Vanadium in peridotites as a proxy for paleo-fO2 during partial melting : prospects, limitations, and implications

The compatibility of vanadium (V) during mantle melting is a function of oxygen fugacity (fO₂): at high fO₂’s, V becomes more incompatible. The prospects and limitations of using the V content of peridotites as a proxy for paleo-fO₂ at the time of melt extraction were investigated here by assessing the uncertainties in V measurements and the sensitivity of V as a function of degree of melt extracted and fO₂. V-MgO and V-Al₂O₃ systematics were found to be sensitive to fO₂ variations, but consideration of the uncertainties in measurements and model parameters indicates that V is sensitive only to relative fO₂ differences greater than ∼2 log units. Post-Archean oceanic mantle peridotites, as represented by abyssal peridotites and obducted massif peridotites, have V-MgO and -Al₂O₃ systematics that can be modeled by 1.5 GPa melting between FMQ − 3 and FMQ − 1. This is consistent with fO₂’s of the mantle source for mid-ocean ridge basalts (MORBs) as determined by the Fe³⁺ activity of peridotitic minerals and basaltic glasses. Some arc-related peridotites have slightly lower V for a given degree of melting than oceanic mantle peridotites, and can be modeled by 1.5 GPa melting at fO₂’s as high as FMQ. However, the majority of arc-related peridotites have V-MgO systematics overlapping that of oceanic mantle peridotites, suggesting that although some arc mantle may melt under slightly oxidizing conditions, most arc mantle does not. The fact that thermobarometrically determined fO₂’s in arc peridotites and lavas can be significantly higher than that inferred from V systematics, suggests that V retains a record of the fO₂ during partial melting, whereas the activity of Fe³⁺ in arc peridotitic minerals and lavas reflect subsequent metasomatic overprints and magmatic differentiation/emplacement processes, respectively.Peridotites associated with middle to late Archean cratonic mantle are characterized by highly variable V-MgO systematics. Tanzanian cratonic peridotites have V systematics indistinguishable from post-Archean oceanic mantle and can be modeled by 3 GPa partial melting at ∼FMQ − 3. In contrast, many South African and Siberian cratonic peridotites have much lower V contents for a given degree of melting, suggesting at first glance that partial melting occurred at high fO₂’s. More likely, however, their unusually low V contents for a given degree of melting may be artifacts of excess orthopyroxene, a feature that pervades many South African and Siberian peridotites but not the Tanzanian peridotites. This is indicated by the fact that the V contents of South African and Siberian peridotites are correlated with increases in SiO₂ content, generating data arrays that cannot be modeled by partial melting but can instead be generated by the addition of orthopyroxene through processes unrelated to primary melt depletion. Correction for orthopyroxene addition suggests that the South African and Siberian peridotites have V-MgO systematics similar to those of Tanzanian peridotites. Thus, if the Tanzanian peridotites represent the original partial melting residues, and if the South African and Siberian peridotites have been modified by orthopyroxene addition, then there is no indication that Archean cratonic mantle formed under fO₂’s significantly greater than that of modern oceanic mantle. Instead, the fO₂’s inferred from the V systematics in these three cratonic peridotite suites are within range of modern oceanic mantle. This also suggests that the transition from a highly reducing mantle in equilibrium with a metallic core to the present oxidized state must have occurred by late Archean times.     

Validation of Landslide Susceptibility Maps; Examples and Applications from a Case Study in Northern Spain

A procedure for validating landslide susceptibility maps wasapplied in a study area in northern Spain and the results obtained compared. Validationwas used to carry out sensitivity analysis for individual variables and combinationsof variables. The validity of different map-making methods was tested, as well as theutility of different types of Favourability Functions. The results obtained show thatvalidation is essential to determine the predictive value of susceptibility maps. Italso helps to better select the most suitable function and significant variables, thus improving the efficiency of the mapping process. Validation based on a temporal strategy makes it possible to derive hazard maps from susceptibility maps.     

Quantitative charge state analysis of manganese biominerals in aqueous suspension using scanning transmission X-ray microscopy (STXM)

We have applied Scanning Transmission Soft X-ray Microscopy (STXM) to investigate the charge state distribution of Mn in two kinds of Mn-biominerals, Mn nodules collected from Lake Michigan sediments and Mn precipitates formed by spores of a marine bacillus SG-1 under transport limited reaction conditions. A data analysis technique was developed, which allows for extraction of spatially resolved 2-d charge state maps of manganese on a submicron level. We find that the charge state of Mn dominates the spectral shape of L-edge spectra of environmentally important single oxidation state Mn minerals and that spectra of mixed oxidation state oxides can be modelled by a combination of appropriate single oxidation state reference spectra. Two-dimensional maps of charge state distributions clearly reveal domains of different oxidation states within single particles of Mn-micronodules. Spots of preferred accumulation of Mn(II) were found, which indicates biogenic precipitation of Mn(II)-species as a first step of nodule formation. The presence of Mn(III) in the studied sediment samples suggests the involvement of one-electron oxidation processes and reaction conditions which inhibit or slow down the disproportionation of Mn(III)-products. Under transport limited conditions, Mn oxidation products formed by spores of the marine bacillus SG-1 can vary from cell to cell. The presence of significant amounts of Mn(III) containing species points to the involvement of one-electron oxidation reactions as in the case of the micro-nodules. Our technique and the results obtained form a new basis for the mechanistic understanding of the formation of Mn biominerals in the environment.     

A methane fuse for the Cambrian explosion: carbon cycles and true polar wander

The dramatic diversification of animal groups known as the Cambrian Explosion (evolution's ‘Big Bang’) remains an unsolved puzzle in Earth Science. The Vendian–Cambrian interval is characterized by anomalously high rates of apparent plate motion, interpreted as True Polar Wander (TPW), and by more than a dozen large, high-frequency perturbations in carbon isotopes that dwarf all others observed through the past 65 million years. We suggest that these biological, tectonic, and geochemical events are intimately related in the following fashion. First, tropical continental margins and shelf-slopes which formed during fragmentation of the supercontinent Rodinia accumulated massive quantities of isotopically-light organic carbon during Late Neoproterozoic time, as indicated by strikingly heavy isotope ratios in inorganic carbon during interglacial intervals. Second, an initial phase of Vendian TPW moved these organic-rich deposits to high latitude, where conditions favored trapping biogenic methane in layers of gas hydrate and perhaps permafrost. Continued sedimentation during Late Vendian time added additional hydrate/gas storage volume and stabilized underlying units until the geothermal gradient moved them out of the clathrate stability field, building up deep reservoirs of highly pressurized methane. Finally, a burst of TPW brought these deposits back to the Tropics, where they gradually warmed and were subjected to regional-scale thermohaline eddy variation and related sedimentation regime changes. Responding to the stochastic character of such changes, each reservoir reached a critical failure point independently at times throughout the Cambrian. By analogy with the Late Paleocene Thermal Maximum event, these methane deposits yield transient, greenhouse-induced pulses of global warming when they erupt. Temperature correlates powerfully with biodiversity; the biochemical kinetics of metabolism at higher temperature decrease generation time and maintain relatively rich and dense invertebrate populations. Repeated thermal pulses along with progressive disruption and alteration of global ocean circulation patterns by TPW could cause the increase in diversity that accompanied the radiation of metazoans. We suggest that a methane ‘fuse’ ignited the Cambrian Evolutionary Explosion.     

A bilinear approximation of the surface relief in terrain correction computations

A new method is presented for the computation of the gravitational attraction of topographic masses when their height information is given on a regular grid. It is shown that the representation of the terrain relief by means of a bilinear surface not only offers a serious alternative to the polyhedra modeling, but also approaches even more smoothly the continuous reality. Inserting a bilinear approximation into the known scheme of deriving closed analytical expressions for the potential and its first-order derivatives for an arbitrarily shaped polyhedron leads to a one-dimensional integration with – apparently – no analytical solution. However, due to the high degree of smoothness of the integrand function, the numerical computation of this integral is very efficient. Numerical tests using synthetic data and a densely sampled digital terrain model in the Bavarian Alps prove that the new method is comparable to or even faster than a terrain modeling using polyhedra.     

Atmospheric Methyl Iodide at Cape Grim, Tasmania, from AGAGE Observations

Atmospheric mixing ratios of methyl iodide (CH₃I) and other methyl halides have been measured at Cape Grim, Tasmania (41°S, 145°E), since early 1998 as part of the Advanced Global Atmospheric Gases Experiment (AGAGE). This paper analyses about 1700 ambient air CH₃I measurements from the 14-month period (March 1998–April 1999). Mixing ratios peaked during the summer, despite faster photolytic loss, suggesting local oceanic emissions were about 2.2–3.6 times stronger in summer than in winter. Back trajectories show that CH₃I levels are strongly dependent on air mass origin, with highest mixing ratios in air from the Tasman Sea/Bass Strait region and lowest levels in air originating from the Southern Ocean at higher latitudes. CH₃I mixing ratios were not well correlated with other methyl halides in unpolluted marine air. The large variations with season and air mass origin suggest that high frequency, continuous data from key locations will make a significant contribution to the understanding of sources and sinks of this important short-lived atmospheric species.     

Long-term investigations on the water budget quantities predicted by the hydro-thermodynamic soil vegetation scheme (HTSVS) – Part II: Evaluation, sensitivity, and uncertainty

Summary ¶Various water budget elements (water supply to the atmosphere, ground water recharge, change in storage) are predicted by HTSVS for a period of 2050 days. The predicted water budget elements are evaluated by routine lysimeter data. The results show that land surface models need parameterizations for soil frost, snow effects and water uptake to catch the broad cycle of soil water budget elements. In principle, HTSVS is able to simulate the general characteristics of the seasonal changes in these water budget elements and their long-term accumulated sums. Compared to lysimeter data, there is a discrepancy in the predicted water supply to the atmosphere for summer and winter which may be attributed to the hardly observed plant physiological parameters like root depth, LAI, shielding factor, etc., the lack of measured downward long-wave radiation, and some simplifications made in the parameterizations of soil frost and snow effects. The fact that high resolution data for the evaluation of model results are missing and evaluation is made on the basis of the data from routine stations of a network is typical for the results of long-term studies on climate. Taking into account the coarse resolution of climate models, the coarse vertical resolution that is used in their LSMs, and the lack of suitable parameters needed, it seems that discrepancies in the order of magnitude found in this study are a general uncertainty in the results of land surface modeling on typical spatial and temporal scales of the climate system.Received October 8, 2001; revised February 15, 2002; accepted September 20, 2002 Published online: April 10, 2003     

Recent Changes in the Climate At the Dead Sea – a Preliminary Study

In the last decade pan evaporation measured at the Southern Dead Sea has significantly increased. Wind, temperature and humidity measurements at the Dead Sea starting in the 1930s as well as 3-D model simulations all seem to indicate a statistically significant change in the local climate of the Dead Sea region. The potential contribution to this climatic change through the weakening of the local land-sea breeze circulation caused by the reduction in the Dead Sea surface area in 1979–1981, is examined. It is suggested that since the breeze tempers the Dead Sea climate, its weakening has caused the air temperature to increase, the relative humidity to decrease and thus increased the pan evaporation. The climatic changes as implied by the MM4 Mesoscale PSU/NCAR model simulations, seem to fit the observed changes and to suggest a local tendency to the more arid climate that now prevails to the south of the study region.