Chemical and textural equilibration of garnet during amphibolite facies metamorphism: The influence of coupled dissolution–reprecipitation

Metamorphic equilibration requires chemical communication between minerals and may be inhibited through sluggish volume diffusion and or slow rates of dissolution in a fluid phase. Relatively slow diffusion and the perceived robust nature of chemical growth zoning may preclude garnet porphyroblasts from readily participating in low‐temperature amphibolite facies metamorphic reactions. Garnet is widely assumed to be a reactant in staurolite‐isograd reactions, and the evidence for this has been assessed in the Late Proterozoic Dalradian pelitic schists of the Scottish Highlands. The 3D imaging of garnet porphyroblasts in staurolite‐bearing schists reveals a good crystal shape and little evidence of marginal dissolution; however, there is also lack of evidence for the involvement of either chlorite or chloritoid in the reaction. Staurolite forms directly adjacent to the garnet, and its nucleation is strongly associated with deformation of the muscovite‐rich fabrics around the porphyroblasts. “Cloudy” fluid inclusion‐rich garnet forms in both marginal and internal parts of the garnet porphyroblast and is linked both to the production of staurolite and to the introduction of abundant quartz inclusions within the garnet. Such cloudy garnet typically has a Mg‐rich, Mn‐poor composition and is interpreted to have formed during a coupled dissolution–reprecipitation process, triggered by a local influx of fluid. All garnet in the muscovite‐bearing schists present in this area is potentially reactive, irrespective of the garnet composition, but very few of the schists contain staurolite. The staurolite‐producing reaction appears to be substantially overstepped during the relatively high‐pressure Barrovian regional metamorphism reflecting the limited permeability of the schists in peak metamorphic conditions. Fluid influx and hence reaction progress appear to be strongly controlled by subtle differences in deformation history. The remaining garnet fails to achieve chemical equilibrium during the reaction creating distinctive patchy compositional zoning. Such zoning in metamorphic garnet created during coupled dissolution–reprecipitation reactions may be difficult to recognize in higher grade pelites due to subsequent diffusive re‐equilibration. Fundamental assumptions about metamorphic processes are questioned by the lack of chemical equilibrium during this reaction and the restricted permeability of the regional metamorphic pelitic schists. In addition, the partial loss of prograde chemical and textural information from the garnet porphyroblasts cautions against their routine use as a reliable monitor of metamorphic history. However, the partial re‐equilibration of the porphyroblasts during coupled dissolution–reprecipitation opens possibilities of mapping reaction progress in garnet as a means of assessing fluid access during peak metamorphic conditions.     

Gravel‐bed rivers: from particles to patterns

The papers in this special issue reflect several of the major themes and topics from the 7^th International Workshop on Gravel‐Bed Rivers. The papers focus primarily on aspects of bed material transport in gravel‐bed rivers and larger scale morpho‐dynamics. Research in gravel‐bed rivers is increasingly integrating processes over a wide range of temporal and spatial scales by combining field observation, lab experimentation, numerical modeling and theory testing in a range of river types, aided by new technological developments in particle tracking, computational modeling and high resolution spatial data. This is leading to greater understanding of the processes leading to distinctive morpho‐dynamics of river types and a more reliable basis for river management. Copyright © 2012 John Wiley & Sons, Ltd.     

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Relationship among titanium,rare earth elements,U–Pb ages and deformation microstructures in zircon: Implications for Ti-in-zircon thermometry

A zircon grain in an orthopyroxene–garnet–phlogopite–zircon–rutile-bearing xenolith from Udachnaya, Siberia, preserves a pattern of crystallographic misorientation and subgrain microstructure associated with crystal–plastic deformation. The zircon grain records significant variations in titanium (Ti) from 2.6 to 30 ppm that corresponds to a difference in calculated Ti-in-zircon temperatures of over several hundred degrees Celsius. The highest Ti concentration is measured at subgrain centres (30 ppm), and Ti is variably depleted at low-angle boundaries (down to 2.6 ppm). Variations in cathodoluminescence coincide with the deformation microstructure and indicate localised, differential enrichment of rare earth elements (REE) at low-angle boundaries. Variable enrichment of U and Th and systematic increase of Th/U from 1.61 to 3.52 occurs at low-angle boundaries. Individual SHRIMP-derived U–Pb ages from more deformed zones (mean age of 1799 ± 40, n = 22) are systematically younger than subgrain cores (mean age of 1851 ± 65 Ma, n = 7), and indicate that open system behaviour of Ti–Th–U occurred shortly after zircon growth, prior to the accumulation of significant radiogenic Pb. Modelling of trace-element diffusion distances for geologically reasonable thermal histories indicates that the observed variations are ~ 5 orders of magnitude greater than can be accounted for by volume diffusion. The data are best explained by enhanced diffusion of U, Th and Ti along deformation-related fast-diffusion pathways, such as dislocations and low-angle (< 5°) boundaries. These results indicate chemical exchange between zircon and the surrounding matrix and show that Ti-in-zircon thermometry and U–Pb geochronology from deformed zircon may not yield information relating to the conditions and timing of primary crystallisation.     

Moisture sorption behaviour of salt mixtures in porous stone

Moisture in stone material is the key factor for all stone deterioration processes and also in weathering of cultural heritage. With additional presence of salts in the material the situation gets even more critical. While the properties of pure salts with moisture are well known, knowledge about the interaction of salt mixtures with moisture is still poor. In different approaches the reactions of salt-contaminated stone material on changing moisture were tested in the laboratory. Experiments with different solutions in the Na-Mg-SO₄-NO₃-H₂O system revealed interesting new results on the moisture behaviour of salt-contaminated samples. Theoretical considerations and computer simulations are helpful to interpret the data obtained, but are not yet sufficient to explain the real processes acting on site at the monuments. More encouraging to this fact are complementary studies on visible efflorescences in the same salt system. It is shown how by experimental approaches the understanding on salt-induced stone deterioration is strongly complemented.     

Siderophile and chalcophile metal variations in Tertiary picrites and basalts from West Greenland with implications for the sulphide saturation history of continental flood basalt magmas

Sixty-five million year old continental flood basalts crop out on Qeqertarssuaq Island and the Nuussuaq Peninsula in West Greenland, and they include ～1,000 m of picritic lavas and discrete 10- to 50-m-thick members of highly contaminated basalts. On Qeqertarssuaq, the lavas are allocated to the Vaîgat and Maligât Formations of which the former includes the Naujánguit member, which consists of picrites with 7–29 wt% MgO, 80–1,400 ppm Ni, 5.7–9.4 ppb Pt and 4.2–12.9 ppb Pd. The Naujánguit member contains two horizons of contaminated basalts, the Asûk and Kûgánguaq, which have elevated SiO2 (52–58 wt%) and low to moderate MgO (7.5–12.8 wt%). These lavas are broadly characterized by low Cu and Ni abundances (average, 40 ppm Ni and 45 ppm Cu) and very low Pt (0.16–0.63 ppb) and Pd (0.13–0.68 ppb) abundances, and in the case of the Asûk, they contain shale xenoliths and droplets of native iron and troilite. The contaminated basalts from Nuussuaq, the B0 to B4 members, are also usually Ni-, Cu-, and platinum-group elements (PGE)-depleted. The geochemical signatures (especially the ratios of incompatible trace elements such as Th/Nb) of all of the contaminated basalts from Qeqertarssuaq and some of those from Nuussuaq record what appears to be a chemical contribution from deltaic shales that lie immediately below the lavas. This suggests that the contamination of the magmas occurred during the migration of the magmas through plumbing systems developed in sedimentary rocks, and hence, at a high crustal level. Nickel, Cu, and PGE depletion together with geochemical signatures produced by crustal contamination are also a feature of Siberian Trap basalts from the Noril’sk region. These basalts belong to the 0- to 500-m thick, ～5,000- to 10,000-km³ Nadezhdinsky Formation, which is centered in the Noril’sk Region. A major difference between Siberia and West Greenland is that PGE depletion in the Nadezhdinsky Formation samples with the lowest Cu and Ni contents is much more severe than that of the West Greenland contaminated basalts. Moreover, the volumes of the contaminated and metal-depleted volcanic rocks in West Greenland pale is significant when compared to the Nadezhdinsky Formation; local centers rarely contain more than 15 thin flows with a combined thickness of <50 m and more typically 10–20 m, so the volume of the eruptive portions of each system is probably two orders of magnitude smaller than the Nadezhdinsky edifice. The West Greenland centres are juxtaposed along fault zones that appear to be linked to the subsidence of the Tertiary delta, and so emplacement along N–S structures appears to be a principal control on the distribution of lavas and feeder intrusions. This leads us to suggest that the Greenland system is small and segregation of sulphide took place at high levels in the crust, whereas at Noril’sk, the saturation event took place at depth with subsequent emplacement of sulphide-bearing magmas into high levels of the crust. As a consequence, it may be unreasonable to expect that the West Greenland flood basalts experienced mineralizing processes on the scale of the Noril’sk system.     

Baroclinic instabilities in Jupiter's zonal flow

The baroclinic stability of Jupiter's zonal flow is investigated using a model consisting of two continuously stratified fluid layers. The upper layer, containing a zonal shear flow and representing the Jovian cloudy regions above p ～ 5 bars, is the same as Eady's (1949) model for the Earth. The lower layer has a relatively large but finite depth with a quiescent basic state, representing the deep Jovian fluid bulk below p ～ 5 bars. Due to the presence of the lower layer, the linearized non-dimensional growth rates are drastically reduced from the O(1) growth rates of the original Early model. Only very long wavelengths relative to the upper fluid's radius of deformation L₁ are unstable. Eddy transports of heat are also reduced relative to estimates based on scaling arguments alone. Since the hydrostatic approximation for the lower-layer perturbation breaks down at great depths, a second model is presented in which energy propagates downward in an infinitely deep lower fluid obeying the full linearized fluid equations. In this model, the growth rates are again very small, but now all wavelengths are unstable with maximum growth rates occurring for wavelengths O(1) relative to L₁. These results illustrate the importance for the upper-layer meteorology of the interface boundary condition with the lower fluid, which is radically different from the rigid lower boundary of the Earth's troposphere.     

Analysis of the surface temperature and wind forecast errors of the NCAR-AirDat operational CONUS 4-km WRF forecasting system

Investigating the characteristics of model-forecast errors using various statistical and object-oriented methods is necessary for providing useful guidance to end-users and model developers as well. To this end, the random and systematic errors (i.e., biases) of the 2-m temperature and 10-m wind predictions of the NCAR-AirDat weather research and forecasting (WRF)-based real-time four-dimensional data assimilation (RTFDDA) and forecasting system are analyzed. This system has been running operationally over a contiguous United States (CONUS) domain at a 4-km grid spacing with four forecast cycles daily from June 2009 to September 2010. In the result an exceptionally useful forecast dataset was generated and used for studying the error properties of the model forecasts, in terms of both a longer time period and a broader coverage of geographic regions than previously studied. Spatiotemporal characteristics of the errors are investigated based on the 24-h forecasts between June 2009 and April 2010, and the 72-h forecasts between May and September 2010. It was found that the biases of both wind and temperature forecasts vary greatly seasonally and diurnally, with dependency on the forecast length, station elevation, geographical location, and meteorological conditions. The temperature showed systematic cold biases during the daytime at all station elevations and warm biases during the nighttime above 1,000 m above sea level (ASL), while below 600 m ASL cold biases occurred during the nighttime. The forecasts of surface wind speed exhibited strong positive biases during the nighttime, while the negative biases were observed in the spring and summer afternoons. The surface wind speed was mostly over-predicted except for the stations located between 1,000 and 2,100 m ASL, for which negative biases were identified for most forecast cycles. The highest wind-speed errors were found over the high terrain and near sea-level stations. The wind-direction errors were relatively large at the high-terrain elevation in the Rocky and Appalachian mountain ranges and the western coastal areas and the error structure exhibited notable diurnal variability.     

Treatment of Malting Wastewater in a Granular Sludge Sequencing Batch Reactor (SBR)

Aerobic granular sludge was successfully cultivated in a sequencing batch reactor (SBR) treating wastewater from the malting process with a high content of particulate organic matter. At an organic loading rate of 3.2 kg/(m³ d) COD_total and an influent particle concentration of 0.95 g/L MLSS an average removal of 50% in COD_total and 80% in COD_dissolved could be achieved. A comparison of granular and flocculent sludge grown under the same operating conditions showed no significant difference in removal efficiency although granules exhibited a higher metabolic activity in terms of specific oxygen uptake rate (r_{O2, X}). Two distinct mechanisms of particle removal were observed for granular sludge: during initial granule formation, particles were incorporated into the biofilm matrix. For mature granules, a high level of protozoa growth on the granule surface accounted for the ability to remove particulate COD. Combined evaluation of the development in MLSS content and sludge bed settling rate (i.e., mean derivative of the normalized sludge volume) was found to be an adequate method for monitoring the characteristic settling properties of a granulizing sludge bed. By means of this method, a distinct substrate gradient out of several operating conditions was concluded to have the biggest impact on the formation of aerobic granular sludge.     

Ce and Nd isotope geochemistry on island arc volcanic rocks with negative Ce anomaly: existence of sources with concave REE patterns in the mantle beneath the Solomon and Bonin island arcs

¹³⁸Ce/¹⁴²Ce isotope ratios in Cenozoic island arc volcanic rocks are reported for the first time, together with isotope ratios of Nd and Sr and abundances of REE, Ba and Sr. The island arc volcanics studies here are boninites from Chichijima, the Bonin Islands, and basalts and andesites from the Solomon Islands. REE patterns of the island arc volcanic rocks from the Solmon Islands and the Bonin Islands are confirmed to have negative Ce anomalies. It is also disclosed that the majority of these island arc volcanic rocks show mainly positive values for both _Ce and _Nd. It is shown that these _Ce and _Ce values can hardly be interpreted by simple mixing between MORB and oceanic or continental crustal rocks; the former have positive _Nd and negative _Ce and the latter have negative _Ce and positive or negative _Nd. Existence of sources having positive _Ce and _Nd values is strongly suggested. If the sources are assumed to have been fractionated from CHUR (chondritic uniform reservoir) at the early or middle Precambrian era, the sources from which the volcanics were derived are concluded to have kept concave REE patterns with larger (La/Ce)_N and smaller (Nd/Sm)_N ratios than chondritic values over a substantial period of time, until the time of Cenozoic magmatism forming island arc volcanic rocks in question. During the periods of the Cenozoic magmatic activities and their related events, Ce anomalies are considered to have been created. From Ce and Nd isotope ratios, however, it is difficult to determine which of the following processes was responsible for the Ce anomaly; the incorporation process of subducted oceanic crust into magma at the mantle or the slab dehydration and metasomatism process. Nevertheless, so far as Ce and Nd isotopic ratios are concerned, incorporation of oceanic sediments did not take place to any clearly detectable degree.