Kinetics of the Reactions of IO with HO2 and O(3P)

A discharge-flow tube coupled with resonance fluorescence and chemiluminescence detection has been used to investigate the reactions IO + HO₂ products (1) and IO + O(³P) I + O₂(2), at T = 296 ± 1 K and P = 1.7 - 2 Torr. The rate constants k_-1 and k₂ have been found to be (7.1 ± 1.6) × 10^-11 cm³ molecule^-1 s^-1 and (1.35 ± 0.15) × 10^-10 cm³ molecule^-1 s^-1, respectively.     

Chemical processes affecting alkalis and alkaline earths during continental weathering

The alkali and alkaline earth concentrations in the Toorongo Granodiorite weathering profile are controlled by two competing processes; leaching of cations from primary minerals during their degradation to clays; fixation, by exchange and adsorption, of the same cations onto the secondary clay minerals. Degradation and leaching dominate the early weathering stages whereas during the advanced stages, exchange and adsorption onto clays are of most influence.The alkali and alkaline earth compositional changes in the Toorongo Granodiorite weathering profile are typical of changes occurring during weathering of the continents, consequently the following generalizations apply to continental weathering. Ca, Sr and Na are most rapidly and most strongly removed (as dissolved species) during weathering of fresh continental rocks. Although large quantities of Mg are transported to the marine environment as dissolved species, appreciable amounts remain (fixed in secondary clay minerals) at the weathering site to be removed during mass wasting of continental weathering profiles. Large quantities of Rb, Cs and Ba, fixed in continental weathering profiles by exchange and adsorption onto secondary clays, are transported from the continents only during mass wasting of the continents.     

The effect of manganese on olivine-quartz-orthopyroxene stability

The effect of manganese on the stability of ferrosilite relative to fayalite + quartz has been experimentally determined to assess its importance to orthopyroxene barometry. Reaction reversals in a piston-cylinder apparatus were obtained to within 0.1-kbar intervals indicating instability of Fs₉₅Rh₅ below 10.3, 10.9, 11.4, 12.2, 12.9, 13.7 kbar and Fs₉₀Rh₁₀ below 9.8, 10.4, 10.9, 11.6, 12.4 and 13.2 kbar at 750, 800, 850, 900, 950 and 1000°C, respectively. Each mole % MnSiO₃ extends the pyroxene stability by approximately 0.12 kbar relative to FeSiO₃. Electron microprobe analyses of run products indicate a small preference of Mn for pyroxene over olivine withK_DMn-Fe^opx-oliv = 1.2?1.5, similar to values observed for natural pairs. Mössbauer spectra are consistent with a random distribution of Mn between the M1 and M2 sites in the orthopyroxene. These experimental data allow downward revision of pressure estimates based on the orthopyroxene barometer in areas where Mn is a significant component in orthopyroxene.     

Dissolved free amino acids in interstitial waters of Georgia salt marsh soils

The patterns of concentration of dissolved free amino acids (DFAA) are different and more variable in pore water of soils from a Georgia salt marsh than in most surface waters. Elevated concentrations of DFAA (up to 8850 nmoles liter^?1) and high relative levels of alanine and glutamic acid suggest that bacteria may produce these amino acids. In addition to the common protein amino acids, an unidentified compound was present and was the dominant free amino acid in some sections. This compound appeared to be specific to pore waters as it was not observed in surface waters or in hydrolysates of sediments, bacteria or plants from the marsk.     

An experimental determination of rare earth partition coefficients between a chloride containing vapor phase and silicate melts

The partitioning behavior of cerium, europium, gadolinium and ytterbium between an aqueous “vapor” phase and water saturated silicate melt have been experimentally examined using a new experimental approach employing radioactive tracers and a double-capsule technique. Equilibrium was established by reversing the partition coefficient¹ and by betatrack autoradiography. Aqueous solution compositions were varied by adding different amounts of chloride and in some cases fluoride or carbon dioxide. The H₂O contents of the Spruce Pine pegmatite melts were varied by conducting experiments at 4.0 kb, 800°C and at 1.25 kb, 800°C. A jadeite-nepheline composition (75 wt% Jadeite) also was employed at 4.0 kb, 800°C.The chloride experiments (Spruce Pine 4 kb, 800°C) show a linear relationship between the cube of the chloride molality and the partition coefficients of the trivalent rare earths. Europium, under the experimental fO₂ conditions (quartz-fayalite-magnetite buffer), varied linearly as the fifth power of the chloride molality. At the chloride molalities examined (<1.1 mC1), all the rare earths partitioned preferentially into the melt phase (K_P^RE <1). Relative to pure water, the presence of chloride and fluoride fon increased the partitioning of the individual rare earths into the vapor phase, while carbon dioxide did not. Europium anomalies were recorded 1n all experiments, particularly those involving the Spruce P1ne melt at 4.0 kb and 800°C which displayed a large positive europium anomaly at all chloride molalities. Furthermore, a relative fractionation of the trivalent rare earths was also observed in these experiments, such that K_P^Ce>K_P^Gd>K_P^Yb. The smaller ytterbium ion was consistently concentrated in the melt phase relative to the other rare earths in all experiments on the Spruce Pine composition. Experiments on the jadeite-nepheline composition showed no relative fractionation and a positive europium anomaly. The 1.25 kb experiment on the Spruce Pine composition showed a negative europium anomaly in plots of K_p^RE vs. REE.The overall rare earth partitioning at a constant chloride molality (mCl = .914) was such that K_P^SP(1.25 kb) > K_P^SP(4.0 kb) > K_P^Jd-Ne(4.0 kb), where SP = Spruce Pine, Jd-Ne = jadeitenepheli Using the model of Burnnam (1975), It is suggested that the trivalent rare earth partitioning is related to the cube of the melt octahedral site concentration; a property which 1n hydrous melts 1s dependent on melt composition and hydroxyl molality. Excellent agreement was found for the Spruce Pine melt, whereas the jadeite-nepheline melt gave apparent hydroxyl molalities which were too high for the measured partition coefficient. Additional octahedral sites are proposed for this unusual composition perhaps due to some aluminum in 6-fold coordination. The apparent compositional variation of europium partitioning at a constant oxygen fugacity is believed to be related to both the octahedral melt site concentration for trlvalent europium and an 8-coordinated site concentration for divalent europium. Any parameter which affects the numbers of these sites (_PH₂O, melt composition) will affect the rare earth partitioning. The observed dependency of the partition coefficient on the structural state of the melt could be as significant as its dependency on crystalline structural constraints. Furthermore, since _PH₂O can drastically effect the melt structural state, its effects could be reflected in melt/crystal partition coefficients.     

Low temperature alteration processes affecting ultramafic bodies

At low temperatures, in the presence of an aqueous solution, olivine and orthopyroxene are not stable relative to the hydrous phases brucite, serpentine and talc. Alteration of dunite and peridotite to serpentine or steatite bodies must therefore proceed via non-equilibrium processes. The compositions of natural solutions emanating from dunites and peridotites demonstrate that the dissolution of forsterite and/or enstatite is rapid compared with the precipitation of the hydrous phases; consequently, dissolution of anhydrous minerals controls the chemistry of such solutions. In the presence of an aqueous phase, precipitation of hydrous minerals is the rate-controlling step.Brucite-bearing and -deficient serpentinites alter at low temperature by non-equilibrium processes, as evidenced by the composition of natural solutions from these bodies. The solutions approach equilibrium with the least stable hydrous phase and, as a consequence, are supersaturated with other hydrous phases. Dissolution of the least stable phase is rapid compared to precipitation of other phases, so that the dissolving mineral controls the solution chemistry.Non-equilibrium alteration of anhydrous ultramafic bodies continues until at least one anhydrous phase equilibrates with brucite, chrysotile or talc. The lowest temperature (at a given pressure) at which this happens is defined by the reaction:

$\text{3H}{}_2\text{O + 2Mg}{}_2\text{SiO}{}_4\text{? Mg}{}_3\text{Si}{}_2\text{O}{}_5\text{(OH)}{}_4\text{+ Mg(OH)}{}_2$

(Johannes, 1968, Contrib. Mineral. Petrol. 19, 309–315) so that non-equilibrium alteration may occur well into greenschist facies metamorphic conditions.     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.