluene and for fuel/water partitioning coefficients (K_fw). Toluene solubility increased ∼23-fold by raising the temperature from ambient to 200 C but was not affected at ambient temperature by changing the pressure from 1 to 50 bar. The increases in partitioning of benzene, toluene, ethylbenzene, xylenes, and naphthalene from gasoline into liquid water with increasing temperature ranged from 10-fold for benzene to 60-fold for naphthalene when the temperature was raised from ambient to 200 C. Similarly, the increases in partitioning of polycyclic aromatic hydrocarbons from diesel fuel into liquid water ranged from ∼130-fold for naphthalene to 470-fold for methylnaphthalene when the temperature was raised from ambient to 250 C. The effect of temperature on the partitioning of naphthalene into water from gasoline and from diesel fuel was similar, indicating that the fuel composition had little effect on the fuel/water partitioning behavior