Fe–Mg partitioning between ringwoodite and magnesiowüstite and the effect of pressure, temperature and oxygen fugacity

 The partitioning of Mg and Fe between magnesiowüstite and ringwoodite solid solutions has been measured between 15 and 23 GPa and 1200–1600 ^∘C using both Fe and Re capsule materials to vary the oxidation conditions. The partitioning results show a clear dependence on the capsule material used due to the variation in Fe³⁺ concentrations as a consequence of the different oxidation environments. Using results from experiments performed in Fe capsules, where metallic Fe was also added to the starting materials, the difference in the interaction parameters for the two solid solutions (W _FeMg ^mw−W _FeMg ^ring) is calculated to be 8.5±1 kJ mol⁻¹. Similar experiments performed in Re metal capsules result in a value for W _FeMg ^mw−W _FeMg ^ring that is apparently 4 kJ higher, if all Fe is assumed to be FeO. Electron energy-loss near-edge structure (ELNES) spectroscopic analyses, however, show Fe³⁺ concentrations to be approximately three times higher in magnesiowüstite produced in Re capsules than in Fe capsules and that Fe³⁺ partitions preferentially into magnesiowüstite, with K _{D Fe3+} ^ring/mw estimated between 0.1 and 0.6. Using an existing activity composition model for magnesiowüstite, a least–squares fit to the partitioning data collected in Fe capsules results in a value for the ringwoodite interaction parameter (W _FeMg ^ring) of 3.5±1 kJ mol⁻¹. The equivalent regular interaction parameter for magnesiowüstite (W _FeMg ^mw) is 12.1±1.8 kJ mol. These determinations take into account the Fe³⁺ concentrations that occur in both phases in the presence of metallic Fe. The free energy change in J mol⁻¹ for the Fe exchange reaction can be described, over the range of experimental conditions, by 912 + 4.15 (T−298)+18.9P with T in K, P in kbar. The estimated volume change for this reaction is smaller than that predicted using current compilations of equation of state data and is much closer to the volume change at ambient conditions. These results are therefore a useful test of high pressure and temperature equation of state data. Using thermodynamic data consistent with this study the reaction of ringwoodite to form magnesiowüstite and stishovite is calculated from the data collected using Fe capsules. Comparison of these results with previous studies shows that the presence of Fe³⁺ in phases produced in multianvil experiments using Re capsules can have a marked effect on apparent phase relations and determined thermodynamic properties. Received: 13 September 2000 / Accepted: 25 March 2001     

The rock magnetic signal of climate change in the maar lake sequence of Lac St Front (France)

Rock magnetic properties of the maar lake sediments of Lac St Front (Massif Central, France) reflect environmental changes during the last climatic cycle. High magnetic concentrations are measured in the sediments deposited under glacial climatic conditions, while lower concentrations correspond with more temperate climatic periods. Low- and high-temperature measurements indicate that the remanence is carried by (titanium-poor) magnetite. However, some maghemite and haematite is present in sediments deposited under temperate conditions.
Normalized intensities and coercivities of the anhysteretic remanent magnetization (ARM) are clearly higher for the sediments deposited during the temperate climatic periods of the Eemian, St Germain I, II and Mid-glacial than for glacial sediments, but other magnetic parameters hardly differ between these groups. Due to slight differences in magnetic composition and possible effects of grain interactions, it is not straightforward to relate this different ARM behaviour to magnetic grain-size variations. For the Holocene sediments, rock magnetic parameters indicate a larger grain size. This trend is also suggested by granulometric experiments with an optical laser granulometer. Dissolution of smaller grains is the most likely explanation for this larger grain size.
Changes in magnetic composition and grain size are extremely limited for the glacial sediments, but magnetic concentration varies considerably. Magnetic concentration maxima in the glacial sediments of Lac St Front correlate with those of the nearby Lac du Bouchet (Thouveny et al. 1994). Correlating the susceptibility records of these sequences with the δ¹⁸O record of the GRIP ice cores (Thouveny et al. 1994) suggests that magnetic concentration maxima may correspond with short cold climatic episodes, associated with Heinrich events.     

Tectonic evolution of the Eastern Pilbara,Australia (extended abstract)

Geologie en Mijnbouw -     

Water-level changes in the Hammock River marsh palaeovalley, Connecticut between 13,000 and 6000 (C) yrs B.P.

Detailed analysis of basal organic deposits underlying Hammock River marsh, Connecticut allowed documentation of water-level changes that occurred between 13,000 and 6000 yrs B.P. Four main periods of groundwater- and lake-level movements and related environmental changes can be identified.

1. (1) 12,500-10,200 yrs B.P. (lake stage): very rapid rise of the groundwater table of about 2 to 3 m, resulting in a shallow lake, followed by a more gradual rise of about 2.5 to 1.5 m.

2. (2) 10,200-7000 yrs B.P. (freshwater marsh, stage 1): slow overall rise of the water table interrupted by a drop of at least 1 m between about 9500 and 9000 yrs B.P. and of at least 0.8 m between about 8000 and 7500 yrs B.P., each event leading to oxidation and maceration of organic material.

3. (3) 7000-6400 yrs B.P. (complete desiccation of the swamp): rapid fall of the water table of at least 3.9 m. causing large-scale down-wasting of the accumulated peat.

4. (4) After 6400 yrs B.P. (freshwater marsh, stage 2): rapid rise of the water table.

The water-table rise of period 1 and the lowering of period 3 are attributed to predominantly local causes, while the groundwater fluctuations during period 2 are probably climate-related. The final water-level increase reflects the influence of Holocene relative sea-level rise.     

The surface free energies of talc and pyrophyllite

The components of the interfacial surface tension of talc and pyrophyllite were determined by measuring the rate of the capillary rise of a number of liquids through thin, sedimented deposits of the powdered minerals. The rate of capillary rise of a liquid in a powder is related to the contact angle between the liquid and the solid by the Washburn equation. The contact angles thus derived were used to determine the apolar (Lifshitzvan der Waals) component, γ ^LW , and the polar, electronacceptor and electron-donor parameters, γ ^⊕ and γ ^? respectively, of the Lewis acid/base component of the total interfacial surface energy using the Young equation. The values of γ ^LW for talc and pyrophyllite (31.5 and 34.4 mJ/m²) are slightly smaller than for smectite clay minerals (e.g., the value for hectorite is 39.9 mJ/m²), the electron donor parameter values are roughly comparable for talc and pyrophyllite (γ ^⊕ = 2.4 and 1.7 mJ/m²) as are the values of the electron acceptor parameter (γ ^? = 2.7 and 3.2 mJ/m²). The well-known hydrophobicity of these two minerals is due to the remarkably small value (for silicate minerals) of γ ^?(γ^⊕ is normally small or zero for silicates and many other oxides). The small values of both γ ^⊕ and γ ^? mean that the Lewis acid/base interactions between talc or pyrophyllite and highly polar water molecules are very weak. In contrast, low-charge smectites, the minerals most similar chemically and structurally to talc and pyrophyllite, have much greater values of γ ^? (≥ 30 mJ/m²) and are hydrophyllic.     

Cokriging nonstationary data

Universal cokriging is used to obtain predictions when dealing with multivariate random functions. An important type of nonstationarity is defined in terms of multivariate random functions with increments which are stationary of orderk. The covariance between increments of different variables is modeled by means of the pseudo-cross-covariance function. Criteria are formulated to which the parameters of pseudo-cross-covariance functions must comply so as to ensure positive-definiteness. Cokriging equations and the induced cokriging equations are given. The study is illustrated by an example from soil science.     

Heavy metal distribution in sediments of Krishna River basin,India

Suspended and bed sediments collected from the entire region of the Krishna River and its major tributaries were analyzed for heavy metals (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pb) by the thin-film energy dispersive x-ray fluorescence technique. There is considerable variation in the concentration of elements towards downstream, which may be due to the variation in the subbasin geology and various degrees of human impact. Suspended particles are enriched in heavy metals throughout the basin relative to bed sediments. The heavy metals are enriched in coarse size fractions (10–90 µm) throughout the Krishna River except its tributary Bhima, where finer fractions (2 µm) dominate. Transition elements correlate very well with each other. There is a striking similarity between the bed sediments of Krishna River and the Indian average. When the annual heavy metal flux carried by the Krishna River was estimated, and viewed in relation to the other major riverine transport, the Krishna is seen to be a minor contributor of heavy metals to the Bay of Bengal.