An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Cr-spinel/olivine and Cr-spinel/liquid nickel partition coefficients from natural samples

The Nernst partition coefficient of nickel (D^Ni) between Cr-spinel and silicate melt in natural systems has been investigated using mid-ocean ridge basalts (MORB) and other volcanic rocks. The Cr-spinel/olivine D^Ni values in volcanic rocks are between 1.2 and 0.3, indicating that the Cr-spinel/liquid D^Ni values vary from slightly higher to significantly lower than the olivine/liquid D^Ni values in natural systems. The Cr-spinel/liquid D^Ni values from the MORB samples vary between 6 and 11, slightly higher than those from the S-bearing experiments of Satari et al. [Satari P., Brenan J. M., Horn I. and McDonough W. F. (2002) Experimental constraints on the sulfide- and chromite-silicate melt partitioning behavior of rhenium and platinum-group elements. Economic Geology97, 385-398]. The results of the MORB samples and the experiments of Satari et al. (2002) indicate a negative correlation between the Cr-spinel/liquid D^Ni and the X_Cr values in Cr-spinels (Cr cation number on the basis of 3 total cations in the spinel structure). Variations of Cr-spinel/liquid D^Ni values with Cr-spinel compositions can be estimated from an empirical equation based on the results of the MORB samples and the experiments by Satari et al. (2002). The choice of Cr-spinel/liquid D^Ni = 10 for numerical modeling by Righter et al. [Righter K., Leeman W. P. and Hervig R. L. (2006) Partitioning of Ni, Co, and V between spinel-structured oxides and silicate melts: importance of spinel composition. Chemical Geology227, 1-25] is reasonable for basaltic systems. For picritic and komatiitic systems a lower value of ∼5 is more appropriate.     

Iron isotope fractionation in subterranean estuaries

Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redox-stratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ⁵⁶Fe values between 0.3 and −1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ⁵⁶Fe values down to −5‰. These low δ⁵⁶Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Fe-oxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ⁵⁶Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ⁵⁶Fe values between −2 and 1.5‰. The relationship between Fe concentration and δ⁵⁶Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ⁵⁶Fe values relative to river values.     

Simple models for dynamic melting in an upwelling heterogeneous mantle column: Analytical solutions

Several lines of evidence suggest that the melt generation and segregation regions of the mantle are heterogeneous, consisting of chemically and lithologically distinct domains of variable size and dimension. Partial melting of such heterogeneous mantle source regions gives rise to a diverse range of basaltic magmas. In order to better assess the role of source heterogeneity during mantle melting, we have undertaken a theoretical study of trace element distribution and fractionation during concurrent melting and melt migration in an upwelling, chemically heterogeneous, two-porosity double lithology melting column. Analytical solutions for the abundance of a trace element in the matrix and channel were obtained under the assumptions that the porosity, melt and solid velocities, and solid-melt partition coefficients are constant and uniform. For simplicity, we neglected diffusion and dispersion in the melt. Chemical source heterogeneities of arbitrary size and shape were integrated into the simple melting models by allowing trace element abundance in the source region to vary as a function of time and space. Concurrent melting and melt migration in an upwelling heterogeneous mantle may be approximated as a quasi-steady state problem in which time-dependent concentration patterns produced by melting of heterogeneous source regions are superimposed on a reference steady-state concentration distribution established by melting of the ambient or background mantle. Chromatographic fractionation is especially important for the matrix melt and solid when chemical heterogeneities are involved during melting and melt migration in the mantle, giving rise to significant phase-shift between two incompatible trace elements in the matrix melt and scattered correlations among incompatible trace elements in residual peridotites. Mixing is the chief mass transfer process in the dunite channel where the chromatographic effect is negligible for most of the incompatible trace elements. The lack of chromatographic fractionation among incompatible trace elements and isotopic ratios in MORB suggests either most MORB are channel melts or mixing in magma conduit and chamber is very efficient such that the phase-shift is averaged out during magma transport and storage processes. Advection brings melt produced by smaller-degree of melting in the deeper part of the melting column to the overlying melting region, increasing the incompatible trace element abundance in the matrix and the channel. This advection-induced self-enrichment is especially important when heterogeneous sources are involved and may account for some of the enriched incompatible trace element patterns observed in residual peridotite that were previously interpreted to be a result of mantle metasomatism. Systematic studies of high-resolution spatially correlated mantle samples may help to constrain the melting history and the size and nature of chemical heterogeneities in the mantle.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

Monitoring Large-Scale Tests for Nuclear Waste Disposal

Two large-scale “in situ” demonstration experiments and their instrumentation are described. The first test (FEBEX Experiment) involves the hydration of a compacted bentonite barrier under the combined effect of an inner source of heat and an outer water flow from the confining saturated granite rock. In the second case, the progressive de-saturation of Opalinus clay induced by maintained ventilation of an unlined tunnel is analyzed. The paper shows the performance of different sensors (capacitive cells, psychrometers, TDR’s) and a comparison of fill behaviour with modelling results. The long term performance of some instruments could also be evaluated specially in the case of FEBEX test. Capacitive sensors provide relative humidity data during long transient periods characterised by very large variations of suction within the bentonite.     

柴达木盆地北缘侏罗系两类不同有机质丰度泥岩的 生物标志物特征对比研究

在柴达木盆地北缘地区,分别选取有机碳含量很低和较高的侏罗系泥岩样品,对比分析了它们在生物标志物组成上的差异。结果发现,高有机质丰度泥岩的生标组成与我国西北地区侏罗纪煤系有机质的特征差异不大,相比而言,低有机质丰度泥岩的正烷烃以前主峰为特征,Pr/Ph比值在1.0左右,三环萜烷和伽马蜡烷丰度较高,并在部分样品中检出了25 降藿烷系列。结合泥岩的有机岩石学特征,认为这些差异可能反映了泥岩沉积环境和生烃母质的不同:高有机质丰度泥岩的有机显微组分以相对弱还原条件下的形态有机质为主,包括藻类体、孢子体和角质体等,而低有机质丰度泥岩的有机显微组分以相对强还原条件下的矿物沥青基质为主,其母质可能来源于低等显微菌藻类。进一步通过对比不同有机质丰度泥岩,以及区内原油生标组成之间的相互关系,讨论了研究区的油源问题。     

延边东部五道沟岩群的单颗粒锆石SHRIMP U-Pb 年代学及其地质意义

通过对延边地区东部五道沟岩群黑云阳起石片岩的单颗粒锆石SHRIMP U-Pb年龄测定.获得21个单点年龄,其中包括7组谐和年龄和1组不谐和年龄.谐和年龄分别为1347.8 Ma、844.8 Ma、340.2～313.7 Ma(平均值为323±23 Ma,N=4,MSWD=0.23,置信度=0.88)、292.9～288.3 Ma(平均值=291±25 Ma,N=3,MSWD=0.031.置信度=0.86)、279.2～266.2 Ma(平均值为279±28 Ma,N=4,MSWD=0.031,置信度=0.86)、127.4～124.2 Ma(206Pb/208U年龄平均值为126.5±3.7 Ma,N=5,MSWD=0.12;置信度=O.97)、116.1～106.3 Ma(平均值为115±39 Ma,N=2,MSWD=1.2置信度=0.27),不谐和年龄的下交点年龄为(451±120)Ma、上交点年龄为(1811±400)Ma(MSWD=7.2);这一结果表明:阳起石片岩的原岩主要是来自中元古代、新元古代和早古生代的碎屑物,指示五道沟群的沉积成岩作用发生在石炭世(323±23 Ma),变质作用发生在晚二叠世(291±25 Ma),之后在279.2～266.2 Ma、126.5～106.3 Ma先后受两次岩浆用和蚀变作用的改造.     

浙江杭州地区中下奥陶统岩石地层研究

笔者以城市基岩地质填图和剖面研究资料为基础,选择临安市板桥乡南山上中下奥陶统剖面为候选层型,根据剖面的地层层序、岩性组合、分界标志,结合区域变质的总体特征,重新厘定、划分了4个组级岩石地层单位,并依据荆山岭与板桥剖面的地层、生物化石对比,确定其地层时代为早中奥陶世。这对重建杭州地区层型剖面与地质遗迹保护、岩石地层填图、奥陶纪石灰岩矿产资源的开发利用都具有重要意义。     

都思兔河中段河水化学成分的形成机制分析

在分析研究区地质及水文地质条件的基础上,根据对各类水样资料的研究,发现在都思兔河中段,对于相对惰性的组分,河水的化学成分由湖水与地下水混合形成;但对于易发生化学反应的组分,湖水在向下游运动的过程中,其化学成分明显受到了化学反应的影响。论文使用Cl-质量平衡方法,计算出该段河水中地下水的补给比例在50%以上;并且根据研究区的具体条件及矿物饱和指数的计算结果,确定石膏的溶解、方解石和白云石的沉淀以及CO2逸出是河水化学成分形成的主要化学作用,通过对化学反应量的计算,恢复了湖水与地下水仅发生了简单混合作用的混合水的成分。