基于高光谱的富钴结壳主要成矿元素可反演性研究

Assessment of the Hyperspectral Retrievability of Major Metallogenic Elements in Cobalt-rich Crusts

  • 摘要: 本研究以西太平洋麦哲伦海山群77个富钴结壳粉末样品为对象,利用LabSpec®4 Hi-Res地物光谱仪获取350~2 500 nm反射光谱,结合元素数据,构建“高光谱—元素”数据集,开展光谱响应研究、可反演性评价和机制分析,揭示富钴结壳元素含量与高光谱反射率之间的响应关系及其矿物学机制,评价主要成矿元素含量的高光谱可反演性。首先采用非负矩阵分解(Non-negative Matrix Factorization, NMF)解析样品混合光谱的主要变化方向及其可能的矿物学来源;随后通过逐波段皮尔逊相关分析和连续统去除(Continuum Removal, CR)提取元素吸收特征,识别元素敏感波段;最后采用偏最小二乘回归(Partial Least Squares Regression, PLSR)构建元素含量反演模型,并结合交叉验证指标和RPD(Residual Prediction Deviation)对元素光谱可反演性进行分级评价。结果表明:①NMF端元数为5时,模型在重构误差和端元稳定性之间达到较好平衡。5个数学端元具有不同的谱形特征,反映多组分混合控制下的主要光谱变化方向,其光谱响应主要受Fe-Mn氧化物吸收背景、磷酸盐/碳酸盐组分、硅铝质/碎屑组分及元素协变关系的共同控制;②元素含量与高光谱反射率的相关响应主要集中于可见光—近红外前段,主要响应区间为463~1058 nm,其中450~700 nm附近相关性最强;P、Ca等在该区间呈正相关,而Fe、Mn、Co、Ni、Ti、V等呈负相关;③PLSR交叉验证结果显示,不同元素的光谱可反演性差异明显。Ca和P具有相对较高的建模能力,最优模型交叉验证 R_cv^2 分别为0.553和0.519,RPD分别为1.506和1.451;Fe、Mn、Co等多个主要成矿元素的模型交叉验证 R_cv^2 >0.4,RPD>1。总体而言,富钴结壳高光谱主要响应Fe-Mn氧化物背景、磷酸盐/碳酸盐组分、硅铝质/碎屑组分以及H2O/OH相关短波红外变化等混合光谱结构,混合光谱中包含以离子吸附或晶格替代形式赋存的主要元素弱信号,可用于部分元素的定量或半定量预测以及其他元素的初步筛查。

     

    Abstract: This study focused on 77 powdered cobalt-rich crust samples from the Magellan Seamounts in the western Pacific. Reflectance spectra over the range of 350-2500 nm were acquired using a LabSpec® 4 Hi-Res field spectrometer. Combined with chemical elemental data, a hyperspectral–element dataset was established to investigate spectral responses, evaluate retrievability, and analyse the underlying mechanisms. This study aimed to reveal the relationships between elemental contents and hyperspectral reflectance in cobalt-rich crusts, clarify their mineralogical mechanisms, and assess the hyperspectral retrievability of elemental contents. The study first used non-negative matrix factorization (NMF) to analyse the main variation directions of the mixed spectra of the samples and their possible mineralogical sources. Then, bandwise Pearson correlation analysis and continuum removal (CR) were applied to extract elemental absorption features and identify element-sensitive bands. Finally, partial least squares regression (PLSR) was used to construct retrieval models, and the spectral retrievability of elements was classified based on cross-validation metrics and RPD. The results show that: ① The selection of the number of NMF endmembers indicates that k=5 achieves a favourable balance between reconstruction error and endmember stability. The five mathematical endmembers exhibit different spectral characteristics, indicating the main spectral variation directions controlled by multi-component mixing. These responses are jointly controlled by the Fe-Mn oxide absorption background, phosphate/carbonate components, aluminosilicate/detrital components, and elemental covariation. ② The correlations between elemental concentrations and hyperspectral reflectance are mainly concentrated in the visible to early near-infrared region, with the principal response interval occurring at 463-1058 nm and the strongest correlations around 450-700 nm. P and Ca show positive correlations within this interval, whereas Fe, Mn, Co, Ni, Ti, and V show negative correlations. ③ PLSR cross-validation results reveal clear differences in spectral retrievability among elements. Ca and P show relatively better modeling performance, with the optimal models yielding cross-validated coefficients of determination ( R_\textcv^2 ) of 0.553 and 0.519 and RPD values of 1.506 and 1.451, respectively. Several major metallogenic elements, including Fe, Mn, and Co, also achieved R_\textcv^2 >0.4 and RPD>1. Overall, the hyperspectral signatures of cobalt-rich crusts are primarily controlled by the mixed spectral effects of the Fe-Mn oxide background, phosphate/carbonate components, aluminosilicate/detrital components, and H2O/OH-related shortwave infrared absorption features. The mixed spectra also contain weak spectral signals associated with major elements occurring through ion adsorption or lattice substitution mechanisms. These signals can be utilized for the quantitative or semi-quantitative prediction of certain elements, as well as for the preliminary screening of others.

     

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