酸淋滤对古老蚀变大洋玄武岩Sr-Nd-Hf-Pb同位素的影响

The effect of acid-leaching on the Sr-Nd-Hf-Pb isotopic compositions of ancient oceanic basalts

  • 摘要: Sr-Nd-Hf-Pb同位素是示踪大洋玄武岩源区和揭示其岩石成因的重要手段。准确获得蚀变玄武岩真实的Sr-Nd-Hf-Pb同位素组成,是研究玄武岩地幔源区组成的基础。海水蚀变可能改变大洋玄武岩的同位素组成,在溶样前对其进行酸淋滤可有效降低或去除海水蚀变的影响。常用的酸淋滤方案大都是探讨其能否有效去除海水蚀变对年轻的大洋玄武岩Sr-Nd-Hf-Pb同位素的影响;然而,对于古老的、蚀变程度高的大洋玄武岩,因为与海水长时间的相互作用,可能经历了更为复杂的蚀变过程。使用年轻大洋玄武岩的淋滤方案能否有效去除海水蚀变对古老蚀变大洋玄武岩Sr-Nd-Hf-Pb同位素的影响,以及在对其同位素进行年龄校正时如何选择样品微量元素母子体比值(未淋滤或淋滤后),仍需要进一步的探讨。本研究用3种方案对西太平洋拉蒙特海山(81.6~87.1 Ma)和采薇海山(91.3 Ma)的4个玄武岩样品进行了酸淋滤处理,并对淋滤后的样品进行了微量元素和Sr-Nd-Hf-Pb同位素分析。结果显示,淋滤样品的Sr和Pb同位素组成与未淋滤样品存在明显差异,Nd和Hf同位素组成则相似,表明海水蚀变对Sr和Pb同位素影响较大,而对Nd和Hf同位素影响较小。用方案1(6 mol/L热(60 ℃)HCl反复超声清洗直至上层酸液变无色)和方案3(多步骤淋滤,即依次用2 mol/L HCl、6 mol/L HCl、4 mol/L HNO3和6 mol/L HCl在60 ℃电热板上分别反应2、2、2和12 h)处理后的4个样品具有相似的Sr-Nd-Hf-Pb同位素比值(除样品MASD65-1的Pb同位素比值相差较大外)。与用方案1和方案3处理后相比,方案2(6 mol/L热(60 ℃)HCl淋滤12 h)处理后的2个采薇海山样品Pb同位素比值较低,表明方案2并未有效去除海水蚀变形成的次生矿物。由于海水蚀变会改变大洋玄武岩的Rb、U和Pb等元素组成,因此未淋滤样品的Rb/Sr、U/Pb和Th/Pb比值不能代表其原始组成。用未淋滤和淋滤后的拉蒙特和采薇海山样品的Rb/Sr、U/Pb和Th/Pb比值对淋滤后样品的Sr和Pb同位素进行年龄校正,得到的Sr-Pb同位素初始值有较大偏差,而Nd-Hf同位素初始值相似。进一步校正结果表明,对于年龄大于5 Ma的蚀变海底岩石样品,为尽可能准确获得其岩浆来源的Sr-Nd-Pb同位素初始值,需分析同一份酸淋滤后样品的Rb/Sr、Sm/Nd、U/Pb和Th/Pb比值,对酸淋滤后样品的Sr-Nd-Pb同位素进行年龄校正,而Hf同位素则不需要。综合不同酸淋滤方案的效率差异,为去除海水蚀变的影响,本研究推荐使用方案1或方案3对蚀变的古老大洋玄武岩进行处理,并分析同一份淋滤后样品的微量元素和Sr-Nd-Pb同位素比值,用其母/子体元素比值来对同位素进行年龄校正,以获得准确的初始值。

     

    Abstract: Sr-Nd-Hf-Pb isotope data are important tools for tracing the mantle sources and decoding the petrogenesis of oceanic basalts, and thus it is crucial to obtain the real Sr-Nd-Hf-Pb isotopic compositions of altered oceanic basalts. Seawater alteration can modify the isotopic compositions of oceanic basalts, and acid-leaching prior to sample dissolution can efficiently reduce or remove the influence of seawater alteration. Most acid-leaching protocols focused on whether they can efficiently eliminate the effect of seawater alteration on Sr-Nd-Hf-Pb isotopes of young oceanic basalts. However, for ancient, highly altered oceanic basalts, prolonged interaction with seawater may have led to more complex alteration processes. It remains unclear whether the leaching protocols applied to young oceanic basalts can sufficiently remove the effects of seawater alteration on Sr-Nd-Hf-Pb isotopes of ancient altered oceanic basalts. Furthermore, when applying age correction to these isotopic values, whether to use the parent-daughter element ratios of unleached or leached samples requires further investigation. This study applied three acid-leaching procedures to basalts from the Lamont (81.6-87.1 Ma) and Caiwei (91.3 Ma) seamounts in the Western Pacific. The leached samples were analyzed for trace element and Sr-Nd-Hf-Pb isotope data. The results show that all leached samples have different Sr and Pb isotopic values from the unleached samples, but similar Nd and Hf isotopic values, indicating that seawater alteration have a great effect on Sr and Pb but negligible effect on Nd and Hf isotopic compositions. The four samples treated with procedure 1 (ultrasonically leaching 8-10 times with 6 mol/L HCl at 60 ℃) and procedure 3 (sequential leaching on an electric hotplate at 60 ℃ with 2 mol/L HCl for 2 h, 6 mol/L HCl for 2 h, 4 mol/L HNO3 for 2 h, and 6 mol/L HCl for 12 h)—have similar Sr-Nd-Hf-Pb isotopic ratios (except for sample MASD65-1 showing slightly different Pb isotopic ratios). Comparing to procedures 1 and 3, two samples from Caiwei guyot treated with procedure 2 (leaching with 6 mol/L hot (60 ℃) HCl for 12 hours) have lower Pb isotopic ratios, indicating that procedure 2 did not efficiently remove seawater alteration effect on these two samples. Since seawater alteration can modify Rb, U, and Pb concentrations in oceanic basalts, the Rb/Sr, U/Pb, and Th/Pb ratios of unleached samples cannot represent their original compositions. When using the Rb/Sr, U/Pb, and Th/Pb ratios of both unleached and leached Lamont and Caiwei seamount samples to perform age corrections on the Sr and Pb isotopes of the leached samples, the correction results in significant deviations in the initial Sr-Pb isotopic values, whereas it does not change the initial Nd-Hf isotopic values. Furthermore, we found that for altered oceanic basalts older than 5 Ma, in order to obtain the accurate initial Sr-Nd-Pb isotopic values, it is necessary to analyze the Rb/Sr, Sm/Nd, U/Pb, and Th/Pb ratios from the same acid-leached aliquot and use the parent/daughter element ratios to perform age corrections on the Sr-Nd-Pb isotopes of the leached samples. Hf isotopic data do not require this correction. Considering the efficiency differences among the three acid-leaching protocols, this study recommends the use of procedure 1 or procedure 3 for processing ancient (>5 Ma) altered oceanic basalts. Subsequently, trace element and Sr-Nd-Pb isotopic data should be analyzed on the same leached aliquot, and the initial Sr-Nd-Pb isotope ratios should be age-corrected using the parent/daughter element ratios on the same leached aliquot.

     

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