浓硫酸钠水溶液中的离子对

不同浓度的Na2SO4水溶液的拉曼光谱显示了SO42-的四个拉曼活性带:980 cm-1处的SO42-的对称伸缩振动模式v1带,1 106 cm-1处的反对称伸缩振动模式v3带,448 cm-1处的变形振动模式v2带和617 cm-1处的变形振动模式v4带。482 cm-1处的肩膀峰是由于NaSO4-离子对的形成对448 cm-1的v2带的影响而形成的SO42-的一个新的振动峰。浓Na2SO4水溶液中,水共享离子对[Na+.H2O.SO42-]-是主要的离子对物种。随着Na2SO4水溶液浓度的增加,Na+和SO42-的相互作用增强,NaSO4-离子对所占的摩尔分数增加。     

Fluid generation and evolution during exhumation of deeply subducted UHP continental crust: Petrogenesis of composite granite–quartz veins in the Sulu belt,China

Composite granite–quartz veins occur in retrogressed ultrahigh pressure (UHP) eclogite enclosed in gneiss at General's Hill in the central Sulu belt, eastern China. The granite in the veins has a high‐pressure (HP) mineral assemblage of dominantly quartz+phengite+allanite/epidote+garnet that yields pressures of 2.5–2.1 GPa (Si‐in‐phengite barometry) and temperatures of 850–780°C (Ti‐in‐zircon thermometry) at 2.5 GPa (~20°C lower at 2.1 GPa). Zircon overgrowths on inherited cores and new grains of zircon from both components of the composite veins crystallized at c. 221 Ma. This age overlaps the timing of HP retrograde recrystallization dated at 225–215 Ma from multiple localities in the Sulu belt, consistent with the HP conditions retrieved from the granite. The ε_Hf(t) values of new zircon from both components of the composite veins and the Sr–Nd isotope compositions of the granite consistently lie between values for gneiss and eclogite, whereas δ¹⁸O values of new zircon are similar in the veins and the crustal rocks. These data are consistent with zircon growth from a blended fluid generated internally within the gneiss and the eclogite, without any ingress of fluid from an external source. However, at the peak metamorphic pressure, which could have reached 7 GPa, the rocks were likely fluid absent. During initial exhumation under UHP conditions, exsolution of H₂O from nominally anhydrous minerals generated a grain boundary supercritical fluid in both gneiss and eclogite. As exhumation progressed, the volume of fluid increased allowing it to migrate by diffusing porous flow from grain boundaries into channels and drain from the dominant gneiss through the subordinate eclogite. This produced a blended fluid intermediate in its isotope composition between the two end‐members, as recorded by the composite veins. During exhumation from UHP (coesite) eclogite to HP (quartz) eclogite facies conditions, the supercritical fluid evolved by dissolution of the silicate mineral matrix, becoming increasingly solute‐rich, more ‘granitic’ and more viscous until it became trapped. As crystallization began by diffusive loss of H₂O to the host eclogite concomitant with ongoing exhumation of the crust, the trapped supercritical fluid intersected the solvus for the granite–H₂O system, allowing phase separation and formation of the composite granite–quartz veins. Subsequently, during the transition from HP eclogite to amphibolite facies conditions, minor phengite breakdown melting is recorded in both the granite and the gneiss by K‐feldspar+plagioclase+biotite aggregates located around phengite and by K‐feldspar veinlets along grain boundaries. Phase equilibria modelling of the granite indicates that this late‐stage melting records P–T conditions towards the end of the exhumation, with the subsolidus assemblage yielding 0.7–1.1 GPa at <670°C. Thus, the composite granite–quartz veins represent a rare example of a natural system recording how the fluid phase evolved during exhumation of continental crust. The successive availability of different fluid phases attending retrograde metamorphism from UHP eclogite to amphibolite facies conditions will affect the transport of trace elements through the continental crust and the role of these fluids as metasomatic agents interacting with the mantle wedge in the subduction channel.     

Using raw regional climate model outputs for quantifying climate change impacts on hydrology

General circulation model outputs are rarely used directly for quantifying climate change impacts on hydrology, due to their coarse resolution and inherent bias. Bias correction methods are usually applied to correct the statistical deviations of climate model outputs from the observed data. However, the use of bias correction methods for impact studies is often disputable, due to the lack of physical basis and the bias nonstationarity of climate model outputs. With the improvement in model resolution and reliability, it is now possible to investigate the direct use of regional climate model (RCM) outputs for impact studies. This study proposes an approach to use RCM simulations directly for quantifying the hydrological impacts of climate change over North America. With this method, a hydrological model (HSAMI) is specifically calibrated using the RCM simulations at the recent past period. The change in hydrological regimes for a future period (2041–2065) over the reference (1971–1995), simulated using bias‐corrected and nonbias‐corrected simulations, is compared using mean flow, spring high flow, and summer–autumn low flow as indicators. Three RCMs driven by three different general circulation models are used to investigate the uncertainty of hydrological simulations associated with the choice of a bias‐corrected or nonbias‐corrected RCM simulation. The results indicate that the uncertainty envelope is generally watershed and indicator dependent. It is difficult to draw a firm conclusion about whether one method is better than the other. In other words, the bias correction method could bring further uncertainty to future hydrological simulations, in addition to uncertainty related to the choice of a bias correction method. This implies that the nonbias‐corrected results should be provided to end users along with the bias‐corrected ones, along with a detailed explanation of the bias correction procedure. This information would be especially helpful to assist end users in making the most informed decisions.     

Soil property variation mapping through data mining of soil category maps

Spatial information on soil properties is an important input to hydrological models. In current hydrological modelling practices, soil property information is often derived from soil category maps by the linking method in which a representative soil property value is linked to each soil polygon. Limited by the area‐class nature of soil category maps, the derived soil property variation is discontinuous and less detailed than high resolution digital terrain or remote sensing data. This research proposed dmSoil, a data‐mining‐based approach to derive continuous and spatially detailed soil property information from soil category maps. First, the soil–environment relationships are extracted through data mining of a soil map. The similarity of the soil at each location to different soil types in the soil map is then estimated using the mined relationships. Prediction of soil property values at each location is made by combining the similarities of the soil at that location to different soil types and the representative soil property values of these soil types. The new approach was applied in the Raffelson Watershed and Pleasant Valley in the Driftless Area of Wisconsin, United States to map soil A horizon texture (in both areas) and depth to soil C horizon (in Pleasant Valley). The property maps from the dmSoil approach capture the spatial gradation and details of soil properties better than those from the linking method. The new approach also shows consistent accuracy improvement at validation points. In addition to the improved performances, the inputs for the dmSoil approach are easy to prepare, and the approach itself is simple to deploy. It provides an effective way to derive better soil property information from soil category maps for hydrological modelling. Copyright © 2014 John Wiley & Sons, Ltd.     

A tree‐ring width based drought reconstruction for southeastern China: links to Pacific Ocean climate variability

We present a drought reconstruction for southeastern China based on a tree‐ring width chronology of Cryptomeria fortunei developed from two sampling sites in central Fujian. A reconstruction of July–February drought variability, spanning AD 1855–2011, was developed by calibrating total tree‐ring width data with the self‐calibrating Palmer drought severity index (scPDSI). The reconstruction was verified against an independent data set, and accounts for 36% of the actual scPDSI variance during the period 1955–2011. Relatively dry intervals were reconstructed between AD 1859–1880, 1899–1911, 1927–1933, 1946–1959, 1964–1970 and 1987–1997. Relatively wet conditions prevailed during 1855–1858, 1881–1898, 1912–1926, 1934–1945, 1960–1963, 1971–1986 and 1998–2011. Comparisons between our scPDSI reconstruction and a moisture‐sensitive tree‐ring width record from Vietnam revealed consistencies between the two data sets, suggesting similar drought regimes. Spectral peaks of 2.2–6.4 years may be indicative of El Niño‐Southern Oscillation (ENSO) activity, as also suggested by the significant correlations with sea surface temperatures (SSTs) in the eastern equatorial and southeastern Pacific Ocean and an extreme event analysis. The analysis of links between our scPDSI reconstruction and the large‐scale regional climatic variation shows that there is a relationship between regional drought variation and East Asian summer monsoon (EASM) intensity.