Experimental determination of REE partition coefficients between zircon,garnet and melt: a key to understanding high‐T crustal processes

The partitioning of rare earth elements (REE) between zircon, garnet and silicate melt was determined using synthetic compositions designed to represent partial melts formed in the lower crust during anatexis. The experiments, performed using internally heated gas pressure vessels at 7 kbar and 900–1000 °C, represent equilibrium partitioning of the middle to heavy REE between zircon and garnet during high‐grade metamorphism in the mid to lower crust. The D_REE (zircon/garnet) values show a clear partitioning signature close to unity from Gd to Lu. Because the light REE have low concentrations in both minerals, values are calculated from strain modelling of the middle to heavy REE experimental data; these results show that zircon is favoured over garnet by up to two orders of magnitude. The resulting general concave‐up shape to the partitioning pattern across the REE reflects the preferential incorporation of middle REE into garnet, with D_Gd (zircon/garnet) ranging from 0.7 to 1.1, D_Ho (zircon/garnet) from 0.4 to 0.7 and D_Lu (zircon/garnet) from 0.6 to 1.3. There is no significant temperature dependence in the zircon–garnet REE partitioning at 7 kbar and 900–1000 °C, suggesting that these values can be applied to the interpretation of zircon–garnet equilibrium and timing relationships in the ultrahigh‐T metamorphism of low‐Ca pelitic and aluminous granulites.     

Constraints on the timing and conditions of high‐grade metamorphism,charnockite formation and fluid–rock interaction in the Trivandrum Block,southern India

Incipient charnockites have been widely used as evidence for the infiltration of CO₂‐rich fluids driving dehydration of the lower crust. Rocks exposed at Kakkod quarry in the Trivandrum Block of southern India allow for a thorough investigation of the metamorphic evolution by preserving not only orthopyroxene‐bearing charnockite patches in a host garnet–biotite felsic gneiss, but also layers of garnet–sillimanite metapelite gneiss. Thermodynamic phase equilibria modelling of all three bulk compositions indicates consistent peak‐metamorphic conditions of 830–925 °C and 6–9 kbar with retrograde evolution involving suprasolidus decompression at high temperature. These models suggest that orthopyroxene was most likely stabilized close to the metamorphic peak as a result of small compositional heterogeneities in the host garnet–biotite gneiss. There is insufficient evidence to determine whether the heterogeneities were inherited from the protolith or introduced during syn‐metamorphic fluid flow. U–Pb geochronology of monazite and zircon from all three rock types constrains the peak of metamorphism and orthopyroxene growth to have occurred between the onset of high‐grade metamorphism at c. 590 Ma and the onset of melt crystallization at c. 540 Ma. The majority of metamorphic zircon growth occurred during protracted melt crystallization between c. 540 and 510 Ma. Melt crystallization was followed by the influx of aqueous, alkali‐rich fluids likely derived from melts crystallizing at depth. This late fluid flow led to retrogression of orthopyroxene, the observed outcrop pattern and to the textural and isotopic modification of monazite grains at c. 525–490 Ma.     

A 2000‐year lipid biomarker record preserved in a stalagmite from north‐west Scotland

Previous studies on lipid biomarkers preserved in Chinese stalagmites have indicated that ratios of low‐molecular‐weight (LMW) to high‐molecular‐weight (HMW) n‐alkanes, n‐alkan‐2‐ones, n‐alkanols and n‐alkanoic acids can be used as an index of vegetation versus microbial organic matter input to the system and, by extension, a marker of climatic changes, with increases in the proportion of LMW compounds coinciding with colder periods. Here we test whether this hypothesis is equally applicable to a different geographical region (north‐west Scotland), by examining a stalagmite record of the past 200 years, and a wider range of lipid markers. We also test the applicability of other lipid proxies in this context, including the use of n‐alkane ratios, to interpret vegetation changes, and unsaturated alkanoic acid ratios as climatic indicators. The results show that lipid proxies preserved in stalagmites, and especially those related to vegetation, are potentially extremely useful in palaeoenvironmental research. Of particular value is the use of C₂₇/C₃₁ n‐alkane ratios as a proxy for vegetation change, clearly indicating variations between herbaceous and arboreal cover. This proxy has now been successfully applied to samples from diverse environments, and can be considered sufficiently robust to be of use in analysing future stalagmite records. It will be of particular value in areas where reliable pollen records are not available, as is often the case with deeper cave deposits. However, the division between LMW and HMW aliphatic compounds is not a clear‐cut case of microbial versus plant activity, with the changes in LMW compounds relating more closely to those in their HMW analogues than in specific bacterial biomarkers. The use of unsaturated alkanoic acid ratios here gives conflicting results, with the observed variation through time depending on the isomer measured. The discrepancies between the findings of this study and previous work are likely to be due to the varying controls on the lipids (original organic matter input, and compound degradation), which in turn will be affected by whether the main climatic limiting factor on the soil is temperature or precipitation. This suggests that lipid proxies preserved in stalagmites must be interpreted with care, particularly in the case of bacterial compounds which may be derived from within the cave or from the soil. However, many of these issues can be resolved by the use of multi‐proxy studies. Copyright © 2011 John Wiley & Sons, Ltd.     

Supraglacial weathering crust dynamics inferred from cryoconite hole hydrology

Water levels in cryoconite holes were monitored at high resolution over a 3‐week period on Austre Brøggerbreen (Svalbard). These data were combined with melt and energy balance modelling, providing insights into the evolution of the glacier's near‐surface hydrology and confirming that the hydrology of the near‐surface, porous ice known as the ‘weathering crust’ is dynamic and analogous to a shallow‐perched aquifer. A positive correlation between radiative forcing of melt and drainage efficiency was found within the weathering crust. This likely resulted from diurnal contraction and dilation of interstitial pore spaces driven by variations in radiative and turbulent fluxes in the surface energy balance, occasionally causing ‘sudden drainage events’. A linear decrease in water levels in cryoconite holes was also observed and attributed to cumulative increases in near‐surface ice porosity over the measurement period. The transport of particulate matter and microbes between cryoconite holes through the porous weathering crust is shown to be dependent upon weathering crust hydraulics and particle size. Cryoconite holes therefore yield an indication of the hydrological dynamics of the weathering crust and provide long‐term storage loci for cryoconite at the glacier surface. This study highlights the importance of the weathering crust as a crucial component of the hydrology, ecology and biogeochemistry of the glacier ecosystem and glacierized regions and demonstrates the utility of cryoconite holes as natural piezometers on glacier surfaces. Copyright © 2015 John Wiley & Sons, Ltd.     

Interpreting zirconium‐in‐rutile thermometric results

At first sight, experimental results and observations on rocks suggest that the Zr content in rutile, where equilibrated with quartz and zircon, should be a useful thermometer for metamorphic rocks. However, diffusion data for Zr in rutile imply that thermometry should not, for plausible rates of cooling, give the high temperatures commonly observed in high‐grade metamorphic rocks. It is suggested here that such observations can be accounted for by high‐T diffusive closure of Si in rutile, causing the interior of rutile grains to become insensitive to the thermometer equilibrium well above the temperature of Zr diffusive closure. Paired with comparatively slow grain boundary diffusion and problematic zircon nucleation, this allows for cases of Zr retention in rutile through temperatures where Zr is still diffusively mobile within rutile grains. Other observations that may be accounted for in this context are large inter‐grain ranges of rutile Zr contents uncorrelated with rutile grain size, and flat Zr profiles across individual rutile grains, counter to what would be expected from diffusive closure. A consequence is that it is unlikely that Zr‐in‐rutile thermometry will be useful for estimating rock cooling rates.     

Flooding of the continental shelves as a contributor to deglacial CH4 rise

The transition from the last glacial and beginning of Bølling–Allerød and Pre‐Boreal periods in particular is marked by rapid increases in atmospheric methane (CH₄) concentrations. The CH₄ concentrations reached during these intervals, ～650–750 ppb, is twice that at the last glacial maximum and is not exceeded until the onset of industrialization at the end of the Holocene. Periods of rapid sea‐level rise as the Last Glacial Maximum ice sheets retreated and associated with ‘melt‐water pulses’ appear to coincide with the onset of elevated concentrations of CH₄, suggestive of a potential causative link. Here we identify and outline a mechanism involving the flooding of the continental shelves that were exposed and vegetated during the glacial sea‐level low stand and that can help account for some of these observations. Specifically, we hypothesize that waterlogging (and later, flooding) of large tracts of forest and savanna in the Tropics and Subtropics during the deglacial transition and early Holocene would have resulted in rapid anaerobic decomposition of standing biomass and emission of methane to the atmosphere. This novel mechanism, akin to the consequences of filling new hydroelectric reservoirs, provides a mechanistic explanation for the apparent synchronicity between rate of sea‐level rise and occurrence of elevated concentrations of ice core CH₄. However, shelf flooding and the creation of transient wetlands are unlikely to explain more than ～60 ppb of the increase in atmospheric CH₄ during the deglacial transition, requiring additional mechanisms to explain the bulk of the glacial to interglacial increase. Similarly, this mechanism has the potential also to play some role in the rapid changes in atmospheric methane associated with the Dansgaard–Oeschger cycles. Copyright © 2012 John Wiley & Sons, Ltd.     

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ⁵⁶Fe and δ³⁰Si with increasing silica content as well as a systematic increase in δ⁵⁶Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ⁵⁶Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ⁵⁶Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ⁵⁶Fe = +0.05 ± 0.02 ‰; δ³⁰Si = ?0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.     

The Moon

Recent geochemical and geophysical data from the Moon enable a revision of earlier interpretations regarding lunar origin, structure and bulk composition. Earth and Moon show many similarities among their isotopic compositions, but they have evolved in totally dissimilar ways, probably related to the deficiency of water and volatile elements in the Moon as well as the vast differences in size and internal pressure. Some global geochemical differences from the Earth such as volatile depletion based on K/U ratios have been established. However, all current lunar samples come from differentiated regions, making the establishment of a bulk composition more reliant on bulk geophysical properties or isotopic similarities; it remains unclear how the latter arose or relate to whole Moon composition. The lack of fractionation effects among the refractory and super-refractory elements indicates that the proto-lunar material seems unlikely to have been vaporized while the presence of volatile elements may place lower limits on proto-lunar temperatures. The apparent lack of geochemical evidence of an impacting body enables other possible impactors, such as comets, to be considered. Although the origin of the Moon remains currently unknown, it is generally believed that the Moon originated as the result of a giant impact on the Earth.