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Experimental study of platinum solubility in silicate melt to 14 GPa and 2273 K: Implications for accretion and core formation in Earth

机译:铂在硅酸盐熔体中溶解度为14 Gpa和2273 K的实验研究:对地球中吸积和核心形成的影响

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摘要

We determined the solubility limit of Pt in molten haplo-basalt (1 atm anorthite-diopside eutectic composition) in piston-cylinder and multi-anvil experiments at pressures between 0.5 and 14 GPa and temperatures from 1698 to 2223 K. Experiments were internally buffered at ∼IW + 1. Pt concentrations in quenched-glass samples were measured by laser-ablation inductively coupled-plasma mass spectrometry (LA-ICPMS). This technique allows detection of small-scale heterogeneities in the run products while supplying three-dimensional information about the distribution of Pt in the glass samples. Analytical variations in 195Pt indicate that all experiments contain Pt nanonuggets after quenching. Averages of multiple, time-integrated spot analyses (corresponding to bulk analyses) typically have large standard deviations, and calculated Pt solubilities in silicate melt exhibit no statistically significant covariance with temperature or pressure. In contrast, averages of minimum 195Pt signal levels show less inter-spot variation, and solubility shows significant covariance with pressure and temperature. We interpret these results to mean that nanonuggets are not quench particles, that is, they were not dissolved in the silicate melt, but were part of the equilibrium metal assemblage at run conditions. We assume that the average of minimum measured Pt abundances in multiple probe spots is representative of the actual solubility. The metal/silicate partition coefficients (Dmet/sil) is the inverse of solubility, and we parameterize Dmet/sil in the data set by multivariate regression. The statistically robust regression shows that increasing both pressure and temperature causes Dmet/silto decrease, that is, Pt becomes more soluble in silicate melt. Dmet/sil decreases by less than an order of magnitude at constant temperature from 1 to 14 GPa, whereas isobaric increase in temperature produces a more dramatic effect, with Dmet/sil decreasing by more than one order of magnitude between 1623 and 2223 K. The Pt abundance in the Earth’s mantle requires that Dmet/sil is ∼1000 assuming core-mantle equilibration. Geochemical models for core formation in Earth based on moderately and slightly siderophile elements are generally consistent with equilibrium metal segregation at conditions generally in the range of 20–60 GPa and 2000–4000 K. Model extrapolations to these conditions show that the Pt abundance of the mantle can only be matched if oxygen fugacity is high (∼IW) and if Pt mixes ideally in molten iron, both very unlikely conditions. For more realistic values of oxygen fugacity (∼IW − 2) and experimentally-based constraints on non-ideal mixing, models show that Dmet/sil would be several orders of magnitude too high even at the most favorable conditions of pressure and temperature. These results suggest that the mantle Pt budget, and by implication other highly siderophile elements, was added by late addition of a ‘late veneer’ phase to the accreting proto-Earth.
机译:我们确定了Pt在活塞缸和多砧实验中在0.5-14 GPa的压力和1698-2222 K的温度下在熔融的单倍玄武岩(1 atm钙长石-透辉石共晶成分)中的溶解度极限。 〜IW + 1.通过激光烧蚀电感耦合等离子体质谱法(LA-ICPMS)测量淬火玻璃样品中的Pt浓度。该技术可以检测运行产品中的小规模异质性,同时提供有关玻璃样品中Pt分布的三维信息。 195Pt的分析变化表明,所有实验在淬灭后均包含Pt纳米块。多次时间积分斑点分析(对应于本体分析)的平均值通常具有较大的标准偏差,并且计算得出的硅酸盐熔体中Pt溶解度与温度或压力之间无统计学意义的协方差。相反,最低195Pt信号电平的平均值显示出较小的点间变化,而溶解度显示出与压力和温度的显着协方差。我们将这些结果解释为意味着纳米核不是淬火颗粒,也就是说,它们没有溶解在硅酸盐熔体中,而是在运行条件下成为平衡金属集合体的一部分。我们假设在多个探针点中测得的最小Pt丰度的平均值代表实际溶解度。金属/硅酸盐分配系数(Dmet / sil)是溶解度的倒数,我们通过多元回归参数化数据集中的Dmet / sil。统计上可靠的回归表明,压力和温度的升高都会导致Dmet / silto降低,即Pt在硅酸盐熔体中的溶解度更高。在1至14 GPa的恒定温度下,Dmet / sil的降低幅度小于一个数量级,而等压压升高的温度则产生了更为显着的效果,在1623至2223 K之间,Dmet / sil的降低幅度大于一个数量级。假设地幔平衡,地幔中Pt的丰度要求Dmet / sil为〜1000。在中度和轻度嗜铁粒元素的基础上地球核心形成的地球化学模型通常与平衡金属的偏析相一致,一般在20-60 GPa和2000-4000 K的范围内。对这些条件的模型外推表明,Pt的丰度只有在氧气逸度较高(〜IW)且Pt理想地混入铁水中的情况下,才能匹配地幔,这两种情况都不太可能。对于更实际的氧气逸度值(〜IW-2)和基于实验的非理想混合约束,模型显示,即使在最有利的压力和温度条件下,Dmet / sil的数量级也会过高。这些结果表明,地幔Pt的预算,以及其他高度嗜铁亲铁元素的暗示,是通过在成岩的原始地球后期添加“晚期单板”相而增加的。

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