Genesis of the Guangou karstic bauxite deposit in western Henan,China

The Guangou bauxite deposit in western Henan, China, is located in the North China Block and to the north of the North Qinling orogenic belt. The orebody is hosted within the lower member of the Carboniferous Benxi Formation, which overlies unconformably upon the Ordovician Majiagou Formation. In the lower member of the Benxi Formation, the bauxite orebody (with a diaspore–illite–anatase mineral assemblage) is sandwiched between underlying ferric clay (illite–hematite–goethite) and overlying top clay (kaolinite–quartz–goethite). According to field observations and geochemical evidence including trace- and rare-earth-element (REE) compositions, especially Zr/Hf ratios, the ferric clays were weathered from the underlying argillaceous limestones in the Majiagou Formation. During this weathering process, trace elements S, Zn, Ni, Cr, V, Sc, F, Ba, and Be are depleted; Li, Rb, and B are enriched; and Zr, Hf, Bi, Ta, Ga, Nb, and Th are relatively immobile. REEs exhibit evident differentiation with enrichment of La, Ce, Pr, and Nd and depletion of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The bauxite formed in weak reducing, slightly basic water conditions according to the geneses of coexisting diaspore and anatase, and it was altered during the epigenetic and second exposure periods, forming kaolinite and goethite, respectively. Interelemental relationship analyses of the ores suggest that the elemental behaviors of trace elements and REEs in the bauxitization process are mainly controlled by the mineral compositions in bauxite ore and chemical properties of the elements. For instance, zircon, rutile, and anatase contain Zr, Hf, Nb, Ta, W, and U. Based on geochemical evidence, together with age data and chemical compositions of the detrital minerals, both distant igneous rocks in the plate margin and Paleozoic carbonates and Precambrian rocks inside North China Block provide the miscellaneous material for the bauxite ore and the top clay.     

桂西平果教美矿区堆积型铝土矿形成过程中矿物转化与元素迁移

桂西地区铝土矿为典型喀斯特型,包括二叠系沉积型和第四系堆积型两亚类。堆积型铝土矿是沉积型铝土矿经抬升、破碎、风化,最后堆积于喀斯特洼地中形成。以平果教美铝土矿为研究对象,探索堆积型铝土矿形成过程中矿物的变化与元素迁移。沉积型矿石的矿物组成包括硬水铝石、鲕绿泥石、锐钛矿及少量针铁矿、金红石和高岭石;堆积型矿石的矿物组成主要为硬水铝石、锐钛矿、高岭石及少量三水铝石和鲕绿泥石。转化过程中堆积型矿石中的硬水铝石含量明显增加,鲕绿泥石含量明显减少。沉积型铝土矿的主要化学组成为Al₂O₃、SiO₂、FeO和TiO₂;堆积型为Al₂O₃、SiO₂、TiO₂和Fe₂O₃。两类矿石中元素Zr 、Ba、Nb、V含量均较高,稀土总量变化大,富集轻稀土。质量平衡计算表明堆积型铝土矿形成过程中Al、Ba、Sr、Y等元素增加,而Si、Fe、Ti、Nb、V、Ce等元素减少,其余元素变化不明显。     

桂西田阳堆积型铝土矿矿物学及地球化学

[摘 要]桂西田阳堆积型铝土矿产于第四纪红土层中。本文通过对桂西田阳第四系堆积型铝土矿进行一系列矿物学与地球化学研究,探索铝土矿的物质来源。矿物学分析显示铝土矿石中主要矿物为硬水铝石、赤铁矿和锐钛矿,含有少量高岭石、鲕绿泥石、三水铝石、针铁矿、金红石、伊利石、蒙脱石和石英等。地球化学分析显示,组成铝土矿石的主要化学组分有Al₂O₃、Fe₂O₃、SiO₂、TiO₂、FeO 和H₂O⁺;微量元素分析显示,铝土矿石相对地壳和原始地幔富集B、Li、Ga、Zr、Hf、Nb、Ta、W、Th、U 等元素,而亏损Ni、Cr 等元素。矿石中明显富集稀土元素,稀土总量变化大,轻重稀土分异明显,轻稀土元素富集明显;矿石具有明显的铈异常和铕异常,且铕异常相对稳定,为一致的负异常。元素相关性分析显示常量元素间相关性较差;部分微量元素如Zr、Hf、Nb 和Ta 间呈现出较高的正相关性。通过Zr/ Hf、Nb/ Ta 图解、Eu/ Eu* - TiO₂/ Al₂O₃图解和Zr-Cr-Ga 图解综合分析显示铝土矿物质来源复杂,底板碳酸盐岩和周围火成岩都为铝土矿提供物源。     

贵州修文小山坝铝土矿中稀土元素地球化学特征

前人已经积累了大量贵州铝土矿的研究成果,但关于铝土矿与其中稀土元素的关系至今不清。本研究以修文小山坝铝土矿为例,通过ICP-MS分析测试,研究了矿石和围岩的稀土元素组成。结果表明,矿石中稀土配分模式为轻稀土富集向右倾斜型,具明显Eu负异常,与下寒武统娄山关群含泥质白云岩稀土特征参数和配分模式相似,指出该矿床成矿物质来源以下寒武统娄山关群含泥质白云岩为主,在相对氧化环境下经风化作用成矿。矿床中稀土元素主要富集于矿体及其周围,与Al2O3含量具正相关关系。矿石中稀土元素含量大多达到或超过综合利用标准,具有巨大的潜在经济价值。     

Discovery of the REE minerals and its geological significance in the Quyang bauxite deposit,West Guangxi,China

Most of the karstic bauxite deposits in China are enriched in REE, and the REE has commonly been considered to be adsorbed on the surface of clay or diaspore minerals as ion state. However, occurrence of REE minerals in the bauxite deposits has not been reported by far. In the Quyang bauxite deposit from Guangxi province, we find REE minerals. The minerals are parisite and churchite. Parisite is widely distributed in the ooids and matrix, inducing positive Ce anomaly of the ores; whereas, churchite is rare and occurred in the core of ooid. The compositions of the REE minerals show the Eu anomaly can change gently during the weathering, and the Eu anomaly analyses suggest that the REE in the ores are mostly derived from the underlying carbonates. The parisite is formed in an alkaline condition, while churchite in an acidic situation; the co-existence of the two minerals in the ores suggests the Permian environment for bauxite formation is complex with great change of pH value. Moreover, parisite is inferred to be formed earlier than the churchite.     

Origin and geochemical evolution from ferrallitized clays to karst bauxite: An example from the Lower Cretaceous of NE Spain

Four outcrops of Lower Cretaceous (Barremian) karst bauxites located in Teruel (NE Spain) were analysed. The deposits show a heterogeneous-chaotic lithostructure consisting of pisolitic bauxite blocks embedded in lateritic red clays filling karst cavities. The research has focused on the geochemical study of major, minor, and trace elements (including some critical to industry) of both the bauxites and clays. The objective was to investigate the bauxite precursor material and to characterize the system’s geochemical evolution. Geochemical analyses were carried out by inductively-coupled plasma optical emission and mass spectroscopy. An absolute weathering index has been calculated to estimate element mobility, assuming Ti as an immobile element and the Upper Continental Crust (UCC) as parent material. Further, selected samples were observed by field emission scanning electron microscopy. The data indicate that both the bauxites and red clays originated by intense chemical weathering from more mafic argillaceous sediments than the UCC. Ongoing weathering caused the bauxitization of the upper parts of the original profile, preventing the lower parts from being bauxitized, thus producing the ferrallitized clays underlying the pisolitic bauxites. Subsequent karst reactivation gave rise to the current lithostructure. Ferrallitization is related to Fe, Sc, and V enrichment. On the other hand, although bauxites are relatively enriched in some elements compared to clays, the more intense chemical weathering associated with bauxitization led to chemical homogenization and widespread element depletion. During the bauxitization, Al, Ti, Zr, Cr, and probably Hf and the critical element Nb behaved as more immobile elements in the system. Bauxitization also enhanced homogenization and depletion of the REE, which is more pronounced for the LREE. HREE trends seem to be partly related to the concentration of Ti oxides in the bauxites, whereas P-bearing phases, more frequent in the clays, control the LREE. Subsequent to bauxitization, partial kaolinization of the bauxite took place related to the circulation of acid solutions that also caused the karst reactivation. These late processes caused some Al depletion in the bauxites and enhanced Fe loss together with V and, to a lesser extent, Ge.     

Mineralogical and geochemical investigations of the Dajia Salento-type bauxite deposits,western Guangxi,China

The Dajia Salento-type bauxite deposit in western Guangxi is hosted within the Quaternary ferrallitic soil profile, and it formed via breaking up, weathering and oxidizing of Permian bauxite orebodies occurring as a semi-continuous layer in the upper Permian. Mineralogical analyses reveal that diaspore, hematite and kaolinite are the major minerals in bauxite ores with small amounts of anatase, chamosite, gibbsite, goethite, illite, zircon, quartz and pyrite. The ore texture and mineral assemblage reveal that the depositional/diagenetic environment of the Dajia bauxite was much close to phreatic environment. Both the ore texture and the morphology of zircon grains also indicate that most of the bauxitic soils were transported a short distance. Diaspore is suggested to be non-metamorphic in origin and mainly formed in a reducing condition of diagenetic environment, while kaolinite is the product of the in situ epigenetic replacement of alumina in diaspore by dissolved silica. Geochemical analyses indicate that Al₂O₃, Fe₂O₃, SiO₂ and TiO₂ are the main components of the bauxite ores and trace elements such as Zr, Hf, Nb, Ta, Th and U were enriched during the bauxitization process. Simultaneously, Zr vs. Hf and Nb vs. Ta show a high correlation. Geochemical indices such as Zr/Hf, Nb/Ta and Eu/Eu* (among others) denote that the magmatic rocks related to the Emeishan plume in western Guangxi and the carbonates in the underlying Maokou Formation provided the main sources of material for the bauxite ores.     

离子吸附型稀土矿床形成的矿物表/界面反应机制

华南离子吸附型稀土矿床提供了全球超过90%的重稀土,是我国优势的战略性关键金属矿产资源。掌握这类矿床的成矿机制和禀赋特征,可为增加稀土资源储量和高效利用稀土资源提供理论支撑。离子吸附型稀土矿床主要发育在富稀土花岗岩、浅变质岩及火山岩的风化壳中。基岩中的(含)稀土矿物是风化壳中离子态稀土的主要来源,其矿物组合很大程度上决定了稀土矿床的禀赋和分异特征。在物理-化学风化和微生物作用下,造岩矿物、含稀土矿物和稀土独立矿物逐渐溶解,使稀土元素活化和再富集。一方面,母岩风化形成的黏土矿物和铁锰氧化物具有较大的比表面积和一定的表面电荷密度,是稀土离子的主要载体;另一方面,稀土离子通过离子交换、表面吸附与络合、共沉淀,以及形成次生稀土矿物等途径富集在次生矿物表面,其富集-分异特征和赋存状态受矿物类型、pH、微生物活动等因素所控制。利用高分辨透射电镜结合选区电子衍射和电子能量损失谱,以及同步辐射X射线吸收精细结构谱,有望在原子级尺度查明稀土的微观赋存状态。未来研究需更多关注基岩中(含)稀土矿物组合及其演化路径的制约因素、微生物风化对离子吸附型稀土矿床成矿作用的约束,以及稀土元素的微观赋存状态等问题。     

Mineralogical and geochemical investigations of the Mombi bauxite deposit,Zagros Mountains,Iran

The Mombi bauxite deposit is located in 165 km northwest of Dehdasht city, southwestern Iran. The deposit is situated in the Zagros Simply Fold Belt and developed as discontinuous stratified layers in Upper Cretaceous carbonates (Sarvak Formation). Outcrops of the bauxitic horizons occur in NW-SE trending Bangestan anticline and are situated between the marine neritic limestones of the Ilam and Sarvak Formations. From the bottom to top, the deposit is generally consisting of brown, gray, pink, pisolitic, red, and yellow bauxite horizons. Boehmite, diaspore, kaolinite, and hematite are the major mineral components, while gibbsite, goethite, anatase, rutile, pyrite, chlorite, quartz, as well as feldspar occur to a lesser extent. The Eh–pH conditions during bauxitization in the Mombi bauxite deposit show oxidizing to reducing conditions during the Upper Cretaceous. This feature seems to be general and had a significant effect on the mineral composition of Cretaceous bauxite deposits in the Zagros fold belt. Geochemical data show that Al₂O₃, SiO₂, Fe₂O₃ and TiO₂ are the main components in the bauxite ores at Mombi and immobile elements like Al, Ti, Nb, Zr, Hf, Cr, Ta, Y, and Th were enriched while Rb, Ba, K, Sr, and P were depleted during the bauxitization process. Chondrite-normalized REE pattern in the bauxite ores indicate REE enrichment (ΣREE = 162.8–755.28 ppm, ave. ∼399.36 ppm) relative to argillic limestone (ΣREE = 76.26–84.03 ppm, ave. ∼80.145 ppm) and Sarvak Formation (ΣREE = 40.15 ppm). The REE patterns also reflect enrichment in LREE relative to HREE. Both positive and negative Ce anomalies (0.48–2.0) are observed in the Mombi bauxite horizons. These anomalies are related to the change of oxidation state of Ce (from Ce³⁺ to Ce⁴⁺), ionic potential, and complexation of Ce⁴⁺ with carbonate compounds in the studied horizons. It seems that the variations in the chemistry of ore-forming solutions (e.g., Eh and pH), function of carbonate host rock as a geochemical barrier, and leaching degree of lanthanide-bearing minerals are the most important controlling factors in the distribution and concentration of REEs. Several lines of evidences such as Zr/Hf and Nb/Ta ratios as well as similarity in REE patterns indicate that the underlying marly limestone (Sarvak Formation) could be considered as the source of bauxite horizons. Based on mineralogical and geochemical data, it could be inferred that the Mombi deposit has been formed in a karstic environment during karstification and weathering of the Sarvak limy Formation.     

贵州务川瓦厂坪铝土矿床地球化学特征

务川瓦厂坪铝土矿床是近年探明的大型矿床,332+333资源量4397万吨.地球化学研究显示,矿床中Al_2O_3与TiO_2含量成正相关关系,与SiO_2含量成负相关关系;硫同位素组成属于沉积岩范畴,总体显示出变化范围大(-29.20‰～+12.40‰),反映出复杂的成矿环境和轻重硫同位素的多次分离;不同岩、矿石的稀土总量(∑REE)含量变化大,LREE/HREE均大于1,显示轻稀土较富集;铝土矿层中,土状铝土矿稀土元素含量相对高,致密块状铝土矿含量相对低,稀土元素含量与矿石质量总体呈正相关关系.铝土矿层及志留系韩家店组的稀土总量含量较接近.矿床成因属古风化壳沉积型.     

Mineralogical and geochemical studies of boron-rich bauxite ore deposits in the Songqi region,SW Henan,China

The Songqi region, SW Henan, is an important bauxite province in China. The bauxite ore deposits occur unconformably on the top of Middle Ordovician argillaceous carbonates. The bauxite ores from the Songqi region are characterized by unusually high boron contents. In this paper, we report the mineralogical and chemical compositions of selected bauxite ores from the region. These new data, together with existing geochemical data of soils in the region, are used to evaluate the origin of boron enrichment in the bauxite ores. The compositional characteristics of tourmaline in the bauxite ores suggests that this mineral was likely derived from a meta-sedimentary protolith. Mass balance calculation reveals that tourmaline only accounts for a small portion of boron in the bauxite ores; the majority of boron in the ores must occur in other forms, possibly by ion absorption on the surfaces of diaspore and clay minerals. In the Songqi region, the Precambrian meta-sedimentary rocks are known to contain abundant tourmalines whereas the Cambrian–Ordovician argillaceous carbonates and the Upper Proterozoic shales are all enriched in boron in free ion state. We suggest that these rocks provided tourmaline and boron ion to the bauxite deposits in the region. Most known bauxite deposits in the Songqi region occur at the margins of boron-rich soil domains, suggesting that boron in soils is a potential exploration indicator for unknown bauxite deposits in this region.     

华北南缘石炭纪仁村大型喀斯特型铝土矿物质来源与成矿过程研究

华北克拉通在中奥陶世至晚石炭世经历了强烈的风化和喀斯特化作用, 并在晚石炭世形成大规模喀斯特型铝土矿, 但是其物质来源及成矿过程目前仍存争议。本文选取华北南缘仁村大型喀斯特型铝土矿床, 在矿床地质剖析基础上, 对两个钻孔岩心进行矿物学、地球化学、碳-氧同位素分析, 剖析了成矿物质来源和成矿环境条件, 总结了铝土矿形成过程。仁村铝土矿含矿岩系赋存于奥陶系灰岩风化面之上的石炭系本溪组中, 含矿岩系自下而上包括铁质粘土岩、铝土矿和粘土岩。X衍射和扫描电镜-能谱分析显示铁质粘土岩主要矿物为菱铁矿和伊利石, 铝土矿主要矿物为硬水铝石、黄铁矿、菱铁矿、锐钛矿、伊利石和高岭石, 而粘土岩主要矿物为高岭石和勃姆石。铁质粘土岩元素组成以SiO₂、FeO、Al₂O₃为主, 铝土矿以Al₂O₃、SiO₂、FeO、TiO₂为主, 而粘土岩主要为SiO₂。微量元素Zr、Hf、Nb、Ta、Th和U等在含矿岩系呈现整体富集, 稀土元素主要在铝土矿层底部富集。硬水铝石-黄铁矿-菱铁矿矿物集合体、铝土矿层中Ce异常、La/Y和(La/Yb)_N比值以及菱铁矿C-O同位素组成(δ¹³C: -11.35‰~-7.63‰; δ¹⁸O: -9.26‰~-5.93‰)揭示铝土矿主要形成于地表碱性-还原的喀斯特洼地环境, 微生物广泛参与成矿过程。微量-稀土元素组成及稳定元素比率显示含矿岩系成矿物源存在明显垂向变化。其中, 底部铁质粘土岩主体为底板碳酸盐岩原地风化形成, 而顶部铝土矿和粘土岩为异地来源。综合前人研究成果, 提出了华北南缘石炭系本溪组铝粘土矿三阶段形成过程: 早期风化阶段(450~320Ma)形成铁质粘土岩或铁质风化壳; 物源输送阶段(320~310Ma)堆积大规模成矿物质; 成矿及后生改造阶段(< 310Ma)形成大规模铝粘土矿。

     

Geological,geochemical, and mineralogical characteristics of the Mandan and Deh-now bauxite deposits,Zagros Fold Belt,Iran

The Mandan and Deh-now bauxite deposits are located 40 km northeast of the Dehdasht city in the Zagros simply fold belt. These deposits occur in eroded major NW–SE trending anticlines and occupy karst cavities near or at the boundary between the Sarvak and Ilam Formations. Local uplifts at the end of the Cenomanian and the mid-Turonian caused erosion and karstification of the Sarvak Formation. These unconformities in the Upper Cretaceous favoured the formation and enrichment of bauxite deposits in the Zagros fold belt. The bauxite sequence in the Mandan deposit consists of white, gray, black, pisolitic, red, and yellow bauxites. This sequence was repeated in the Deh-Now area, but without gray and black bauxites. The present mineralogical studies of the Sarvak Formation and the Mandan and Deh-now bauxite deposits indicate oxidizing to reducing conditions during the Upper Cretaceous in the Zagros fold belt, which had a significant effect on the compositions of the bauxites. At least two phases of bauxitization can be distinguished in the study area: (i) an oxidizing phase represented by boehmite, diaspore, hematite and kaolinite; and (ii) a reducing phase represented by pyrite and chlorite. Geochemical data show that trace elements, like Zr, Hf, Nb, Ta, Th, and U, were enriched during bauxitization. The bauxite deposits and carbonate rocks show similar REE patterns, namely they are enriched in REEs although the LREEs are more enriched than the HREEs. Mass change calculations demonstrate that Mg, Mn, Ca, K, and P₂O₅ were leached out of the weathered system whereas Al, Fe, and Si become concentrated in the residual system. This study indicates that the Mandan and Deh-now deposits are karst-type bauxites formed by karstification and weathering of the Sarvak Formation.     

Importance of hydrogeological conditions during formation of the karstic bauxite deposits,Central Guizhou Province,Southwest China: A case study at Lindai deposit

Karstic bauxite deposits are widespread in Central Guizhou Province, SW China, and high-grade ores are frequently sandwiched with overlying coal and underlying iron-rich layers and form a special “coal–bauxite–iron” structure. The Lindai deposit, which is one of the most representative karstic bauxite deposits in Central Guizhou Province, was selected as a case study. Based on textural features and iron abundances, bauxite ores in the Lindai deposit are divided into three types of ores, i.e., clastic, compact, and high-iron. The bauxite ores primarily comprise diaspore, boehmite, kaolinite, illite, and hematite with minor quartz, smectite, pyrite, zircon, rutile, anatase, and feldspar. The Al₂O₃ (53–76.8 wt.%) is the main chemical contents of the bauxite ore samples in the Lindai district, followed by SiO₂, Fe₂O₃, TiO₂, CaO, MgO, S, and P etc. Our geological data on the Lindai deposit indicated that the ore-bearing rock series and its underlying stratum have similar rare earth elements distribution pattern and similar Y/Ho, Zr/Hf, and Eu/Eu¹ values; additionally, all ore-bearing rock samples are rich in MgO (range from 0.16 wt.% to 0.68 wt.%), and the plots of the dolomites and laterites lie almost on or close to the weathering line fit by the Al-bearing rocks in Zr vs. Hf and Nb vs. Ta diagrams; suggesting that the underlying Middle Cambrian Shilengshui Formation dolomite is the parent rock of bauxite resources in the Lindai district.Simulated weathering experiments on the modern laterite from the Shilengshui Formation dolomite in the Lindai bauxite deposit show that hydrogeological conditions are important for karstic bauxite formation: Si is most likely to migrate, its migration rate is several magnitudes higher than those of Al and Fe under natural conditions; the reducing inorganic acid condition is the most conducive to Al enrichment and Si removal; Fe does not migrate easily in groundwater, Al enrichment and Fe removal can occur only in acidic and reducing conditions with the presence of organic matter.The geological and experimental studies show that “coal–bauxite–iron” structure in Lindai deposit is formed under certain hydrogeological conditions, i.e., since lateritic bauxite or Al-rich laterite deposited upon the semi-closed karst depressions, Si can be continuously removed out under neutral/acidic groundwater conditions; the coal/carbonaceous rock overlying the bauxitic materials were easily oxidized to produce acidic (H₂S, H₂SO₄, etc.) and reductant groundwater with organic materials that percolated downward, resulting in enrichment of Al in underlying bauxite; it also reduced Fe³⁺ to its easily migrating form Fe²⁺, moving downward to near the basal carbonate culminated in precipitating of ferruginous (FeS₂, FeCO₃, etc.) strata of the “coal–bauxite–iron” structure. Thus, the bauxitic materials experienced Al enrichment and Si and Fe removal under above certain hydrogeological conditions forming the high-quality bauxite.     

河南三门峡贯沟铝土矿矿物组成及其特征

[摘 要] 河南三门峡市贯沟铝土矿属喀斯特型铝土矿。研究区内地层发育相对完全,除上奥陶统、 志留系、泥盆系和下石炭统地层缺失外,从太古界到新生界均有出露。铝土矿层主要产出于中石炭系本 溪组下段。矿石以鲕粒和隐晶质结构为主,少量碎屑结构。矿物学分析显示,铝土矿矿石的主要组成矿 物有硬水铝石、锐钛矿、伊利石,另外,还包括少部分高岭石、锆石等。硬水铝石呈隐晶质结构组成矿石 的基质,少部分呈现细小的板状、长柱状形态。锐钛矿存在两种形态:第一种是锐钛矿与硬水铝石二者 同期形成;第二种锐钛矿以脉状穿插在硬水铝石组成的基质中,形成稍晚于硬水铝石。伊利石主要呈鳞 片状集合体形态组成矿石的基质。锆石主要分散在硬水铝石组成的基质中。进一步研究发现:硬水铝 石电子探针分析显示晶体中存在Fe、Si 和Ti 等其它元素,其主体呈隐晶质与锐钛矿密切共生,指示硬水 铝石主要为简单的成岩结晶成因。矿石中的锐钛矿和硬水铝石共生,互相包含和穿插,反映大量的锐钛 矿是成矿期或成岩期结晶形成。对风化作用中形成的伊利石主要由云母转化而形成,该过程中矿物结 构并未发生明显改变。     

广西某地花岗岩风化壳中稀土元素特征与iREE矿床成矿机制

为了解风化壳中离子交换相稀土元素的特征,对广西某地花岗岩风化壳剖面样品进行了X射线衍射及主量、稀土元素地球化学特征的研究.剖面自上而下可划分为腐殖土层(A₁)、亚粘土层(A₂)、网纹状风化层(B₁)和全风化层(B₂);自A₁至B₂,粘土矿物的含量和化学风化蚀变指数快速降低;与母岩相比A₁、A₂、B₁中全相Ce、Nd和HREE相对富集,B₂中全相稀土与母岩特征相似,所有样品的离子交换相HREE亏损,Y相对富集;离子交换相轻、重稀土一起富集在B₂中.据此推测,花岗岩中褐帘石、榍石等易风化的稀土矿物为离子交换相稀土提供了主要的物源,锆石、磷钇矿等难风化的稀土矿物的残留及表生稀土矿物的形成使全相HREE相对富集;离子交换相轻、重稀土元素的分馏程度随风化程度的增加而变化.      

Transformation from Permian to Quaternary bauxite in southwestern South China Block driven by superimposed orogeny: A case study from Sanhe ore deposit

Permian karstic bauxite and its Quaternary derivative, in western Guangxi, southwestern, South China Block, possess a total tonnage greater than 0.5 billion tons. The primary late Permian karstic bauxite formed in reduced environment in the background of Tethyan accretionary orogenesis. And as one consequence of Cenozoic convergence of the Indian and Eurasia continents, the primary orebody was uplifted, eroded and re-sedimented within Quaternary laterite. The geochemical variation and its controls during the ore transformation from Permian to Quaternary remain poorly understood. Quaternary ore blocks comprise an inner zone of fresh ore, and then it gradually transited through a middle zone to a margin with extensive weathering. One such bauxite block was selected and further subdivided into twenty-three samples for geochemical and mineralogical analysis. The inner and middle zones contain similar mineralogical compositions, dominated by diaspore and amesite, with minor illite, anatase, goethite, pyrite, zircon, and rutile. The margin is composed of diaspore, with small amounts of amesite, boehmite, illite, goethite, anatase, kaolinite, zircon, rutile, and barite. Bauxite in all three zones is composed of mainly Al, Si, Fe, and Ti, and high contents of Zr, Cr, Li, F, S, Zn, V, Sr, Nb, Ba, and REE. Variations in Fe²⁺ and Fe³⁺ between the three zones were observed. The elements Si, Al, Fe²⁺, Mg, Ba, Cr, F, Li, Ni, Zn, and REE decrease from the core of the ore block outwards, corresponding to an increase in S and Fe³⁺. Depletions in Si, Al, Fe²⁺, Mg, Ba, and Cr were caused by the dissolution of amesite. Most of the Al and Si in amesite were lost during the weathering, and minor retained to form kaolinite. Depletions in Li, Ni, and Zn resulted from changes in the depositional environment between the late Permian and Quaternary. Dissolution of REE-bearing fluorocarbonates resulted in depletions of REE and F. The enrichment of Fe³⁺ and S was related to the precipitation of goethite, hematite, and barite in an oxidizing environment, while local enrichment of Ce resulted from the redox change of Ce³⁺ → Ce⁴⁺ under the same condition. This shows that the chemical composition of laterite enwrapping the bauxite also took part in Quaternary bauxite transformation. This study shows that the elements migrations during bauxite transformation were influenced by multiple independent factors except for the elemental attributes.     

Genesis of REE minerals in the karstic bauxite in western Guangxi,China, and its constraints on the deposit formation conditions

Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnäsite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnäsite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnäsite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnäsite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce^3 +, released from bastnäsite rapidly, entered the rhabdophane lattice before being oxidized to Ce^4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce^3 + was oxidized into Ce^4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnäsite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore.     

华北石炭纪艾雨头大型喀斯特铝土矿成因机制研究

喀斯特型铝土矿中硬水铝石的成因机制对准确认识该矿床的成因至关重要, 也是业界长期争论的焦点。早期普遍认为风化作用阶段形成的三水铝石经历后期压实变质作用脱水形成硬水铝石, 然而近期大量研究显示自然界铝土矿中硬水铝石多为地表喀斯特型环境下结晶形成。华北晚石炭世发育大规模硬水铝石型喀斯特铝土矿, 本文选取华北北部艾雨头大型铝土矿床为研究对象, 在翔实的矿床地质研究基础上, 借助X射线粉末衍射(XRD)、扫描电镜-能谱分析(SEM-EDS)及激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)技术, 探索硬水铝石的地表结晶条件和铝土矿的形成过程。艾雨头铝土矿含矿岩系剖面自下而上依次包括铁质粘土岩、铝土矿和粘土岩, 其中: 铁质粘土岩矿物组成主要为伊利石、高岭石、针铁矿、赤铁矿、硬水铝石和锐钛矿; 铝土矿主要为硬水铝石、高岭石、赤铁矿、针铁矿和锐钛矿; 粘土岩为高岭石、针铁矿、赤铁矿和锐钛矿。艾雨头喀斯特铝土矿顶底板岩石未发生变质作用, 而且原位分析显示硬水铝石中含有较高含量的Si、Fe、Ti、Cr、V、Pb等元素, 指示硬水铝石为表生沉淀成因。矿石中发现硬水铝石与赤铁矿和针铁矿密切共生, 表明硬水铝石可在氧化条件下形成(Eh>0.2)。硬水铝石中氧化还原敏感元素间良好的线性关系(包括V/Mn-Cr/Mn、V/Fe-Cr/Fe、V/Fe-U/Fe和U-Cr)以及V、Cr、U元素的共同富集, 指示硬水铝石沉淀时氧化还原阈值为T₁-T₃(即低氧-还原环境(-0.4 < Eh < 0.4))。硬水铝石中较高含量的Fe元素以及与硬水铝石共生的赤铁矿和针铁矿中较高含量的Al元素反映成矿前期已形成了大量的铁铝固溶体(Al_xFe_1-x(OH_y)^3-y)。这些不稳定的铁铝固溶体在成岩阶段转变为含铁硬水铝石(Fe-AlOOH)和含铝针铁矿、赤铁矿(Al-FeOOH、Al-Fe₂O₃); 含铁硬水铝石在后期压实成岩过程中进一步转变为硬水铝石。该研究结果解释了艾雨头铝土矿中硬水铝石地表大规模结晶的基本条件和过程, 对全面认识华北喀斯特铝土矿具有重要意义。

     

Rare earth geochemistry in the dissolved, suspended and sedimentary loads in karstic rivers, Southwest China

The watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) is a karstic area. Rare earth elements (REEs) of dissolved loads, suspended particulate material (SPM) and sediments of riverbed are first synthetically reported to investigate REE geochemistry in the three phases in karstic watershed during the high-flow season. Results show that the low dissolved REE concentrations in the CQW are attributed to these rivers draining carbonate rocks. The dissolved REE have significant negative Eu anomaly and coexistence of middle and light REE (MREE??PAAS-normalized La _N /Sm _N and Gd _N /Yb _N ; LREE??PAAS-normalized La _N /Yb _N )-enrichment, which are due to the dissolution of impure Triassic carbonates. REE concentrations in most of SPM exceed that of sediments in the CQW and the average continental crust (UCC). The SPM and the sediments show some common features: positive Eu, Ce anomalies, and MREE enrichment. The controls on the patterns seem to be from weathering profiles: the oxidation state, the REE-bearing secondary minerals (cerianite, potassium feldspar and plagioclase), which are also supported by the evidence of Y/Ho fractionations in the three phases.