Reliability assessment and calibration of elemental signal values by XRF core scanning in Qinghai Lake
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摘要:
XRF岩芯连续扫描因其快速、连续、无损、高分辨率等优势在近30年常被用于不同相沉积物的元素半定量分析，特别是在湖泊沉积岩芯中的应用极为广泛。然而，XRF扫描信号值易受仪器设置和岩芯物理属性的影响，亟需全面评估其结果可靠性和校正效果。基于青海湖2.39 m长的完整沉积岩芯（QHH）高分辨率XRF连续扫描，结合其含水量、粒度、烧失量、元素实际含量等理化特征分析，有效识别了XRF连续扫描信号值及其元素比值的准确性和影响因素，进一步评估了国际通用的Normalized Median-scaled（NMS）和Multivariate Log-ratio Calibration（MLC）模型校正结果的可靠性。结果表明，XRF连续扫描的Zr元素信号值可准确反映QHH岩芯中的实际含量分布，而Si元素和Ti元素因相关性较弱均无法指示其在QHH岩芯中的真实情况。此外，QHH岩芯段较高的含水量明显削弱了Al、Si、K、Ca、Ti、Fe、Mn等原子量较小的元素信号值强度和波动幅度，而干燥岩芯段中XRF扫描的上述元素结果因其高分辨率和颗粒组成差异展现出较大的波动，降低了与实际含量的相关性。Rb、Sr和Zr等原子量较大的微量元素扫描信号值分布受含水量和颗粒组成的影响较小。最后，基于XRF连续扫描的相邻元素比值是快速消除多种因素一致影响的有效方法，而MLC模型对QHH整根岩芯及各段中单一元素信号值校正均有较好效果。上述结果为合理利用湖泊沉积物的XRF连续扫描数据提供借鉴，也为重建青藏高原东北部气候变化及人地关系奠定科学基础。
Abstract:XRF core scanning has been extensively employed for semi-quantitative analysis of elements in various sediment types over the past three decades, particularly in lacustrine deposits due to its rapid, continuous, non-destructive, and high-resolution advantages. However, despite the susceptibility of element signal values obtained through XRF core scanning to instrument settings and core physical properties, there remains a scarcity of comprehensive evaluation regarding data reliability and calibration effects. In this study, a 2.39-m–long sedimentary core from Qinghai Hu (Lake) (QHH) was obtained for high-resolution scanning using an XRF core scanner. Physical and chemical characteristics in water content, grain size distribution, loss on ignition, and actual elemental composition were analyzed for each subsample. Moreover, the accuracy of element signal values and ratios by XRF core scanning and their influencing factors was effectively assessed, and the reliability of calibration results was simultaneously calibrated using internationally recognized models such as Normalized Median-scaled Calibration and Multivariate Log-ratio Calibration (MLC). Results demonstrate that the Zr signal values corresponded accurately to the actual contents in the sediment core sequence, while weak correlations were observed for Si and Ti, indicating their limited significance. Additionally, the presence of higher water content in the core sections significantly attenuated in signal intensity and fluctuation amplitude for elements of Al, Si, K, Ca, Ti, Fe and Mn. Reversely, dry core sections exhibited greater fluctuations in signals of above elements due to high-resolution scanning and variations in particle composition, thereby attenuating their correlations with actual concentrations. Trace elements of higher atomic weights, such as Rb, Sr, and Zr, demonstrated reduced susceptibility to the variations in water content and particle composition in terms of signal distributions. Finally, using the ratio between adjacent elements based on the XRF core scanning was proven a highly effective approach for quickly eliminating the consistent influence of multiple factors. Furthermore, the multivariate log-ratio calibration (MLC) model exhibited superior calibration effects on individual element signal values throughout the QHH core and within each core section. These findings not only offered valuable reference to the scientific application of high-resolution data acquired by XRF core scanning for lake sediments, but also established a foundation for the reconstruction of climate change and for comprehension of human-environment relationships in the northeastern Tibetan Plateau.
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Keywords:
- XRF core scanning /
- element ratio /
- calibration model /
- lacustrine deposit /
- Qinghai Lake
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图 2 QHH沉积岩芯XRF连续扫描元素信号值（黑色线）和实际含量（橙色线）分布
Figure 2. The distributions of elements signal values by XRF core scanning (blank lines) and their actual compositions (orange lines) along the QHH sedimentary sequence
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图 3 QHH沉积岩芯亮度（L*）、Cl元素信号值、含水量、粒度、烧失量分布
Figure 3. The distributions of luminance (L*), Cl element signal values, water content, grain size, and loss on ignition in the QHH sedimentary sequence
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图 4 QHH岩芯及各段的XRF连续扫描元素信号值与实际含量的相关性分析
Figure 4. Correlation analysis of elements signal values by XRF core scanning and their actual contents of the whole sedimentary sequence and two sections in QHH
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图 5 QHH岩芯XRF连续扫描的元素信号比值与实际含量比值的相关性分析
Figure 5. Correlation analysis of elements signal ratios and their actual concentrations ratios in the whole sedimentary sequence of the core in QHH
表 1 QHH-21a岩芯段粗颗粒层（n=9）和细颗粒层（n=42）的XRF连续扫描元素信号值与实际含量的相关性系数
Table 1 Correlation coefficients between elements signal values by XRF core scanning and their actual concentrations in coarse layers (n=9) and fine layers (n=42) in the QHH-21a sequence
Al Si K Ca Ti Fe Mn Rb Sr Zr 粗颗粒层（48～65 cm） −0.67 0.83 −0.47 −0.13 −0.29 −0.22 −0.26 0.48 0.60 0.62 细颗粒层（0～47 cm, 66～101 cm） 0.73 −0.33 0.65 0.48 0.42 0.45 0.61 0.36 0.45 0.94 
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表 2 QHH岩芯及各段XRF连续扫描元素信号值、NMS及MLC校正结果分别与实际含量的相关性系数
Table 2 Correlation coefficients among elements signal values by XRF core scanning, the NMS calibration data, the MLC calibration data, and their actual concentrations of the whole sedimentary sequence and the two sections in QHH
元素 QHH QHH-21a QHH-21b 扫描值 NMS MLC 扫描值 NMS MLC 扫描值 NMS MLC Al 0.47 0.49 0.92 0.71 0.73 0.93 0.16 0.17 0.91 Si −0.31 −0.36 0.92 −0.39 −0.44 0.97 −0.20 −0.27 0.67 K 0.47 0.49 0.94 0.62 0.65 0.94 0.29 0.60 0.92 Ca 0.44 0.50 0.96 0.49 0.55 0.98 0.42 0.42 0.92 Ti 0.22 0.21 0.74 0.36 0.36 0.66 0.12 0.11 0.73 Fe 0.43 0.48 0.94 0.46 0.56 0.95 0.39 0.40 0.90 Mn 0.51 0.56 0.92 0.57 0.67 0.94 0.46 0.47 0.88 Rb 0.46 0.56 0.92 0.41 0.58 0.93 0.58 0.55 0.89 Sr 0.58 0.70 0.94 0.43 0.64 0.94 0.77 0.80 0.93 Zr 0.92 0.89 0.95 0.95 0.94 0.96 0.79 0.73 0.85
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