Petroleum Hydrocarbon Bioventing Kinetics Determined in Soil Core, Microcosm, and Tubing Cluster Studies

Aerobic biodegradation of vapor-phase petroleum hydrocarbons was evaluated in an intact soil core from the site of an aviation gasoline release. An unsaturated zone soil core was subjected to a flow of nitrogen gas, oxygen, water vapor, and vapor-phase hydrocarbons in a configuration analogous to a biofilter or an in situ bioventing or sparging situation. The vertical profiles of vapor-phase hydrocarbon concentration in the soil core were determined by gas chromatography of vapor samples. Biodegradation reduced low influent hydrocarbon concentrations by 45 to 92 percent over a 0.6-m interval of an intact soil core. The estimated total hydrocarbon concentration was reduced by 75 percent from 26 to 7 parts per million. Steady-state concentrations were input to a simple analytical model balancing advection and first-order biodegradation of hydrocarbons. First-order rate constants for the major hydrocarbon compounds were used to calibrate the model to the concentration profiles. Rate constants for the seven individual hydrocarbon compounds varied by a factor of 4. Compounds with lower molecular weights, fewer methyl groups, and no quaternary carbons tended to have higher rate constants. The first-order rate constants were consistent with kinetic parameters determined from both microcosm and tubing cluster studies at the field site.     

Pyrometamorphism and partial melting of shales during combustion metamorphism: mineralogical,textural, and chemical effects

Eocene shales metamorphosed by a naturally ignited coal seam in the Powder River Basin, Wyoming record a continuum of mineralogic and textural changes from relatively unaltered shale to melt developed during pyrometamorphism. Samples collected along a section 2 m in length, corresponding to a temperature range of approximately 1300°C, were examined optically and by XRD, SEM, and STEM. The low temperature samples are comprised primarily of silt-sized quartz, K-feldspar, and minor amounts of other detrital minerals in a continuous matrix of illite/smectite (I/S). Delamination of phyllosilicates due to dehydroxylation occurs early in the sequence with curling of individual layers from rim to core. Within one-half meter of melted areas, phyllosilicates have undergone an essentially isochemical reconstitution with nucleation and growth of mullite crystals with maximum diameters of 50 nm, randomly distributed within a non-crystalline phase that replaces I/S. Large detrital grains remain for the most part unaffected except for the inversion of quartz to tridymite/cristobalite. Within 1 mm of the solid/melt interface, the mullitebearing clay mineral matrix is essentially homogeneous in composition with obscure grain boundaries, caused by apparent homogenization of poorly crystalline material. This material is similar in composition to parent clays and acts as a matrix to angular, remnant tridymite/cristobalite grains. Rounded, smaller silica grains have reaction rims with the non-crystalline matrix; K-feldspar is no longer present (apparently reacted with the matrix) and the matrix contains abundant pore space due to shrinkage upon dehydroxylation. As isolated pods of paralava (glass) or fractures are approached, Fe–Ti–Al oxides become abundant. Vesicular glass is separated from clinker by a well-defined interface and contains numerous phenocrysts. XRF analyses and reduced area rastering using EDS imply enrichment of the melt phase in Fe, Ca, Mg and Mn, apparently due to vapor transport from other layers lower in the sedimentary sequence.Contribution No. 490, the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan     

Kinetic study of the kaolinite-mullite reaction sequence. Part II: Mullite formation

The present work is a follow-up of the investigation on the decomposition reaction of kaolinite as a function of the defectivity of the starting material and the temperature of reaction. In the present work we study the high temperature reaction of mullite synthesis from kaolinite, from the starting point of the results obtained in the first part.Time resolved energy-dispersive powder diffraction patterns have been measured using synchrotron radiation in isothermal conditions. The apparent activation energy for mullite nucleation and growth is found to be related to the defective structure of the starting kaolinite, which thus must have an influence on the chemical homogeneity of the amorphous intermediate phase.     

Reducing global warming — The role of rice

Activities to provide energy for an expanding population are increasingly disrupting and changing the concentration of atmospheric gases that increase global temperature. Increased CO₂ and temperature have a clear effect on growth and production of rice as they are key factors in photosynthesis. Rice yields could be increased with increased levels of CO₂, however, the rise of CO₂ may be accompanied by an increase in global temperature. The effect of doubling CO₂ levels on rice production was predicted using rice crop models. They showed different effects of climate change in different countries. A simulation of the Southeast Asian region indicated that a doubling of CO₂ increases yield, whereas an increase in temperature decreases yield.Enhanced UV-B radiation resulting for stratographic ozone depletion has been demonstrated to significantly reduce plant height, leaf area and dry weight of two rice cultivars under glasshouse conditions. Data are still insufficient, however, for conclusive results on the effect of UV-B radiation on rice growth under field conditions.Rice production itself has a significant effect on global warming and atmospheric chemistry through methane emission from flooded ricefields. Water regime, soil properties and the rice plant are major factors controlling the flux of methane in ricefields. Global and regional estimates of methane emission rates are still highly uncertain and tentative. Integration of mechanistic modeling of methane fluxes with geographic information systems of factors controlling these processes are required to improve estimates and predictions.     

Paraffin hydrocarbon patterns in petroleum-polluted mussels

This paper explains how modern analytical techniques can be used to detect hydrocarbons in marine organisms at extremely low concentrations, below those detectable by taste or smell.     

Oxide minerals in lithic fragments from Luna 20 fines

One hundred and seventy-six oxide mineral grains in the Luna 20 samples were analyzed by electron microprobe. Spinel is the most abundant oxide, occurring in troctolite fragments. Next most abundant is ilmenite, which occurs in all rock types except those containing spinel. Chromite also occurs in all rock types except those containing spinel. Minor amounts of ulvöspinel, armalcolite, zirkelite, baddeleyite and an unidentified TiO₂-rich phase were also found.Spinel grains are predominantly spinel-hercynite solid solutions, commonly with very minor chromite. The $\text{Fe}\text{(Fe + Mg)}$ ratio is generally lower than in spinel from Apollo 14 rocks. Chromites in non-mare rocks are similar to those from mare rocks. Ilmenite of mare origin is Mg-poor and Zr-rich compared to non-mare ilmenite; these elements may therefore be useful in determining the origin of ilmenite grains.Phase equilibria considerations suggest that spinel troctolite crystallized from a melt high in alumina; a likely candidate is the high-alumina basalt of Prinzet al. (1973a).Sub-micron wide rods of metallic Fe occur in plagioclase grains and may have formed by sub-solidus reduction processes.     

High-temperature condensates in chondrites and the environment in which they formed

Chemical compositions of melilitee and titaniferous pyroxenes in calcium- and aluminum-rich inclusions in carbonaceous chondrites are consistent with their origin as hightemperature condensates from a gas of solar composition. Thermodynamic calculations indicate that the highest temperature minerals equilibrated with the gas at temperatures in excess of 1400°K. The lack of evidence for direct condensation of gas to liquid enables us to set an upper limit to the pressure when the inclusions formed which may be as low as 2.2 × 10^?3atm. Glasses, which are commonly found in chondrules, are interpreted as quench products of liquids formed by secondary reheating of primary solid condensates. The high-temperature inclusions constitute evidence that accretion of grains to cm-sized objects occurred at a very early stage in the evolution of the solar nebula.     

A lunar core of Fe-Ni-S

Several workers have proposed that lunar samples were magnetized by a field created by a lunar core of molten Fe. Low abundances of siderophile elements in lunar rocks are compatible with formation of a metallic lunar core. A molten Fe core requires that the bulk of the Moon was above, or close to, the melting point, a requirement which disagrees with most models of the lunar thermal regime.A core (or perhaps a layer or pockets) of molten Fe-Ni-S, at or close to the eutectic composition would act as a lunar dynamo, and be at a temperature (approx. 1000°C) consistent with some reasonable models of lunar thermal history. The existence of a Fe-Ni-S core would also partly explain the depletion in volatile elements in lunar basalts. Such a core, occupying up to 20 per cent of the Moon's radius requires a bulk S content for the moon of only 0.3 wt per cent.