Upper crustal abundances of trace elements: A revision and update

We report new estimates of abundances of rarely analyzed elements (As, B, Be, Bi, Cd, Ge, In, Mo, Sb, Sn, Te, Tl, W) in the upper continental crust based on precise ICP-MS analyses of well-characterized upper crustal samples (shales, pelites, loess, graywackes, granitoids and their composites) from Australia, China, Europe, New Zealand and North American. Obtaining a better understanding of the upper crustal abundance and associated uncertainties of these elements is important in placing better constraints on bulk crust composition and, from that, whole Earth models of element cycling and crust generation. We also present revised abundance estimates of some more commonly analyzed trace elements (Li, Cr, Ni, and Tm) that vary by > 20% compared to previous estimates. The new estimates are mainly based on significant (r² > 0.6) inter-element correlations observed in clastic sediments and sedimentary rocks, which yield upper continental crust elemental ratios that are used in conjunction with well-determined abundances for certain key elements to place constraints on the concentrations of the rarely analyzed elements. Using the well-established upper crustal abundances of La (31 ppm), Th (10.5 ppm), Al₂O₃ (15.40%), K₂O (2.80%) and Fe₂O₃ (5.92%), these ratios lead to revised upper crustal abundances of B = 47 ppm, Bi = 0.23 ppm, Cr = 73 ppm, Li = 41 ppm, Ni = 34 ppm, Sb = 0.075, Te = 0.027 ppm, Tl = 0.53 ppm and W = 1.4 ppm. No significant correlations exist between Mo and Cd and other elements in the clastic sediments and sedimentary rocks, probably due to their enrichment in organic carbon. We thus calculate abundances of these elements by assuming the upper continental crust consists of 65% granitoid rocks plus 35% clastic sedimentary rocks. The validity of this approach is supported by the similarity of SiO₂, Al₂O₃, La and Th abundances calculated in this way with their upper crustal abundances given in Rudnick and Gao [Rudnick, R., Gao, S., 2003. Composition of the continental crust. In: Rudnick, R.L. (Ed.), The Crust. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry, vol. 3. Elsevier–Pergamon, Oxford, pp. 1–64.]. The upper crustal abundances thus obtained are Mo = 0.6 ppm and Cd = 0.06 ppm. Our data also suggest a  20% increase of the Tm, Yb and Lu abundances reported in Rudnick and Gao [Rudnick, R., Gao, S., 2003. Composition of the continental crust. In: Rudnick, R.L. (Ed.), The Crust. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry, vol. 3. Elsevier–Pergamon, Oxford, pp. 1–64.].     

Age and duration of ultrahigh-temperature metamorphism in the Anápolis–Itauçu Complex, Southern Brasília Belt, central Brazil – constraints from U–Pb geochronology, mineral rare earth element chemistry and trace-element thermometry

Integrated petrographic and chemical analysis of zircon, garnet and rutile from ultrahigh‐temperature (UHT) granulites in the Anápolis–Itauçu Complex, Brazil, is used to constrain the significance of zircon ID‐TIMS U–Pb geochronological data. Chondrite‐normalized rare earth element (REE) profiles of zircon cores have positive‐sloping heavy‐REE patterns, commonly inferred to be magmatic, whereas unambiguous metamorphic grains and overgrowths have flat to slightly negatively sloping heavy‐REE patterns. However, in one sample, a core of zircon interpreted as having formed prior to garnet crystallization and a metamorphic zircon formed within microstructures involving garnet breakdown both display elevated heavy‐REE (and Y) with positive‐sloping patterns. D_REE(zrc/grt) partition coefficients suggest an approximation to equilibrium between zircon and garnet cores, although progressive enrichment in heavy REE towards garnet rims occurs in two of the samples investigated. Titanium‐in‐zircon thermometry indicates zircon growth during both the prograde and post‐peak evolution, but not at peak temperatures of the UHT metamorphism. By contrast, zirconium‐in‐rutile thermometry of inclusions armoured by garnet records crystallization temperatures, based on the upper end of the interquartile range of the data, of ～890 to 870 °C and maximum temperature around 980 °C, indicating prograde and retrograde growth close to and after peak conditions. Rutile located in retrograde microstructures records crystallization temperatures of 850 to 820 °C. Rutile intergrown with ilmenite and included within orthopyroxene, which is associated with exsolved zircon, records temperatures ～760 °C, consistent with Ti‐in‐zircon crystallization temperatures. ID‐TIMS U–Pb geochronological data from two of the four samples investigated define upper intercept ages of 641.3 ± 8.4 Ma (MSWD 0.91) and 638.8 ± 2.5 Ma (MSWD 1.03) that correlate with periods of zircon growth along the prograde segment of the P–T path. Individual zircon U–Pb dates retrieved from all samples range from 649 to 634 Ma, indicating a maximum duration of c. 15 Myr for the UHT event. This period is interpreted as recording modest thickening of hot backarc lithosphere located behind the Arenópolis Arc at the edge of the São Francisco Craton consequent upon terminal collision of the Parána Block with the arc during the amalgamation of West Gondwana.     

Geochemical behavior of rare earth elements in hydrothermally altered rocks of the Kuroko mining area,Japan

In this study we analyzed the chemical composition of hydrothermally altered dacite and basalt from the Kuroko mining area, northeastern Honshu, Japan, by REE (rare earth element). Features of rare earth element analyses include: (1) altered footwall dacite exhibits a negative Eu anomaly compared with fresh dacite, suggesting preferential removal of Eu²⁺ from the altered dacite via hydrothermal solutions, (2) altered hangingwall dacite and basalt and dacite and basalt adjacent to ore deposits exhibit positive Eu anomalies compared with fresh dacite and basalt, suggesting addition of Eu²⁺ from hydrothermal solutions, (3) LREE ratio (∑LREE/∑REE) from altered dacite of chlorite–sericite zone and K-feldspar zone show a negative relationship with δ¹⁸O, and La/Sm ratios show a positive correlation with the K₂O index. These trends indicate the addition of light rare earth elements such as La to the altered dacite from hydrothermal solution and/or leaching of heavy rare earth elements such as Sm and Yb, (4) Principal component analysis (PCA) indicates that light rare earth elements enrichment is related to the formation of sericite zone near the Kuroko deposits but not to the formations of chlorite and K-feldspar zones, and (5) The correlations among REE features (LREE ratio, MREE ratio, HREE ratio, Eu/Eu?), δ¹⁸O and K₂O index are not found for montmorillonite zone, mixed layer clay mineral zone and mordenite zone. Therefore, it is inferred that sericite, chlorite and K-feldspar alterations are related to the Kuroko and vein-type mineralization, but montmorillonite and mordenite alterations are not related to the mineralizations, and probably they formed at the post-mineralization stage.     

The Double Solid Reactant Method for modeling the release of trace elements from dissolving solid phases: I. Outline and limitations

A Double Solid Reactant Method was elaborated from a suggestion of Marini (Geological sequestration of carbon dioxide: Thermodynamics, kinetics, and reaction path modeling. Developments in Geochemistry, Elsevier, Amsterdam, 2007) to simulate the release of trace elements during the progressive dissolution of solid phases. The method is based on the definition, for each dissolving solid, of both an entity whose thermodynamic and kinetic properties are known (either a pure mineral or a solid mixture) and a special reactant, that is, a material of known stoichiometry and unknown thermodynamic and kinetic properties. The special reactant is utilised to take into account the concentrations of trace elements in the dissolving solid phase. In this communication, the influence of several trace elements on the ΔG _f ^o, ΔG _r ^o and log K of the minerals considered by Lelli et al. (Environ Geol, 2007) and Accornero and Marini (Geobasi, 2007a; Proceedings of IMWA symposium, Cagliari, 27–31 May 2007b) was evaluated assuming ideal mixing in the solid state. These effects were found to be negligible for albite and the leucite–latitic glass, limited for muscovites and chlorites, and slightly more important for apatites. These influences become progressively higher with increasing concentration of trace elements in these minerals. Based on these deviations in thermodynamic parameters, special reactants should not include oxide components with molar fractions higher than 0.003. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Heavy metals and rare earth elements (REEs) in soil from the Nam Co Basin,Tibetan Plateau

Twenty-eight soil samples collected from the Nam Co Basin, Tibetan Plateau, have been analyzed for heavy metals (Cd, Cr, Ni, Cu, Zn, Pb and Mn), arsenic (As) and rare earth elements (REEs). In addition, for establishing the basic physio-chemical characteristics of the soil, pH, total organic concentration, electrical conductivity, and effective cation exchange capacity were measured. The results indicate that soil in the Nam Co Basin is still at an early alkaline weathering stage (pH = 7.94). Mean concentrations of heavy metals and As decreased as follows: Mn > Cr > Zn > Pb > Ni > Cu > As > Cd. The values of Cd, Cr, As, Pb and REEs in soil from the Nam Co Basin are higher relative to averaged background values over China. The chondrite-normalized diagrams of REEs suggest high REE(ΣLa → Eu)—enrichment, HREE(ΣGd → Lu)—depletion and Eu—depletion. Vertical profiles indicate that both heavy metals (except As) and REEs primarily exist in the surface soil. However, heavy metals and REEs vary in the surface soil between the southern and the northern bank of Nam Co. These differences are controlled mainly by parent materials.     

Chemical weathering of granite under acid rainfall environment, Korea

Chemical weathering was investigated by collecting samples from five selected weathering profiles in a high elevation granitic environment located in Seoul, Korea. The overall changes of chemistry and mineralogical textures were examined reflecting weathering degrees of the samples, using polarization microscopy, X-ray diffraction (XRD), electron probe micro analysis (EPMA), X-ray fluorescence spectroscopy (XRF), and inductively coupled plasma–mass spectroscopy (ICP–MS). The chemical distribution in the weathering profiles shows that few trace elements are slightly immobile, whereas most major (particularly Ca and Na) and trace elements are mobile from the beginning of the granite weathering. On the other hand, there were mineralogical changes initiated from a plagioclase breakdown, which shows a characteristic circular dissolved pattern caused by a preferential leaching of Ca cation along grain boundaries and zoning. The biotite in that region is also supposed to be sensitive to exterior environmental condition and may be easily dissolved by acidic percolated water. As a result, it seems that some rock-forming minerals in the granitic rock located in Seoul are significantly unstable due to the environmental condition of acidic rainfall and steep slopes, where they are susceptible to be dissolved incongruently leading some elements to be highly depleted.     

Petrogenesis of Volcanic Rocks from Saipan and Rota, Mariana Islands, and Implications for the Evolution of Nascent Island Arcs

An ⁴⁰Ar/³⁹Ar age of 45·1 Ma determined for lavas fromnorthern Saipan confirms that these high-silica rhyolites eruptedduring the ‘proto-arc’ stage of volcanism in theIzu–Bonin–Mariana system, which is characterizedelsewhere by eruption of boninitic lavas. Incompatible traceelement concentrations and Sr, Hf, Nd, and Pb isotope ratiosfor these rhyolites are transitional between those of c. 48Ma boninitic lavas and post-38 Ma ‘first-arc’ andesitesand dacites from Saipan and Rota that have typical subduction-relatedcompositions. These transitional compositions are modeled bycrystal fractionation of parental tholeiitic basalt combinedwith assimilation of young boninitic crust. A second stage ofRayleigh fractionation in the upper crust is required by SiO₂concentrations that exceed 77 wt % and near-zero compatibleelement concentrations. First-arc magma compositions are consistentwith fractionation of basalt and assimilation of crust similarin composition to the first-arc magmas themselves. The mantlesources of the proto-arc and first-arc lavas from Saipan andRota are similar to those of Philippine back-arc basin basaltsbased on Nd and Hf isotopic compositions. The Pb isotope compositionsof these lavas are between those of Pacific sea-floor basaltsand Jurassic and younger cherty and clay-rich sediments. Thiscontrasts with the boninitic proto-arc volcanic rocks from Guamand Deep Sea Drilling Project Sites 458 and 459 that have Pbisotope compositions similar to Pacific basin basalts and volcaniclasticsediments. The preferred explanation for the difference in thenature of proto-arc volcanism between Saipan and other fore-arclocations is that the crust ceased extending 3–4 Myr earlierbeneath Saipan. This was caused by a change from mantle upwelling,fore-arc extension, and shallow melting to an environment dominatedby more normal mantle wedge convection, stable crust, and deepermelting. KEY WORDS: rhyolite; andesite; Mariana arc; isotope ratios; trace elements     

定位定向系统数据的航空高光谱影像几何校正

针对航空高光谱数据几何畸变严重的问题,该文探索了利用POS数据辅助航空高光谱影像几何校正的研究现状,分析了基于POS系统的导航数据的线阵推扫高光谱数据解算成像瞬间外方位元素的原理,以及行方位数据支持的线中心投影影像通过改进的共线方程方法几何校正的过程,实现了无地面控制点数据的直接几何校正。采用高光谱影像分块处理方法,实现了高吞吐快速几何校正。HySpex SWIR-384高光谱影像的实验结果表明,该文的校正算法可达到9.15m的绝对定位精度,最终利用少量地面控制点进行几何精校正,其均方根误差达到0.93m。     

武汉市城市空间集聚要素的分布特征与模式

不同城市要素的集聚现象具有不同的空间模式,定量化研究城市要素集聚模式的差异和联系对于理解城市发展机理、合理制定城市规划具有重要意义。本文以武汉市为例,获取不透水表面、商业服务业网点（POI）、人口、容积率、城市道路等城市要素数据;采用核密度估计法识别城市主次中心,从城市要素的分布形态、集聚程度、集聚模式等来研究城市要素的空间分布格局特征。研究发现,武汉市呈现“一主七副”的多中心结构,各城市要素从城市中心向外呈反S型的圈层递减。采用集聚度指数衡量城市要素的集聚水平,结果显示商业POI、人口密度的集聚程度最大,其次是容积率、道路密度、不透水表面占比。高度集聚的商业POI、人口密度呈现出点状模式与带状模式相结合的分布模式,中度集聚的道路密度、容积率呈现点状模式、环状模式与轴状模式相结合的分布模式,低度集聚的不透水表面密度主要表现为环状模式。城市中心的吸引、立体空间开发等促进了城市要素的向心集聚,交通干线、稀缺景观资源的廊道效应等重塑了城市要素的空间分布形态。