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.     

Numerical simulation of agricultural sediment and pesticide runoff: RZWQM and PRZM comparison

Agricultural sediment and pesticide runoff is a widespread ecological and human health concern. Numerical simulation models, such as Root Zone Water Quality Model (RZWQM) and Pesticide Root Zone Model (PRZM), have been increasingly used to quantify off‐site agricultural pollutant movement. However, RZWQM has been criticized for its inability to simulate sedimentation processes. The recent incorporation of the sedimentation module of Groundwater Loading Effects of Agricultural Management Systems has enabled RZWQM to simulate sediment and sediment‐associated pesticides. This study compares the sediment and pesticide transport simulation performance of the newly released RZWQM and PRZM using runoff data from 2 alfalfa fields in Davis, California. A composite metric (based on coefficient of determination, Nash–Sutcliffe efficiency, index of agreement, and percent bias) was developed and employed to ensure robust, comprehensive assessment of model performance. Results showed that surface water runoff was predicted reasonably well (absolute percent bias <31%) by RZWQM and PRZM after adjusting important hydrologic parameters. Even after calibration, underestimation bias (?89% ≤ PBIAS  ≤ ?36%) for sediment yield was observed in both models. This might be attributed to PRZM's incorrect distribution of input water and uncertainty in RZWQM's runoff erosivity coefficient. Moreover, the underestimation of sediment might be less if the origin of measured sediment was considered. Chlorpyrifos losses were simulated with reasonable accuracy especially for Field A (absolute PBIAS  ≤ 22%), whereas diuron losses were underestimated to a great extent (?98% ≤ PBIAS  ≤ ?65%) in both models. This could be attributed to the underprediction of herbicide concentration in the top soil due to the limitations of the instantaneous equilibrium sorption model as well as the high runoff potential of herbicide formulated as water‐dispersible granules. RZWQM and PRZM partitioned pesticides into the water and sediment phases similarly. According to model predictions, the majority of pesticide loads were carried via the water phase. On the basis of this study, both RZWQM and PRZM performed well in predicting runoff that carried highly adsorptive pesticides on an event basis, although the more physically based RZWQM is recommended when field‐measured soil hydraulic properties are available.     

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.     

The response in floodplain respiration of an alpine river to experimental inundation under different temperature regimes

The respiratory potential [i.e. electron transport system activity (ETSA)] of soils and sediments from five floodplain habitats (channel, gravel, islands, riparian forest and grassland) of the Urbach River, Switzerland, and actual respiration rate (R) of the same samples exposed to experimental inundation were measured. Measurements were carried out at three incubation temperatures (4°C, 12°C and 20°C), and ETSA/R ratios (i.e. exploitation of the overall metabolic capacity) were investigated to better understand the effects of temperature and inundation on floodplain functional heterogeneity. Furthermore, ETSA/R ratios obtained during experimental inundation were compared with ETSA/R ratios from field measurements to investigate the exploitation in total metabolic potential at different conditions. Lowest ETSA and R were measured in samples from channel and gravel habitats, followed by those from islands. Substantially higher values were measured in soils from riparian forest and grassland. Both ETSA and R increased with increasing temperature in samples from all habitats, while the ETSA/R ratio decreased because of a rapid response in microbial community respiration to higher temperatures. The metabolic capacity exploitation (i.e. ETSA/R) during experimental inundation was lowest in predominantly terrestrial samples (riparian forest and grassland), indicating the weakest response to wetted conditions. Comparison of experimentally inundated and field conditions revealed that in rarely flooded soils, the metabolic capacity was less exploited during inundation than during non‐flooded conditions. The results suggest high sensitivity in floodplain respiration to changes in temperature and hydrological regime. ETSA/R ratios are considered good indicators of changes in metabolic activity of floodplain soils and sediments, and thus useful to estimate the impact of changes in hydrological regime or to evaluate success of floodplain restoration actions. 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.     

A gradual transition to plate tectonics on Earth between 3.2 to 2.7 billion years ago

Zircon crystals precipitated from granitoid magmas contain a robust record of the age and chemistry of continental magmatism spanning some 4.375 Ga of Earth history, a record that charts initiation of plate tectonics. However, constraining when exactly plate tectonics began to dominate crustal growth processes is challenging as the geochemical signatures of individual rocks may reflect local subduction processes rather than global plate tectonics. Here we apply counting statistics to a global database of coupled U–Pb and Hf isotope analyses on magmatic zircon grains from continental igneous and sedimentary rocks to quantify changes in the compositions of their source rocks. The analysis reveals a globally significant change in the sources of granitoid magmas between 3.2 and 2.7 Ga. These secular changes in zircon chemistry are driven by a coupling of the deep (depleted mantle) and shallow (crustal) Earth reservoirs, consistent with a geodynamic regime dominated by Wilson cycle style plate tectonics.     

Evidence of ameliorated Middle Weichselian climate and sub‐arctic environment in the western Baltic region: coring lake sediments at Klintholm,Møn,Denmark

Coring through glaciotectonically stacked Quaternary sediments situated below sea level on the island of Møn, Denmark, recovered a succession of interstadial sediments of Middle Weichselian age. Plant and animal remains including insects found in laminated sand and mud indicate deposition in a lake surrounded by dwarf shrubs, herbs, mosses and rare trees. The insect fauna indicates a mean July temperature of 8–12 °C, suggesting an arctic to sub‐arctic environment, while winter temperatures around ?8 to ?22 °C suggest periglacial conditions with permafrost. Luminescence dating of sediment samples gave ages from 48–29 ka, and radiocarbon dating indicates deposition of plant fragments between 45 and 36 ka BP. The fossil assemblage from Møn shows close resemblance to those from other sites with similar ages found in the vicinity of the western Baltic Basin.