The lunar geochemistry of chromium and vanadium

Crystal/liquid partition coefficients for Cr, V, Mn, and Fe have been determined experimentally between olivine, orthopyroxene, clinopyroxene and silicate melt possesing the composition of a primitive lunar green glass, at oxygen fugacities appropriate to the lunar interior. These species all behave essentially as compatible elements and possess crystal/liquid partition coefficients mostly between 0.3 and 0.9. Partition coefficients for Cr, V, and Mn are generally similar to those of Fe. This implies that crystal/liquid fractionation processes in the lunar interior which do not involve the participation of spinels would not have been effective in fractionating MnO, CrO, and VO from FeO. The well-known constancy of FeO/MnO ratios in nearly all lunar rocks is a reflection of this behaviour. It is shown that comparably strong correlations between CrO-;FeO and VO-;FeO exist for lunar highland breccias and soils from all sites and that these correlations extend to primitive lunar volcanic glasses associated with mare volcanism, strongly suggesting that the CrO/FeO and VO/FeO ratios so derived are of global importance. The observed ratios characterizing differentiated regions of the Moon can be combined with the corresponding ratios for residual refractory portions of the Moon, using measured partition coefficients for Fe, Mg, Cr, V, and Mn between olivine, orthopyroxene and liquid. Bulk Moon abundances for Cr and V have been calculated for a range of reasonable assumptions concerning the petrogenetic relationships between differentiated portions of the Moon and complementary refractory residua consisting of olivine and orthopyroxene mineralogies. Because of the small differences in crystal liquid partition coefficients between FeO, CrO, and VO, these estimates are insensitive to large variations in the models. The bulk Moon is accordingly estimated to contain 2190–2463 ppm Cr and 79–95 ppm V. These values are very similar to the Cr and V contents of the Earth's mantle, estimated as 3010 ppm Cr and 81 ppm V by Sun (1982). The geochemical implications of these similarities are discussed.     

The transition from peraluminous to peralkaline granitic melts: Evidence from melt inclusions and accessory minerals

Fractional crystallization of peraluminous F- and H₂O-rich granite magmas progressively enriches the remaining melt with volatiles. We show that, at saturation, the melt may separate into two immiscible conjugate melt fractions, one of the fractions shows increasing peraluminosity and the other increasing peralkalinity. These melt fractions also fractionate the incompatible elements to significantly different degrees. Coexisting melt fractions have differing chemical and physical properties and, due to their high density and viscosity contrasts, they will tend to separate readily from each other. Once separated, each melt fraction evolves independently in response to changing T/P/X conditions and further immiscibility events may occur, each generating its own conjugate pair of melt fractions. The strongly peralkaline melt fractions in particular are very reactive and commonly react until equilibrium is attained. Consequently, the peralkaline melt fraction is commonly preserved only in the isolated melt and mineral inclusions.

We demonstrate that the differences between melt fractions that can be seen most clearly in differing melt inclusion compositions are also visible in the composition of the resulting ore-forming and accessory minerals, and are visible on scales from a few micrometers to hundreds of meters.     

Organic pollutants associated with macromolecular soil organic matter: Mode of binding

A study of ether-linked moieties in macromolecular bound residues of polycyclic aromatic hydrocarbons (PAH) generated in bioremediation experiments was performed using high temperature hydrolysis degradation with subsequent analysis of the products by GC-MS. This hydrolysis reaction was specifically designed to cleave ether bonds including relatively stable diarylether structures. Among the reaction products, aromatic alcohols representing typical microbiologically derived metabolites of PAH were found in addition to natural compounds. Thus, parts of the bound residues appeared to be linked within the macromolecular material by ether bonds. Model experiments with an oxidoreductase enzyme and aromatic alcohols indicate the formation of these ether bonds to be an enzyme-catalysed process.     

ELNES spectroscopy of mixed Si coordination minerals

 Si K- and L-edge ELNES spectroscopy and multiple-scattering (MS) calculations are used to examine mixed Si coordination compounds varying in Si^VI:Si^IV ratio. As in previous studies, the edges are influenced mainly by silicon coordination (tetrahedral vs. octahedral), as supported by the MS calculations. We demonstrate two methods semi-quantitatively to extract the value of Si^VI/(Si^VI+Si^IV): (1) A linear relationship between the L_2,3-L₁ splitting and Si^VI/(Si^VI+Si^IV) is observed, (2) a fitting method based on the coaddition of reference tetrahedral and octahedral Si spectra is applied to both Si K- and L-edge ELNES spectra. Received: February 10, 1997 / Revised, accepted: May 23, 1997     

Floodgate Operations and Fish Communities in Tidal Creeks of the Lower Fraser River (British Columbia,Canada)

Tidal creeks in large coastal deltas can be important habitat for fish but are often highly modified by human activities. Connectivity between tributary creeks and mainstem channels is often constrained by structures such as dikes and floodgates, designed to protect urban and agricultural areas from flooding. While they play important roles in flood mitigation, floodgates can diminish habitat quality and block fish from accessing tidal creeks. It is likely that floodgates differ in their operations and may consequently open for different amounts of time; however, floodgate operations and their effects are not well quantified. We asked the question: how does the mechanical functioning of these floodgates affect fish communities in tidal creeks? We used time-lapse cameras and quantified the timing of gate openings for 22 tributaries of the Lower Fraser River in British Columbia, Canada, and related these operational data to differences in fish communities above and below floodgates. Floodgate operations varied substantially, with some floodgates opening daily while others opened less than 20% of the day, on average. Sites with floodgates that seldom opened were associated with greater differences in fish communities and with reduced upstream native species richness by about one species on average. Where floodgates opened infrequently, we also found lower upstream dissolved oxygen concentrations than at sites where floodgates opened for longer periods of time. Thus, floodgate operations can influence fish communities as well as water quality. These data indicate a large scope for improving floodgate operations for connectivity.     

Volume relaxation of compacted SiO2 glass: a model for the conservation of natural diaplectic glasses

Relaxation experiments on vitreous SiO₂, densified at 900°C, 20 kbar to a permanent density of 2.36 g cm^?3 yield an activation energy of69 ± 5kcal mol^?1 in the temperature range 700–800°C. The data can be used to estimate minimum cooling rates, maximum depositional temperatures or maximum thicknesses of shock-metamorphosed rocks containing diaplectic glasses, if relaxation of a glass densified under dynamic conditions is assumed to be similar to that of statically densified glass.     

Structure proof and significance of stereoisomeric 28,30-bisnorhopanes in petroleum and petroleum source rocks

Two C₂₈H₄₈-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring $\text{D}\text{E}$cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.     

A komatiite component in Apollo 16 highland breccias: implications for the nickel-cobalt systematics and bulk composition of the moon

The lunar crust at the Apollo 16 landing site contains substantial amounts of a “primitive component” in which the ferromagnesian group of elements is concentrated. The composition of this component can be retrieved via an analysis of mixing relationships displayed by lunar breccias. It is found to be a komatiite which is compositionally similar to terrestrial komatiites both in major and minor elements. The komatiite component of the lunar crust is believed to have formed by extensive degrees of melting of the lunar interior at depths greater than were involved in the formation of the lunar magma ocean which was parental to the crust. After formation of the anorthositic crust, it was invaded by extensive flows and intrusions of komatiite magma from these deeper source regions. The komatiites became intimately mixed with the anorthosite by intensive meteoroid impacts about 4.5 b.y. ago, thereby accounting for the observed mixing relationships displayed by the crust. The compositional similarity between lunar and terrestrial komatiites strongly implies a corresponding similarity between the compositions of their source regions in the lunar interior and the Earth's upper mantle. The composition of the lunar interior can be modelled more specifically by combining the komatiite composition with its liquidus olivine composition (as determined experimentally) in proportions chosen so as to produce a cosmochemically acceptable range of Mg/Si ratios for the bulk Moon. Except for higher FeO and lower Na₂O, the range of compositions thereby obtained for the bulk moon is very similar to the composition of the Earth's upper mantle.The effects of meteoritic contamination on the abundances of cobalt and nickel in lunar highland breccias were subtracted on the assumption that the contaminating projectiles were chondritic. The cobalt and nickel residuals thereby obtained were found to correlate strongly with the (Mg + Fe) content of the breccias, demonstrating that the Co and Ni are associated with the ferromagnesian component of the breccias and are genuinely indigenous to the Moon. The lunar highland Co and Ni residuals also display striking Ni/Co versus Ni correlations which follow a similar trend to those displayed by terrestrial basalts, picrites and komatiites. The lunar trends provide further decisive evidence of the indigenous nature of the Co and Ni residuals and suggest the operation of extensive fractionation controlled by olivine-liquid equilibria in producing the primitive component of the lunar breccias. Indigenous nickel abundances at the Apollo 14, 15 and 17 sites are much lower than at the Apollo 16 site, although rocks from all sites follow the same Ni/Co versus Ni trends. It is suggested that the primitive component at the Apollo 14, 15 and 17 sites was generally of basaltic composition, in contrast to the komatiitic nature of the Apollo 16 primitive component.     

Oxygen deficient perovskites in the system CaSiO3–CaAlO2.5 and implications for the Earth’s interior

Oxygen deficient perovskites of the system CaSiO₃–CaAlO_2.5 have been synthesised at high-pressure and -temperature conditions relevant to the Earth’s transition zone in order to investigate their stabilities in the Earth’s mantle and determine structural properties associated with vacancy incorporation. Two polysomes of thermodynamically stable defect perovskites with Ca(Al_0.4Si_0.6)O_2.8 and Ca(Al_0.5Si_0.5)O_2.75 stoichiometry have been identified. The ordering of oxygen defects into pseudo-cubic (111) layers results in well-ordered ten- or eightfold superstructures, respectively. At all other compositions examined, a metastable formation of perovskites has been observed instead, which are assumed to grow initially disordered. These are now characterised by tiny domains, formed due to subsequent ordering of vacancies along various pseudo-cubic {111} layers. Both ordered defect perovskites show a large P–T stability field ranging from about 9–18 GPa and 4–12 GPa, respectively. Microstructural TEM analyses revealed the presence of growth and ferroelastic twins, which indicate a phase transition from rhombohedral to monoclinic symmetry during quenching. Electron energy loss spectroscopy of Si and Al K edges point at the presence of tetrahedral, octahedral and maybe some pentacoordinated silicon, whereas aluminium is predominantly octahedrally coordinated with minor fractions in lower coordination. Observed properties are interpreted in terms of a new structural model, explaining the observed phase transition and formation of different twin laws as well as giving reasons for the development of such large superstructures. With respect to phase relations of the transition zone, the potential occurrence of such defect perovskites in the Earth’s interior is discussed.