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.     

Variability in the power spectrum of solar five-minute oscillations

Two-dimensional power spectra of solar five-minute oscillations display prominent ridge structures in (k, ω) space, where k is the horizontal wavenumber and ω is the temporal frequency. The positions of these ridges in k and ω can be used to probe temperature and velocity structures in the subphotosphere. We have been carrying out a continuing program of observations of five-minute oscillations with the diode array instrument on the vacuum tower telescope at Sacramento Peak Observatory (SPO). We have sought to establish whether power spectra taken on separate days show shifts in ridge locations; these may arise from different velocity and temperature patterns having been brought into our sampling region by solar rotation. Power spectra have been obtained for six days of observations of Doppler velocities using the Mgi λ5173 and Fei λ5434 spectral lines. Each data set covers 8 to 11 hr in time and samples a region 256″ × 1024″ in spatial extent, with a spatial resolution of 2″ and temporal sampling of 65 s. We have detected shifts in ridge locations between certain data sets which are statistically significant. The character of these displacements when analyzed in terms of eastward and westward propagating waves implies that changes have occurred in both temperature and horizontal velocity fields underlying our observing window. We estimate the magnitude of the velocity changes to be on the order of 100 m s^-1; we may be detecting the effects of large-scale convection akin to giant cells.     

Morphological analysis of the drainage system in the Eastern Alps

We study the morphology of the major rivers draining the Eastern Alps to test whether the active tectonics of this part of the orogen is reflected in the shape of channel profiles of the river network. In our approach we compare channel profiles measured from digital elevation models with numerically modelled channel profiles using a stream power approach. It is shown that regions of high stream power coincide largely with regions of highest topography and largest uplift rates, while the forelands and the Pannonian Basin are characterised by a significantly lower stream power. From stream power modelling we conclude that there is young uplift at the very east of the Eastern Alps, in the Bohemian Massif and in the Pohorje Range. The impact of the Pleistocene glaciations is explored by comparing properties of rivers that drain in proximal and distal positions relative to the ice sheet during the last glacial maximum. Our analysis shows that most knick points, wind gaps and other non-equilibrium features of catchments covered by ice during the last glaciations (Salzach, Enns) can be correlated with glacial processes. In contrast the ice free catchments of the Mur and Drava are characterized by channels in morphological equilibrium at the first approximation and are showing only weak evidence of the strong tectonic activity within these catchments. Finally, the channel profiles of the Adige and the divide between the upper Rhine and Danube catchments differ significantly from the other catchments. We relate this to the fact that the Adige and the Rhine respond to different base levels from the remainder of the Eastern Alps: The Adige may preserve a record from the Messininan base level change and the Rhine is subject to the base level lowering in the Rhine Graben.     

The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.     

Carbon biogeochemistry of the Betsiboka estuary (north-western Madagascar)

Madagascar’s largest estuary (Betsiboka) was sampled along the salinity gradient during the dry season to document the distribution and sources of particulate and dissolved organic carbon (POC, DOC) as well as dissolved inorganic carbon (DIC). The Betsiboka was characterized by a relatively high suspended matter load, and in line with this, low DOC/POC ratios (0.4–2.5). The partial pressure of CO₂ (pCO₂) was generally above atmospheric equilibrium (270–1530 ppm), but relatively low in comparison to other tropical and subtropical estuaries, resulting in low average CO₂ emission to the atmosphere (9.1 ± 14.2 mmol m⁻² d⁻¹). Despite the fact that C4 vegetation is reported to cover >80% of the catchment area, stable isotope data on DOC and POC suggest that C4 derived material comprises only 30% of both pools in the freshwater zone, increasing to 60–70% and 50–60%, respectively, in the oligohaline zone due to additional lateral inputs. Sediments from intertidal mangroves in the estuary showed low organic carbon concentrations (<1%) and δ¹³C values (average −19.8‰) consistent with important inputs of riverine imported C4 material. This contribution was reflected in δ¹³C signatures of bacterial phospholipid derived fatty acids (i + a15:0), suggesting the potential importance of terrestrial organic matter sources for mineralization and secondary production in coastal ecosystems.     

Thermal stability of ladderane lipids as determined by hydrous pyrolysis

Anaerobic ammonium oxidation (anammox) has been recognized as a major process resulting in loss of fixed inorganic nitrogen in the marine environment. Ladderane lipids, membrane lipids unique to anammox bacteria, have been used as markers for the detection of anammox in marine settings. However, the fate of ladderane lipids after sediment burial and maturation is unknown. In this study, anammox bacterial cell material was artificially matured by hydrous pyrolysis at constant temperatures ranging from 120 to 365 °C for 72 h to study the stability of ladderane lipids during progressive dia- and catagenesis. HPLC-MS/MS analysis revealed that structural alterations of ladderane lipids already occurred at 120 °C. At temperatures >140 °C, ladderane lipids were absent and only more thermally stable products could be detected, i.e., ladderane derivatives in which some of the cyclobutane rings were opened. These diagenetic products of ladderane lipids were still detectable up to temperatures of 260 °C using GC-MS. Thus, ladderane lipids are unlikely to occur in ancient sediments and sedimentary rocks, but specific diagenetic products of ladderane lipids will likely be present in sediments and sedimentary rocks of relatively low maturity (i.e., C₃₁ hopane 22S/(22S + 22R) ratio <0.2 or ββ/(αβ + βα + ββ) ratio of >0.5).     

Numerical modeling for analyzing thermal surface anomalies induced by underground coal fires

Coal seams burning underneath the surface are recognized all over the world and have drawn increasing public attention in the past years. Frequently, such fires are analyzed by detecting anomalies like increased exhaust gas concentrations and soil temperatures at the surface. A proper analysis presumes the understanding of involved processes, which determine the spatial distribution and dynamic behavior of the anomalies.In this paper, we explain the relevance of mechanical and energy transport processes with respect to the occurrence of temperature anomalies at the surface. Two approaches are presented, aiming to obtain insight into the underground coal fire situation: In-situ temperature mapping and numerical simulation. In 2000 to 2005, annual temperature mapping in the Wuda (Inner Mongolia, PR China) coal fire area showed that most thermal anomalies on the surface are closely related to fractures, where hot exhaust gases from the coal fire are released. Those fractures develop due to rock mechanical failure after volume reduction in the seams. The measured signals at the surface are therefore strongly affected by mechanical processes.More insight into causes and effects of involved energy transport processes is obtained by numerical simulation of the dynamic behavior of coal fires. Simulations show the inter-relation between release and transport of thermal energy in and around underground coal fires. Our simulation results show a time delay between the coal fire propagation and the observed appearance of the surface temperature signal. Additionally, the overall energy flux away from the burning coal seam into the surrounding bedrock is about 30-times higher than the flux through the surface. This is of particular importance for an estimation of the energy released based on surface temperature measurements. Finally, the simulation results also prove that a fire propagation rate estimated from the interpretation of surface anomalies can differ from the actual rate in the seam.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Phytoreduction and volatilization of mercury by ascorbate in Arabidopsis thaliana, European beech and Norway spruce

Mercury vapor (Hg⁰) emission from plants contributes to the atmospheric Hg cycle. Young barley (Hordeum vulgare L.) plants grown on a hydroponic cultivation medium containing Hg(II) have previously been shown to increase their Hg⁰ emission significantly by reduction of Hg(II) with endogenous ascorbic acid. Regarding the potential contribution to the Hg cycle from the vast forest-covered areas, it was important to investigate this mechanism in trees. The increase in Hg⁰ emission from young European beech plants cultivated on a HgCl₂ medium exceeded that from controls by ca. tenfold and was proportional to the Hg(II) concentration. From these experiments, a flux of 12.8 μg Hg⁰/h/m² was estimated at an exposure of the roots to 20 μM Hg(II). Mercury vapor release from homogenates of Norway spruce needles exceeded that from European beech leaves by a factor of 2.3–4, i.e. in proportion to the reported AA concentrations; the reduction was maximal at alkaline pH which is typical for AA. The 8.4-fold difference in Hg⁰ release between homogenates from wild-type Arabidopsis thaliana and from its AA-deficient mutant vtc 1-1 also paralleled the reported difference in AA levels of both species. It is concluded that the phytoreduction and vaporization of Hg by AA is an important mechanism as much for Hg detoxification in trees as for Hg emission to the atmosphere. The efficiency of this process seems to result from the optimal coordination of transfer and biochemical transformation of mercuric ions and Hg vapor. There is no evidence for a relevant difference in the mechanisms of biogenic Hg(II) reduction between grass plants and trees.     

The hydrochemistry of a semi-arid pan basin case study: Sua Pan,Makgadikgadi, Botswana

This study presents results on the fluid and salt chemistry for the Makgadikgadi, a substantial continental basin in the semi-arid Kalahari. The aims of the study are to improve understanding of the hydrology of such a system and to identify the sources of the solutes and the controls on their cycling within pans. Sampling took place against the backdrop of unusually severe flooding as well as significant anthropogenic extraction of subsurface brines. This paper examines in particular the relationship between the chemistry of soil leachates, fresh stream water, salty lake water, surface salts and subsurface brines at Sua Pan, Botswana with the aim of improving the understanding of the system’s hydrology. Occasionally during the short wet season (December–March) surface water enters the saline environment and precipitates mostly calcite and halite, as well as dolomite and traces of other salts associated with the desiccation of the lake. The hypersaline subsurface brine (up to TDS 190,000 mg/L) is homogenous with minor variations due to pumping by BotAsh mine (Botswana Ash (Pty) Ltd.), which extracts 2400 m³ of brine/h from a depth of 38 m. Notable is the decrease in TDS as the pumping rate increases which may be indicative of subsurface recharge by less saline water. Isotope chemistry for Sr (⁸⁷Sr/⁸⁶Sr average 0.722087) and S (δ³⁴S average 34.35) suggests subsurface brines have been subject to a lithological contribution of undetermined origin. Recharge of the subsurface brine from surface water including the Nata River appears to be negligible.