Fluids in the peridotite–water system up to 6 GPa and 800°C: new experimental constrains on dehydration reactions

The phase assemblages and compositions in a K-free lherzolite + H₂O system were determined between 4 and 6 GPa and 700–800°C, and the dehydration reactions occurring at subarc depth in subduction zones were constrained. Experiments were performed on a rocking multi-anvil apparatus using a diamond-trap setting. The composition of the fluid phase was measured using the recently developed cryogenic LA–ICP–MS technique. Results show that, at 4 GPa, the aqueous fluid coexisting with residual lherzolite (~85 wt% H₂O) doubles its solute load when chlorite transforms to the 10-Å phase between 700 and 750°C. The 10-Å phase breaks down at 4 and 5 GPa between 750 and 800°C and at 6 GPa between 700 and 750°C, leaving a dry lherzolite coexisting with a fluid phase containing 58–67 wt% H₂O, again doubling the total dissolved solute load. The fluid fraction in the system increases from 0.2 when a hydrous mineral is present to 0.4 when coexisting with a dry lherzolite. Our data do not reveal the presence of a hydrous peridotite solidus below 800°C. The directly measured fluid compositions demonstrate a fundamental change in the (MgO + FeO) to SiO₂ mass ratio of fluid solutes occurring at a depth of ca. 120–150 km (in the temperature window of 700–800°C), from (MgO–FeO)-dominated at 4 GPa [with (MgO + FeO)/SiO₂ ratio of 1.41–1.56] to SiO₂-dominated at 5–6 GPa (ratios of 0.61–0.82). The mobility of Al₂O₃ increases by more than one order of magnitude across this P–T interval and demonstrates that Al₂O₃ is compatible in an aqueous fluid coexisting with the anhydrous ol-opx-cpx ± grt assemblage. This shift in the fluid composition correlates with changes in the phase assemblage of the residual silicates. The hitherto unknown fundamental change in (MgO + FeO)/SiO₂ ratio and prominent increase in Al₂O₃ of the aqueous fluid with progressive subduction will likely inspire novel concepts on mantle wedge metasomatism by slab fluids.     

Determining the composition of C–H–O liquids following high-pressure and high-temperature diamond-trap experiments

Here, we present the first analytical technique (the quartz tube system technique—QTS) to directly analyze H₂O and CO₂ contents in liquids following high-pressure, high-temperature experiments in capsules containing mantle minerals and a diamond layer serving as a fluid/melt trap. In this technique, the capsule is frozen prior to opening; the diamond trap is cut out of the capsule and placed inside a N₂-filled quartz tube. The diamond trap is heated up to 900 °C to release the gases to an Infrared Gas Analyzer, which determines the CO₂ and H₂O contents. Three sets of experiments containing SiO₂ and CaCO₃ powders were performed at 6 GPa and 1,000 °C in order to calibrate and validate the technique. These experiments demonstrated that when samples are prepared in a N₂ environment, CO₂ and H₂O can be directly measured with an accuracy and precision of 2–3 and 3–4 %, respectively. The QTS technique (for H₂O and CO₂ determination) together with the cryogenic technique (total dissolved solids content) can be applied to diamond-trap capsules following HP–HT experiments in order to provide direct and complete liquid compositions coexisting with mantle material. The principal advantage of the QTS technique of direct analysis of volatile content in liquids over the indirect approach of mass balance calculations is the possibility of studying carbonated and hydrous liquid compositions in equilibrium with mantle material regardless of chemistry and pressure–temperature experimental conditions.     

A Supplementary Method for Assessing the Reliability of Fluids Sampled from Deep Aquifers

In deep aquifers, temperatures of formation fluids recovered during drill-stem tests were usually higher than regular bottom-hole temperatures recorded at the same borehole and interval. Wherever the opposite was observed, the sampled formation fluids were diluted with mud filtrate or cushion water. Temperature measurements are a useful criterion for differentiating between representative and contaminated formation-fluid samples.     

Mammal remains at Rantis Cave,Israel, and Middle–Late Pleistocene human subsistence and ecology in the Southern Levant

Rantis Cave is a recently discovered filled cave in central Israel, displaying a rich faunal accumulation of micromammals, ungulates and carnivores. U–Th dating assigns the beginning of accumulation to ca. 140 ka. The accumulation is culturally assigned to the late half of the Middle Paleolithic (MP) period. Single‐grain optically stimulated luminescence measurements attest to a complex sedimentological history. We present the cross‐disciplinary results of taphonomic and geomorphological analyses, which point to the cave serving as a natural pitfall trap for the large fauna, with little human or carnivore activity. The fauna is dominated by Dama among the ungulates and by Microtus among the micromammals. These data in conjunction with ungulate tooth mesowear analysis suggest a xeric Mediterranean environment on the eastern margin of the southern Levantine foothills. The relative taxonomic abundance of ungulate taxa shows some differences from anthropogenic MP sites, possibly reflecting the prey choice patterns of MP hunters. Overall, the natural accumulation scenario for Rantis Cave provides a rare paleoenvironmental and paleoeconomic reference to the rich anthropogenic MP faunas of the Southern Levant, enabling the reconstruction of a rich and diverse environmental setting for this important human dispersal route. Copyright © 2011 John Wiley & Sons, Ltd.     

Geomagnetic field intensity: How high can it get? How fast can it change? Constraints from Iron Age copper slag

The intensity of the geomagnetic field varies over different time scales. Yet, constraints on the maximum intensity of the field as well as for its maximum rate of change are inadequate due to poor temporal resolution and large uncertainties in the geomagnetic record. The purpose of this study is to place firm limits on these fundamental properties by constructing a high-resolution archaeointensity record of the Levant from the 11th century to the early 9th century BCE, a period over which the geomagnetic field reached its maximum intensity in Eurasia over the past 50,000 years. We investigate a ¹⁴C-dated sequence of ten layers of slag material, which accumulated within an ancient industrial waste mound of an Iron Age copper-smelting site in southern Israel. Depositional stratigraphy constrains relative ages of samples analyzed for paleointensity, and ¹⁴C dates from different horizons of the mound constrain the age of the whole sequence. The analysis yielded 35 paleointenisty data points with accuracy better than 94% and precision better than 6%, covering a period of less than 350 years, most probably 200 years. We construct a new high-resolution quasi-continuous archaeointensity curve of the Levant that displays two dramatic spikes in geomagnetic intensity, each corresponding to virtual axial dipole moment (VADM) in excess of 200 ZAm². The geomagnetic spikes rise and fall over a period of less than 30 years and are associated with VADM fluctuations of at least 70 ZAm². Thus, the Levantine archaeomagnetic record places new constraints on maximum geomagnetic intensity as well as for its rate of change. Yet, it is not clear whether the geomagnetic spikes are local non-dipolar features or a geomagnetic dipolar phenomenon.     

Spatial heterogeneity in estuarine mud dynamics

The fate of mud in an estuary over an entire year was unravelled using complementary, independent, spatially explicit techniques. Sequential ERS-2 SAR and Envisat MERIS-FR data were used to derive synoptic changes in intertidal bottom mud and suspended particulate matter (SPM) in the top of the water column, respectively. These satellite data were combined with in situ measurements and with a high resolution three-dimensional cohesive sediment model, simulating mud transport, resuspension, settling and deposition under the influence of tides, wind, waves and freshwater discharge. The spatial distribution of both bottom mud and SPM as observed by in situ and satellite techniques was largely explained by modelled estuarine circulation, tidal and wind-induced variations in vertical mixing and horizontal advection. The three data sources also showed similar spring-neap and seasonal variations in SPM (all factor 1.5 to 2), but semi-diurnal tidal variations were underestimated by the model. Satellite data revealed that changes in intertidal bottom mud were spatially heterogeneous, but on average mud content doubled during summer, which was confirmed by in situ data. The model did not show such seasonal variation in bed sediment, suggesting that seasonal dynamics are not well explained by the physical factors presently implemented in the model, but may be largely attributed to other (internal) factors, including increased floc size in summer, temporal stabilisation of the sediment by microphytobenthos and a substantially lower roughness of the intertidal bed in summer as observed by the satellite. The effects of such factors on estuarine mud dynamics were evaluated.     

Experimental determination of the activity of chromite in multicomponent spinels

We determined activity-composition relationships in Pt-Cr and Pt-Fe-Cr alloys at 1300°C experimentally and used the results to constrain the thermodynamic properties of chromite-picrochromite spinels. The Pt-Cr binary is characterized by strong negative deviations from ideality throughout the investigated composition range and the activity-composition relationship can be fit by a four-suffix asymmetric regular solution with three binary interaction parameters. The ternary alloy was modeled as a four-suffix asymmetric regular solution; the three ternary interaction parameters in this model were constrained by combining interaction parameters for the three bounding binaries taken from this and previous work with results for a set of experiments in which the activity of Cr in Pt-Fe-Cr-alloys was fixed by coexisting Cr₂O₃ at known f_O2.The free energy of formation of FeCr₂O₄ at 1300°C was determined using the activities of Fe and Cr in Pt-alloys in equilibrium with oxide mixes of FeCr₂O₄ and Cr₂O₃. The free energy of formation of chromite from Fe+Cr₂O₃+O₂ is −202.7 ± 0.4 kJ/mol (1σ), indistinguishable from literature values. The corresponding free energy of formation of FeCr₂O₄ from the elements is −923.5 ± 2.1 kJ/mol (1σ), and the enthalpy of formation at 298 K is −1438 kJ/mol. The activity-composition relationship for the chromite component in (Fe,Mg)Cr₂O₄ solid solutions was determined from a set of experiments in which Pt-alloys were equilibrated with spinel + Cr₂O₃. (Fe,Mg)Cr₂O₄ spinels are nearly ideal at 1300°C; modeling our data with a one-site symmetric regular solution yields an interaction parameter of +2.14 ± 0.62 kJ/mol (1σ), similar to values based on data from the literature.     

The thermal history of equilibrated ordinary chondrites and the relationship between textural maturity and temperature

The compositions and textures of phases in eleven equilibrated ordinary chondrites from the H, L, and LL groups spanning petrographic types 4-6 were studied and used to constrain the thermal histories of their parent bodies. Based on Fe-Mg exchange between olivine and spinel, average equilibration temperatures for type 4-6 chondrites encompass a small range, 586-777 °C, relative to what is commonly assumed for peak temperatures (600-950 °C). The maximum temperatures recorded by individual chondrites, which are minima relative to peak metamorphic temperatures, increase subtly but systematically with metamorphic type and are tightly clustered for H4-6 (733-754 °C) and LL4-6 (670-777 °C). For the Ls, Ausson (L5) records a higher maximum olivine-spinel temperature (761 °C) than does the L4 chondrite Saratov (673 °C) or the L6 chondrite Glatton (712 °C). Our data combined with olivine-spinel equilibration temperatures calculated for other equilibrated ordinary chondrites using mineral compositions from the literature demonstrate that, in general, type 4 chondrites within each chemical group record temperatures lower than or equal to those of types 5-6 chondrites.For H chondrites, the olivine-spinel closure temperature is a function of spinel grain size, such that larger grains, abundant in types 5-6 chondrites, record temperatures of ∼740 °C or more while smaller grains, rare in types 5-6 but abundant in type 4 chondrites, record lower temperatures. Olivine-spinel temperatures in the type 6 chondrites Guareña and Glatton are consistent with rapid (50-100 °C/Myr) cooling from high temperatures in the ordinary chondrite parent bodies. With one exception (∼500 °C/Myr), olivine-spinel data for St.-Séverin (LL6) are consistent with similar cooling rates. Cooling rates of order 100 °C/Myr at ∼750 °C for type 6 chondrites are considerably higher than previously determined cooling rates for lower temperatures (?550 °C) based on metallography, fission tracks, and geochronology. For H chondrites, current thermal models of an “onion shell” parent body are inconsistent with a small range of peak temperatures based on olivine-spinel and two pyroxene thermometry combined with a wide dispersion of cooling rates at low temperatures. Equilibrated chondrites may have sampled regions near a major transition in physical properties such as near the base of a regolith pile.