Assessing soil and groundwater contamination from biofuel spills.

Future modifications of fuels should include evaluation of the proposed constituents for their potential to damage environmental resources such as the subsurface environment. Batch and column experiments were designed to simulate biofuel spills in the subsurface environment and to evaluate the sorption and desorption behavior of target fuel constituents (i.e., monoaromatic and polyaromatic hydrocarbons) in soil. The extent and reversibility of the sorption of aromatic biofuel constituents onto soil were determined. When the ethanol content in ethanol-blended gasoline exceeded 25%, enhanced desorption of the aromatic constituents to water was observed. However, when biodiesel was added to diesel fuel, the sorption of target compounds was not affected. In addition, when the organic carbon content of the soil was higher, the desorption of target compounds into water was lower. The empirical relationships between the organic-carbon normalized sorption coefficient (Koc) and water solubility and between Koc and the octanol-water partition coefficient (Kow) were established. Column experiments were carried out for the comparison of column effluent concentration/mass from biofuel-contaminated soil. The dissolution of target components depended on chemical properties such as the hydrophobicity and total mass of biofuel. This study provides a basis for predicting the fate and transport of hydrophobic organic compounds in the event of a biofuel spill. The spill scenarios generated can assist in the assessment of biofuel-contaminated sites.

Using electrospray-assisted pyrolysis ionization/mass spectrometry for the rapid characterization of trace polar components in crude oil, amber, humic substances, and rubber samples.

We describe the use of electrospray-assisted pyrolysis ionization/mass spectrometry (ESA-Py/MS) to selectively ionize trace polar compounds that coexist with large amounts of nonpolar hydrocarbons in crude oil, amber, humic substances, and rubber samples. Samples of different origins are distinguished rapidly by their positive ion ESA-Py mass spectra without prior separation or chemical pretreatment. During ESA-Py analysis, the samples in their solid or liquid states were pyrolyzed at 590, 630 or 940 degrees C using a commercial Curie-point pyrolysis probe. The gaseous pyrolysates were transferred into a glass reaction cell. The polar compounds (M) in the pyrolysates were then ionized by electrospray ionization (ESI), yielding protonated molecules (MH+). Although the major components of the pyrolysates are nonpolar hydrocarbons, their lack of functional groups that can receive a proton in the ESA-Py source results in no hydrocarbon ion signals being produced; thus, the positive ions detected in ESA-Py mass spectra all result from trace polar components in the pyrolysates.

Determination of the carbon kinetic isotope effects on propane hydroxylation mediated by the methane monooxygenases from Methylococcus capsulatus (Bath) by using stable carbon isotopic analysis.

Authentic propane with known position-specific carbon isotope composition at each carbon atom was subjected to hydroxylation by the particulate and soluble methane monooxygenase (pMMO and sMMO) from Methylococcus capsulatus (Bath), and the corresponding position-specific carbon isotope content was redetermined for the product 2-propanol. Neither the reaction mediated by pMMO nor that with sMMO showed an intermolecular (12)C/(13)C kinetic isotope effect effect on the propane hydroxylation at the secondary carbon; this indicates that there is little structural change at the carbon center attacked during formation of the transition state in the rate-determining step. This finding is in line with the concerted mechanism proposed for pMMO (Bath), and suggested for sMMO (Bath), namely, direct side-on insertion of an active "O" species across the C-H bond, as has been previously reported for singlet carbene insertion.