Migration and Leaching of Phosphorus and Aluminum in Basalt Weathering Profile: Implications for Late Permian Weathering-Depositional Mineralization in Yunnan-Guizhou-Guangxi Region
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摘要: 磷（P）和铝（Al）分别作为生物限制性营养元素和重要金属元素而被广泛关注.在近地表环境中，岩石风化是P和Al元素释放的重要途径. 玄武岩是一种富含磷酸盐矿物（如玄武质玻璃、磷灰石等）和铝硅酸盐矿物（如长石、辉石等）的岩石，是P和Al元素的重要岩石储库. 目前对于玄武岩风化过程中P、Al元素的活动规律还未有深入研究.为进一步理解玄武岩的化学风化作用，对峨眉山大火成岩省分布区的玄武岩风化剖面开展了矿物学、地球化学和磷组分研究，并结合已报道的玄武岩风化剖面数据探讨物理侵蚀对Al、P元素风化淋失的控制机制，分析晚二叠世相关的风化‒沉积成矿效应.黑石风化剖面下部为含有大量长石等原生矿物的半风化层，相对玄武质原岩其化学风化强度明显升高（CIA值分别为40和72~83），上部为含有石英、赤铁矿和黏土矿物的土壤层，呈现极端风化状态（化学风化指数CIA值为90~92）.利用Ti的稳定性与原岩标准化计算来衡量元素的活动性，结果显示Na、Ca、Mg、P和Eu自下而上均发生不同程度的丢失，Fe、K和Ce在半风化层发生显著丢失而在土壤层中呈现相对富集，Al在土壤层相对亏损而Zr则相对富集.土壤层中的高石英含量和低Ti/Zr比值，可能指示了风成长英质粉尘输入的影响.基于黑石风化原岩和风成粉尘组成构建了二元混合曲线，发现风化剖面均具有相对较低的P/Ti比值，而Al/Ti比值仅在土壤层呈现降低的趋势.这一变化特征表明，P元素在早期风化阶段即发生大量（> 50%）淋失，残余土壤中P的赋存状态也经历由原岩溶解态磷到弱吸附态磷再到强吸附态磷的转变；在极端风化条件下，Al元素可随酸性流体、富Al黏土矿物或络合物的渗流和淋洗作用而发生部分（> 20%）迁移和丢失.地表风化状态取决于物理侵蚀与化学风化速率的相对大小，侵蚀速率较高时出露更多弱风化的岩石而有利于P的风化淋失，侵蚀速率较低时发育更多强烈风化的土壤层而有利于Al的风化淋失.综合华南西部晚二叠世玄武质泥岩的风化趋势，认为峨眉山大火成岩省的风化侵蚀状态是控制Al、P风化‒沉积富集的重要因素.Abstract: Phosphorus (P) and aluminum (Al) are respectively recognized as a critical nutrient limiting element for biological processes and a significant metallic element. Within the near-surface environment, rock weathering is the predominant mechanism facilitating the release of these elements. Basalt, featuring abundance of phosphate mineral minerals (including basaltic glass and apatite) and aluminosilicate minerals (such as feldspar and pyroxene), constitutes a substantial rock reservoir for both P and Al elements. Despite the importance of these elements, a comprehensive understanding of the behavior of P and Al during basalt weathering remains an area ripe for further investigation. To enhance the understanding of the chemical weathering process of basalt, this study undertook a detailed examination of the weathering profile within the Emeishan Large Igneous Province(ELIP), employing mineralogical, geochemical, and phosphorus form analyses. Additionally, by integrating published data on basalt weathering profiles, the study explores the control mechanisms of physical erosion on the weathering leaching of P and Al elements and analyzes the weathering-deposition mineralization effects related to the Late Permian period.The basal section of Heishi weathering profile is characterized by a semi-weathered layer that is rich in primary minerals, including a substantial quantity of feldspar. Relative to the basaltic parent rock, this layer exhibits a markedly enhanced degree of chemical weathering, as indicated by Chemical Index of Alteration (CIA) values of 40 for the parent rock and a range of 72 to 83 for the semi-weathered layer. The upper section of the profile comprises a soil layer that incorporates quartz, hematite, and various clay minerals, reflecting an advanced stage of weathering, with CIA values that extend from 90 to 92. Utilizing the stability of Ti and normalization to the parent rock for calculating the mobility of elements, the results indicate that there is a varying degree of loss of Na, Ca, Mg, P, and Eu from the bottom up. Fe, K, and Ce show significant depletion in the semi-weathered layer but are relatively enriched in the soil layer. Al is relatively depleted in the soil layer, while Zr is relatively enriched.The soil layer, characterized by high quartz content and a low Ti/Zr ratio, likely indicates the influence of aeolian input from feldspathic dust.A binary mixing curve was constructed based on the composition of the weathered black stone protolith and aeolian dust, revealing that the weathering profiles have relatively low P/Ti ratios, while the Al/Ti ratio only shows a decreasing trend in the soil layer. This pattern suggests that P is significantly (> 50%) leached during the early stages of weathering, and the state of phosphorus in the residual soil undergoes a transition from dissolved phosphorus in the protolith to weakly adsorbed phosphorus and then to strongly adsorbed phosphorus. Under extreme weathering conditions, Al can be partially (> 20%) mobilized and lost through the percolation and leaching of acidic fluids, Al-rich clay minerals, or complexes. The degree of weathering at the surface is contingent upon the relative rates of physical erosion and chemical weathering. When erosion rates are high, a greater exposure of weakly weathered rocks occurs, which favors the weathering and leaching of P. Conversely, when erosion rates are low, a more extensive development of intensely weathered soil layers takes place, which favors the weathering and leaching of Al. Integrating the weathering trends of Late Permian basaltic mudstones in the western South China, it is posited that the weathering and erosion conditions of the ELIP are significant factors controlling the weathering-deposition enrichment of P and Al.
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图 1 (a) 华南西部大地构造简图(据Qi and Zhou, 2008); (b)研究区地质图; (c)黑石风化剖面的野外露头照片并显示采样位置
Fig. 1. (a) Tectonic of western South China (modified from Qi and Zhou, 2008); (b) geological map of the study area; (c) field photograph of Heishi weathering profile showing sampling locations
图 2 黑石风化剖面的XRD矿物组成及图谱
Qtz.石英；Pl.斜长石；Aug.辉石；Hm.赤铁矿；An.锐钛矿；CM.黏土矿物；AM.非晶质矿物
Fig. 2. XRD mineral composition and spectrum of Heishi weathering profile
图 3 (a) 黑石风化剖面样品的A-CN-K(Al2O3-(CaO*+Na2O)-K2O)三角图; (b)风化原岩标准化的稀土元素配分模式
黑石风化剖面附近出露的峨眉山玄武岩的化学组成与风化剖面的玄武质原岩在A-CN-K图具有一致性
Fig. 3. (a) A-CN-K (Al2O3-(CaO*+Na2O)-K2O) triangle diagram of the Heishi weathering profile samples; (b) the REE distribution patterns (parent rock-normalized)
图 4 黑石风化剖面的CIA值和i/Ti、Ce/Ce*、Eu/Eu*、Ti/Zr比值变化趋势
i/Ti比值的i代表Si、Na、Ca、Mg、Al、Fe、K
Fig. 4. Changes in CIA, i/Ti, Ce/Ce*, Eu/Eu*, and Ti/Zr ratios of Heishi weathering profile
图 5 黑石风化剖面玄武质原岩与黄土 < 20 μm组分的Ti/Zr与Al/Ti(a)和P/Ti(b)元素比值二元混合曲线图
UCC指平均大陆上地壳（Rudnick and Gao, 2003）
Fig. 5. Binary mixing curves of Ti/Zr and Al/Ti (a) and P/Ti (b) element ratios of the parent rock and loess < 20 μm components in the Heishi weathering profile
图 6 黑石风化剖面中(a)P/Ti、Al/Ti、TN、TOC、pH的变化趋势以及(b)磷组分组成
Fig. 6. Change trends of (a) P/Ti, Al/Ti, TN, TOC, and pH and (b) phosphorus forms composition in the Heishi weathering profile
图 7 玄武岩风化剖面的(a)CIA‒(P2O5/TiO2)N的分布; (b) Al2O3‒TiO2的分布; (c~d)玄武岩的P、Al风化侵蚀模型
Fig. 7. (a) CIA‒(P2O5/TiO2)N distribution; (b) Al2O3‒TiO2 distribution of basalt weathering profile; (c‒d) P, Al weathering erosion models of basalt
图 8 右江盆地北缘晚二叠世龙潭组玄武质泥岩的CIA值变化指示峨眉山大火成岩省的风化‒侵蚀模式
灰色圆点为钻孔Zk15916的泥岩数据，在该剖面的对应位置还标注了凝灰岩的高精度锆石U-Pb年龄（Yang et al., 2022），同时也标出了中‒晚二叠世（GLB）、吴家坪‒长兴期（WCB）和二叠‒三叠纪（PTB）3个界线的位置和对应年龄（Cohen et al., 2013）.图中也展示出钻孔Zk31917和ZK34381的泥岩风化趋势（绿色和红色实线）
Fig. 8. Changes in CIA of the basaltic mudstone of the Late Permian Longtan Formation in the northern margin of the Youjiang Basin indicate the weathering-erosion pattern of the Emeishan LIP
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