碳酸盐矿物面扫描U-Pb定年方法及其在复杂流体改造样品中的应用

Surface-Scanning U-Pb Dating of Carbonate Minerals and Its Application to Samples Altered by Complex Fluids

  • 摘要: 碳酸盐U-Pb定年可为盆地流体演化与油气成藏提供直接时间约束。点剥蚀法虽已广泛应用于碳酸盐定年,但碳酸盐矿物普遍存在低U、高普通Pb及多期流体改造等特征,导致数据点U/Pb比值分散度不足,定年成功率低,制约了该技术的应用。本文以三种方解石标样WC-1、GX-5、Tarim以及三个实际样品HY2(川中二叠系页岩中高普通Pb方解石)、GLC-1(川中二叠系灰岩及其低U方解石脉体)、DH1-3(贵州泥盆系灰岩中多期流体改造裂缝方解石)为研究对象,采用激光剥蚀扇形质谱(LA-SF-ICP-MS)面扫描直接U-Pb定年方法,通过点剥蚀法与面扫法对比,评估该方法对复杂碳酸盐样品的适用性及对深度分馏效应的抑制效果。针对上述定年难题,面扫描模式将单点驻留时间缩短至<5 s,并将有效剥蚀脉冲数由约200次降至50次以内,从而减弱深度分馏效应;结合连续线扫描与虚拟点构建,扩大U/Pb比值分布范围,增强此类样品的定年约束。标样验证表明,面扫法年龄误差较点剥蚀法显著缩小(WC-1: ±2.6 Ma → ±1.3 Ma;Tarim: ±6.5 Ma → ±3.4 Ma)。三类实际样品分析验证了该方法适用性:高普通Pb方解石样品HY2,点剥蚀法无法获得有效年龄,而面扫法获得239 ± 19 Ma下交点年龄,与四川盆地早印支运动吻合;低U样品(GLC-1)年龄误差由±41 Ma缩小至±2.9 Ma;多期流体活动样品(DH1-3)一次面扫同时获取母岩(384.4 ± 9.9 Ma)、高Mg方解石(379 ± 44 Ma)及方解石脉(247 ± 15 Ma)三个独立年龄。该方法显著提高了复杂碳酸盐样品的定年精度和成功率,为盆地流体演化与成藏年代学研究提供了可靠技术支撑。

     

    Abstract: Carbonate U-Pb dating provides direct temporal constraints on basin-fluid evolution and hydrocarbon accumulation. Although the spot-ablation method has been widely applied to carbonate dating, carbonate minerals commonly exhibit low U concentrations, high common-Pb contents, and multistage fluid alteration. These characteristics result in insufficient dispersion of U/Pb ratios among analytical spots and consequently lead to low dating success rates, limiting the application of this technique. In this study, three calcite reference materials—WC-1, GX-5, and Tarim—and three natural samples—HY2, high common-Pb calcite from Permian shale in central Sichuan; GLC-1, medium- to low-U calcite veins hosted in the Permian limestones of the central Sichuan Basin; and DH1-3, fracture-filling calcite affected by multistage fluid alteration in Devonian limestone from Guizhou—were investigated using a direct U-Pb dating method based on laser-ablation sector-field inductively coupled plasma-mass spectrometry (LA-SF-ICP-MS) mapping. Comparisons between spot ablation and the mapping method were conducted to evaluate the applicability of the latter to complex carbonate samples and its effectiveness in suppressing downhole fractionation. To address these dating challenges, the mapping method reduced the single-point dwell time to <5 s and decreased the number of effective ablation pulses from approximately 200 to <50, thereby reducing downhole fractionation. Combined with continuous line scanning and virtual spot construction, this method expanded the range of U/Pb ratios and improved the geochronological constraints for such samples. Validation using the reference materials showed that the age uncertainties obtained using the mapping method were substantially smaller than those obtained using spot ablation, decreasing from an uncertainty of ±2.6 Ma to ±1.3 Ma for WC-1 and from ±6.5 Ma to ±3.4 Ma for Tarim. Analyses of the three natural samples further demonstrated the applicability of this method. For HY2, the high common-Pb calcite from Permian shale in central Sichuan, spot ablation failed to yield a valid age, whereas the mapping method produced a lower-intercept age of 239 ± 19 Ma, consistent with the Early Indosinian Movement in the Sichuan Basin. For the low-U sample GLC-1 from Permian limestone in central Sichuan, the age uncertainty decreased from ±41 Ma to ±2.9 Ma. For DH1-3, the sample affected by multistage fluid activity in Devonian limestone from Guizhou, a single mapping run simultaneously yielded three independent ages for the host rock (384.4 ± 9.9 Ma), high-Mg calcite (379 ± 44 Ma), and calcite vein (247 ± 15 Ma). This method significantly improves the dating accuracy and success rate of complex carbonate samples, providing reliable technical support for geochronological studies of basin-fluid evolution and hydrocarbon accumulation.

     

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