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.     

Speciation of volatile arsenic at geothermal features in Yellowstone National Park

Geothermal features in the Yellowstone National Park contain up to several milligram per liter of aqueous arsenic. Part of this arsenic is volatilized and released into the atmosphere. Total volatile arsenic concentrations of 0.5-200 mg/m³ at the surface of the hot springs were found to exceed the previously assumed nanogram per cubic meter range of background concentrations by orders of magnitude. Speciation of the volatile arsenic was performed using solid-phase micro-extraction fibers with analysis by GC-MS. The arsenic species most frequently identified in the samples is (CH₃)₂AsCl, followed by (CH₃)₃As, (CH₃)₂AsSCH₃, and CH₃AsCl₂ in decreasing order of frequency. This report contains the first documented occurrence of chloro- and thioarsines in a natural environment. Toxicity, mobility, and degradation products are unknown.     

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.     

Atmospheric nitrogen inputs into the North Sea: effect on productivity

The ANICE (Atmospheric Nitrogen Inputs into the Coastal Ecosystem) project addressed the atmospheric deposition of nitrogen to the North Sea, with emphasis on coastal effects. ANICE focused on quantifying the deposition of inorganic nitrogen compounds to the North Sea and the governing processes. An overview of the results from modelling and experimental efforts is presented. They serve to identify the role of the atmosphere as a source of biologically essential chemical species to the marine biota. Data from the Weybourne Atmospheric Observatory (UK) are used to evaluate the effect of short episodes with very high atmospheric nitrogen concentrations. One such episode resulted in an average deposition of 0.8 mmol N m⁻² day⁻¹, which has the potential to promote primary productivity of 5.3 mmol C m⁻² day⁻¹. This value is compared to long-term effects determined from model results. The total calculated atmospheric deposition to the North Sea in 1999 is 948 kg N km⁻¹, i.e. 0.19 mmol N m⁻² day⁻¹ which has the potential to promote primary productivity of 1.2 mmol C m⁻² day⁻¹. Detailed results for August 1999 show strong gradients across the North Sea due to adjacent areas where emissions of NO_x and NH₃ are among the highest in Europe. The average atmospheric deposition to the southern part of the North Sea in August 1999 could potentially promote primary production of 2.0 mmol C m⁻² day⁻¹, i.e. 5.5% of the total production at this time of the year in this area of the North Sea. For the entire study area the atmospheric contribution to the primary production per m² is about two-third of this value. Most of the deposition occurs during short periods with high atmospheric concentrations. This atmospheric nitrogen is almost entirely anthropogenic in origin and thus represents a human-induced perturbation of the ecosystem.     

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     

Investigation into albedo-controlled energy loss during the last glaciation

In recent years, attention has increasingly been paid to the question of the stability of the earth's climate. It has been observed that changes in climate are usually related to changes in the earth's surface. On this question, Liedtke writes ‘A change in climate can lead to considerable landscape changes’ (Liedtke 1990, p. 38). There seems to be some form of interaction between climate and the condition of the earth's surface. If solar radiation is taken to be the primary energy source for the earth's climate, the question arises as to how insolation affects the character of the earth's surface, and vice versa, how does the character of the earth's surface affect the insolation which occurs? Reconstructions of the last great Pleistocene glaciation 18,000 years ago show that the form of the earth's surface at that time was considerably different to its present form. In view of the interaction mentioned above between climate and earth surface, does this suggest a difference between the earth's radiation budget 18,000 years ago and that of today? If, as is widely believed, the area of the earth's surface covered by ice 18,000 years ago was approximately three times the current area (Liedtke 1990, p. 42), this presumably would have had at least some influence on the earth's radiation budget. The ice-covered areas may have modified the radiation budget by means of their high reflexivity. In other words, an albedo-related loss of radiation may have occurred. The results of this investigations show, that the global radiation budget at 18,000 B.P was about 7- -10% less than that of today.     

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.