Ferromanganese nodules of freshwater reservoirs of Ol’khon Island (Baikal) and the Kulunda Plain (West Siberia)

Morphology and mineralogical and geochemical compositions of freshwater ferromanganese nodules of Ol’khon Island (Sasa Formation) and Kulunda Plain (Lake Porozhnee) were studied. The study has shown rhythmic structures of the nodules, formed by macro- and microlayers with mineralized microflora. The layers are composed of either crystalline Mn mineral phases and finely dispersed Fe phases (Lake Porozhnee) or, on the contrary, crystalline goethite and X-ray amorphous Mn phases (Ol’khon Island). Separation of Mn and Fe mineral phases in the nodules proceeded during their formation and diagenesis. The freshwater nodules show both high (Lake Porozhnee) and low (Ol’khon Island) Mn/Fe ratios. The predominance of Fe phase in the Ol’khon nodules accounts for their high contents of REE, including Ce. The Porozhnee nodules grew, most likely, more rapidly, which is reflected in their low REE contents and Ce anomaly. The examined chemical and mineral compositions, textures, and structures of the nodules testify to the low-temperature hydrothermal source of their ore substance.     

Behaviour of REE and mass balance calculations in a lateritic profile over chlorite schists in South Cameroon

An in situ weathering profile overlying chlorite schists in the Mbalmayo-Bengbis formations (South Cameroon) was chosen for the study of the behaviour of REE and the evaluation of geochemical mass balance. After physical and mineralogical studies, the chlorite schists and the undisturbed weathered materials were chemically analyzed for major elements (X-ray fluorescence and titrimetry) and REE (ICP-MS). The behaviour of the REE in the Mbalmayo weathering system was established in comparison with the REE of the reference parent rock. Mass balance calculations were applied to both major elements and REE. The mineralogy of the materials was determined with the aid of a Philips 1720, diffractometer. The chlorite schists of the Mbalmayo sector show low REE contents (Σ=153.44 ppm). These rocks are relatively rich in LREE (about 125 times the chondritic value) and relatively poor in HREE (about 20 times the chondritic value). The REE diagram normalized to chondrites shows a slightly split graph ((La/Yb)_N=6.18) with marked enrichment in LREE (LREE/HREE=9.50) in relation to HREE. Moreover, these spectra do not present any Ce anomaly, but a slightly positive Eu anomaly. The imperfectly evolved profile, whose materials are genetically linked, shows an atypical behaviour of REE. In effect, the LREE are more mobile than the HREE during weathering ((La/Yb)NASC<1) with weak Ce anomalies. This has been rarely reported in lateritic profiles characterized by higher HREE mobility than LREE during weathering processes with high Ce anomalies. This is either due to the difference in the stability of REE-bearing minerals, or to the weak acidic to basic pH conditions (6.70<pH<7.80), or even due to the average evolution of the weathering materials. The pathway of the REE along the profile is as follows: (1) leaching in the saprolites and summit of the profile, except for Ce, which precipitates very weakly in the nodular materials and the coarse saprolite materials, (2) at the base of the profile, solutions come in contact with chlorite schist formations, at this level, the pH increases (pH=7.79), HREE and a part of LREE partially void of Ce precipitate and (3) the other part of LREE precipitates further up in the profile. The geochemical mass balance calculations reveal that these elements are leached in the same phases as the relatively high Si, Al, K and Fe²⁺ contents.     

Trace elements in ferromanganese concretions,gibbsite spots,and the surrounding terra rossa overlying dolomite: Their mobilization,redistribution and fractionation

The mobilization, redistribution and fractionation of trace elements during chemical weathering processes have been investigated on a 4.05 m thick terra rossa profile overlying dolomite on the Yunnan-Guizhou Plateau, in Southwest China. In this in situ weathering profile, the ferromanganese concretions and the gibbsite spots coexist in the terra rossa saprolite. The mass-balance evaluation reveals that titanium, Nb and Hf in the terra rossa matrix are conservative elements during chemical weathering compared to Zr. The elements of Li, Sc, V, Cr, Fe, Ga, As, Mo, Cs, Ce, Ta, Tl, Pb and Th in the terra rossa matrix include additions from external sources. Beryllium, Mn, Co, Ni, Cu, Rb, Ba and La are depleted in the shallow parts of the terra rossa profile and enriched in the deep parts. The elements of Zn, Sr, Y, Cd, Sn and U in the terra rossa profile are lost during weathering. Compared to the terra rossa matrix, the ferromanganese concretions are significantly enriched in most trace elements, especially Mn, Co, Cd, Ce, Tl and Pb. In contrast, the gibbsite spots are depleted in all trace elements, except for U. The results regarding specific inter-element relationships indicate that most trace elements have different inter-element relationships in the ferromanganese concretions, the gibbsite spots and the terra rossa matrix. This suggests that the behavior of many trace elements during mobilization and redistribution differs from their behavior during incorporation into secondary mineral phases, especially the Mn and Fe oxides and/or oxyhydroxides in the ferromanganese concretions. It is worthy to note that the fractionation between Ce and Mn occurs under intensive chemical weathering conditions. Correspondingly, beryllium exhibits a similar geochemical behavior as that of rare earth elements (except for Ce) and Y during surface weathering.     

Mineralogy and geochemistry of clay fractions from different saprolites,Egypt: implications for the source of sedimentary kaolin deposits

The clay fractions of saprolites from granites, basalt, and schists in Egypt were subjected to mineralogical and geochemical investigations to examine the effect of source rock on the composition of the saprolites and the possibilities of these saprolites as a source of the nearby sedimentary kaolin deposits. The clay fractions of the studied saprolites show mineralogical and geochemical variations. Saprolites from the granites consist of kaolinite, while saprolites from the basalts are composed entirely of smectite. Schists-derived saprolites are composed of kaolinite in some cases and of a mixture of kaolinite, illite, and chlorite in the other. Saprolite from the basalt is characterized by relatively higher contents of TiO₂ and Ni compared to the saprolites from granites. Saprolites from granites have higher contents of Ba, Li, Pb, Sr, Th, Y, and Zr compared to those of the saprolites from the basalts and schists. Saprolites from different schists show variations in the distributions of many constituents, such as TiO₂, Cr, Ni, Ba, Y, and Zr. Although chondrite-normalized rare earth elements (REE) patterns are characterized by relative enrichments in the light rare earth elements (LREE) compared to the heavy rare earth elements (HREE) in all saprolites, granitic saprolites show negative Eu anomalies, while saprolite from basalt has no Eu anomaly. REE patterns of the saprolites from schists exhibit slight positive Ce anomalies and slight to moderate negative Eu anomalies. Weathering of saprolites from the basalt and metasediments is classified as the bisiallitization type, while weathering of saprolite from the granite is allitization type. Saprolites from schists vary from the bisiallitization (Aswan and Abu Natash) and allitization (Khaboba) types. Saprolites from the Khaboba schist can be considered the possible source of the Carboniferous kaolin deposits in the Hasber and Khaboba areas of Sinai, based on the similarity in the mineralogy and geochemistry of major, trace, and REE between the saprolites and the deposits. On the other hand, Carboniferous sedimentary kaolin deposits in the Abu Natash area, as well as the Cretaceous kaolin deposits in all areas of Sinai, might have been derived from the nearby schist saprolites, based on the similarity in the mineralogy and geochemistry between the saprolites and the kaolin deposits. Granites from the Arabian-Nubian Shield (ANS) and East Sahara Craton (ESC) are the possible sources of the pisolitic and plastic kaolin deposits in the Kalabsha area (Aswan), as indicated by the similarity in the mineralogy and geochemistry of the granitic saprolites and the kaolin deposits.     

Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China: Their mobilization,redistribution, and fractionation

In this study, the mobilization, redistribution, and fractionation of trace and rare earth elements (REE) during chemical weathering in mid-ridge (A), near mountaintop (B), and valley (C) profiles (weak, weak to moderate, and moderate to intense chemical weathering stage, respectively), are characterized. Among the trace elements, U and V were depleted in the regolith in all three profiles, Sr, Nb, Ta, Zr, and Hf displayed slight gains or losses, and Th, Rb, Cs, and Sc remained immobile. Mn, Ba, Zn, Cu, and Cr were enriched at the regolith in profiles A and B, but depleted in profile C. Mn, Pb, and Co were also depleted in the saprock and fractured shale zones in profiles A and B and enriched in profile C. REEs were enriched in the regolith and depleted at the saprock zone in profiles A and B and depleted along profile C. Mobility of trace and REEs increased with increasing weathering intensity. Normalized REE patterns based on the parent shale revealed light REE (LREE) enrichment, middle REE (MREE), and heavy REE (HREE) depletion patterns. LREEs were less mobile compared with MREEs and HREEs, and this differentiation increased with increasing weathering degree. Positive Ce anomalies were higher in profile C than in profiles A and B. The Ce fractionated from other REE showed that Ce changed from trivalent to tetravalent (as CeO₂) under oxidizing conditions. Minimal REE fractionation was observed in the saprock zone in profiles A and B. In contrast, more intense weathering in profile C resulted in preferential retention of LREE (especially Ce), leading to considerable LREE/MREE and LREE/HREE fractionation. (La/Yb)_N and (La/Sm)_N ratios displayed maximum values in the saprock zone within low pH values. Findings demonstrate that acidic solutions can mobilize REEs and result in leaching of REEs out of the highly acidic portions of the saprock material and transport downward into fractured shale. The overall behavior of elements in the three profiles suggests that solution pH, as well as the presence of primary and secondary minerals, play important roles in the mobilization and redistribution of trace elements and REEs during black shale chemical weathering.     

Negative cerium anomalies in the saprolite zone of serpentinite lateritic profiles in the Lomié ultramafic complex,South-East Cameroon

Strong negative cerium anomalies are developed in the saprolite zone of two serpentinite lateritic profiles in the Mada region of the Kongo–Nkamouma massif in the Lomié ultramafic complex (South-East Cameroon).The total lanthanide contents increase strongly from the parent rock (1.328 ppm) to the weathered materials (ranging from 74.32 to 742.18 ppm); the highest value is observed in the black nodules from the western weathering profile and the lowest one in the top of the clayey surface soil from the same profile. The lanthanide contents, except cerium, are highest in the saprolite and decrease along the profile. The light REE contents are very high compared to those of the heavy REE (LREE/HREE ranging from 3.21 to 44.37). The lanthanides normalized with respect to the parent rock reveal: (i) strong negative Ce anomalies with [Ce/Ce¹] ranging from 0.006 to 0.680 in the saprolite zone; (ii) strong positive Ce anomalies with [Ce/Ce¹] ranging from 1.23 to 23.96 from the top of the saprolite to the clayey surface horizon; (iii) positive Eu anomalies with [Eu/Eu¹] ranging from 2.09 to 2.41 in all the weathered materials.Mass balance evaluation shows that, except cerium, lanthanides have been highly accumulated in the saprolite zone and moderately concentrated in the upper part of both profiles. Cerium has been highly accumulated in the nodules of the West Mada profile. The presence of negative Ce anomalies is confirmed by its low degree of accumulation whereas the positive ones are related to its high degree of accumulation.     

Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.     

湖北宜昌崆岭群孔兹岩系地球化学特征

湖北宜昌崆岭群孔兹岩系由富铝片岩-片麻岩及榴线英岩类、长英质岩类及镁铁质麻粒岩类组成,其原岩分别为黏土岩、砂岩-杂砂岩和泥灰岩,富铝片麻岩的稀土元素分配型式接近北美页岩组合样(NASC),Eu显示负异常,而Ce基本无异常.富铝片麻岩和榴线英岩的微量元素分配形式与澳大利亚后太古代页岩(PAAS)接近.根据风化参数CIW,与NASC、PAAS相近的稀土和微量元素的分布特征以及高w(LREE)/w(HREE)值与Eu负异常综合判断崆岭群孔兹岩系的原岩属于以花岗质岩石为蚀源区的陆屑沉积岩.根据富铝片麻岩和榴线英岩的δ(Ce)值(NASC标准化)及岩组中的石墨推断其原岩沉积环境为还原条件,根据δ(Ce)值(球粒陨石标准化)和镁铝含量比进一步判断其原岩沉积为大陆边缘的陆海过渡-海水沉积.由大量的碎屑沉积-少量化学沉积-有不同程度的化学沉积加入的大量碎屑沉积的沉积建造与岩组中石墨的变化推测该孔兹岩系原岩的形成可能与阜平、五台等旋回(期)的前吕梁旋回(期)黄陵-川中古陆块(或扬子陆块) 的陆核形成有关.     

Robust geochemical indices for redox and weathering on a granitic laterite landscape in Central Uganda

Most geochemical studies of laterite formation have been based on detailed examinations of a small number of hopefully “representative” profiles. Due to spatial variability in bedrock composition and geomorphic processes that sort materials by size, density, and other properties, experimental designs developed for the geochemical analysis of single soil profiles are of limited use in landscape investigations. In this study of a laterite landscape on a granitic rock in Uganda, we used element concentrations from neutron activation analysis (NAA) to develop a suite of robust geochemical indices for landscape-scale analysis of weathering and oxidation-reduction (redox) processes in laterite formation. To capture K-feldspar weathering the K/Hf ratio served as a good proxy for feldspar/zircon mineral ratios while K/Na ratios indexed feldspar concentration to quartz. Using principal components analysis, we derived an index of Rare-Earth Elements (REE) leaching (relative to Th), and an index of Heavy to Light REE (HREE/LREE) fractionation. We used the Fe/Sc ratio to ascertain the absolute (redox) vs. relative (weathering) Fe accumulation in laterite formation—with absolute Fe accumulation also associated with lower Fe/As ratios. Mn-Ce-Ba nodules and concretions were identified by characteristically high Ce values—with individual Ce values as high as 5000 μg g⁻¹. The relatively large amounts of K-feldspar (K_avg is 4000 μg g⁻¹) and low degree of HREE/LREE fractionation suggest that this landscape is weathered less than generally assumed. The Fe- and Mn-derived indices highlight the important role of oxidation-reduction processes in iron accumulation. Overall, our findings suggest that the current ferricrete-mantled hilltops were formerly located on a lower, poorly drained part of the landscape.     

超基性岩红土风化壳中REE地球化学:不同气候风化剖面的对比

选择印度尼西亚苏拉威西岛Kolonodale地区和中国云南省元江地区的2个超基性岩红土风化壳为研究对象,对比研究不同气候环境下超基性岩在红土风化过程中REE的地球化学特征及其演化机制.研究发现,印尼Kolonodale和中国元江剖面的REE分布型式具有一定的共性规律,都表现出显著的REE表生富集效应(相对于基岩的最大富集系数分别达44.21和236.19)、不均一的轻重稀土分异(分异程度随剖面深度加大而降低)以及剧烈的Ce异常正负转换现象(风化壳上部是正Ce异常,风化壳下部是负Ce异常).2个剖面中REE最大富集段的产出位置明显错位,表现在Kolonodale剖面中REE最大富集段出现在腐岩层,而在元江剖面中REE最大富集段出现在红土层.质量平衡计算指示,REE在超基性岩红土化过程中发生了显著的迁移和分异现象,其地球化学行为受红土剖面pH值环境与有机质(O.M.)含量的制约.案例对比分析表明,气候环境对超基性岩红土化过程中REE的地球化学演化具有重要影响.在热带雨林环境的印尼Kolonodale剖面中,风化壳中REE主要继承于基岩,在高强度的红土化作用下,REE经历了强烈的重新分配和垂向分异.而在亚热带季风气候环境的中国元江剖面中,风化壳中的REE具有更复杂的物源背景,除继承基岩外还可能叠加了风尘沉积物的影响.元江剖面的红土化程度偏弱,导致REE在表生演化中未发生强烈的淋滤和次生富集作用.      

贵州瓮安陡山沱组磷块岩稀土元素地球化学特征与沉积期后变化

贵州瓮安陡山沱组磷块岩保存了可能是全球最早的后生动物化石 (瓮安动物群 ),对于瓮安动物群出现过程中的古海洋环境重建具有重要科学意义。但必须对成岩后生作用对磷块岩中的稀土元素改造进行评估。通过对贵州瓮安陡山沱组磷块岩的磷质碎屑、磷质和白云质胶结物、磷条带和泥条带等的稀土元素地球化学特征研究,确定沉积期后变化对稀土元素的改造影响不大。上矿层磷块岩沉积期形成的磷质碎屑、成岩期形成的白云质和磷质胶结物具相同的稀土元素配分模式,暗示了沉积期后的改造作用对瓮安陡山沱组磷块岩保存的原生沉积信息影响不大。瓮安陡山沱组磷块岩具有显著的重稀土亏损特征。磷块岩的磷质和白云质胶结物、伴生磷质碎屑、强风化磷块岩相近的ErN/LuN 比值,表明沉积期后的改造作用不是重稀土元素亏损的主要原因。磷块岩的ErN/LuN、LaN/NdN 与Ce/Ce 间的相关性,表明越氧化的沉积环境中,轻和重稀土元素亏损越强。     

Mobilization and redistribution of major and trace elements in two weathering profiles developed on serpentinites in the Lomié ultramafic complex, South-East Cameroon

The behaviour of major and trace elements have been studied along two serpentinite weathering profiles located in the Kongo-Nkamouna and Mang North sites of the Lomié ultramafic complex.The serpentinites are characterized by high SiO₂ and MgO contents, very low trace, rare earth and platinum-group element contents. Lanthanide and PGE contents are higher in the Nkamouna sample than in Mang North. Normalized REE patterns according to the CI chondrites reveal that: (i) all REE are below chondrites abundances in the Mang North sample; (ii) the (La/Yb)_N ratio value is higher in the Nkamouna sample (23.72) than in the Mang one (1.78), this confirms the slightly more weathered nature of the Nkamouna sample. Normalized PGE patterns according to the same CI chondrites reveal a negative Pt anomaly in the Mang sample. The Nkamouna sample is characterized by a flat normalized PGE pattern.All element contents increase highly from the parent rock to the coarse saprolite.In the weathering profiles, Fe₂O₃ contents decrease from the bottom to the top contrarily to Al₂O₃, SiO₂ and TiO₂. The contents of alkali and alkaline oxides are under detection limit.Concerning trace elements, Cr, Ni, Co, Cu, Zn and Sc decrease considerably from the bottom to the top while Zr, Th, U, Be, Sb, Sn, W, Ta, Sr, Rb, Hf, Y, Li, Ga, Nb and Pb increase towards the clayey surface soil. Chromium, Ni and Co contents are high in the weathered materials in particular in the saprolite zone and in the nodules.REE contents are high in the weathered materials, particularly in Nkamouna. Their concentrations decrease along both profiles. Light REE are more abundant than heavy REE. Normalized REE patterns according to the parent rock reveal positive Ce anomalies in all the weathered materials and negative Eu anomalies only at the bottom of the coarse saprolite (Nkamouna site). Positive Ce anomalies are higher in the nodular horizon of both profiles. An additional calculation method of lanthanide anomalies, using NASC data, confirms positive Ce anomalies ([Ce/Ce^*]_NASC = 1.15 to 60.68) in several weathered materials except in nodules ([Ce/Ce^*]_NASC = 0.76) of the upper nodular horizon (Nkamouna profile). The (La/Yb)_N ratios values are lower in the Nkamouna profile than in Mang site.PGE are more abundant in the weathered materials than in the parent rock. The highest contents are obtained in the coarse saprolite and in the nodules. The elements with high contents along both profiles are Pt (63–70 ppb), Ru (49–52 ppb) and Ir (41 ppb). Normalized PGE patterns show positive Pt anomalies and negative Ru anomalies.The mass balance evaluation, using thorium as immobile element, reveals that:

– major elements have been depleted along the weathering profile, except for Fe, Mn and Ti that have been enriched even only in the coarse saprolite;

– all the trace elements have been depleted along both profiles, except for Cr, Co, Zn, Sc, Cu, Ba, Y, Ga, U and Nb that have been enriched in the coarse saprolite;

– rare earth elements have been abundantly accumulated in the coarse saprolite, before their depletion towards the top of the profiles;

– platinum-group elements have been abundantly accumulated in the coarse saprolite but have been depleted towards the clayey surface soil.

Moreover, from a pedogenetical point of view, this study shows that the weathering profiles are autochtonous, except in the upper part of the soils where some allochtonous materials are revealed by the presence of zircon grains.     

贵州水城二叠系茅口组含锰岩系地质地球化学特征与锰矿成因分析

贵州水城二叠系茅口组内发现新锰矿。通过对含锰岩系的地质地球化学研究,其富集Zn,Ni,As,Sb,Sr,Ba,Ga,Ag,V,U元素;锰含量较高层位,Th/U比值小于1,锰含量较低层位,Th/U比值往往高达4～5。Co/Ni比值小于1。含锰岩石的(Fe+Mn)/Ti均大于47,高于20,特别是含锰高的岩石,其(Fe+Mn)/Ti值在300以上。含锰岩石的Al/(Al+Fe+Mn)均远远低于0.35,一般为小于0.02。稀土配分模式与峨眉山玄武岩相似,∑REE较高,LREE/HREE值偏低等特征。根据锰岩系地球化学和区域构造特征分析,水城二叠系茅口组含锰岩系属于热水喷流沉积的产物。     

西藏那茶淌北铅锌矿床矽卡岩地球化学特征及其成因

那茶淌北铅锌矿床位于西藏冈底斯成矿带东段北部,主要由矽卡岩铅锌矿体组成,是一个典型的矽卡岩型矿床。笔者通过对矿床内的矽卡岩、大理岩(灰岩)、黑云母花岗岩的地球化学对比分析表明:在主量元素方面,显示Si、Al、Fe、Ti、Mg、Ca、Mn等元素在矽卡岩、大理岩、黑云母花岗岩之间发生明显的交换;在稀土元素方面,矽卡岩、大理岩和黑云母花岗岩均具有LREE富集,HREE亏损,并且发育Eu和Ce负异常和相似的REE配分模式,说明矽卡岩的成因与大理岩、黑云母花岗岩具有一定关系。结合三种不同岩性的地球化学特征,强烈的轻、重稀土分异,Eu、Ce负异常,推测矽卡岩由中高温还原热液交代碳酸盐而成,矽卡岩成岩过程中可能有少量海水加入。     

桂西南柳桥地区上二叠统大隆组层状硅质岩成因和沉积环境

对桂西南上二叠统大隆组层状硅质岩地球化学的研究发现:陆源主量元素Al、Ti等含量较高,并呈很好的相关性（R>0.90）;热液来源的主量元素Mn和Fe等含量偏低,并具有较小的负相关关系（R=－0.30）;陆源元素(Al、Ti、Hf、Zr、Th等)与总稀土元素含量具有较高正相关性（R为0.70～0.83）;Al Fe Mn三角图解指示研究区的硅质岩为非热液成因。这些说明陆源物质是硅质岩形成的重要物源,结合硅质岩中含有大量的硅质生物（放射虫和海绵骨针等）的事实,我们认为研究区硅质岩是在生物作用为主,并有大量物源物质和少量热液物质（可能与大断裂导致的玄武岩喷发有关）和火山物质混入的条件下形成的。Ce/Ce*、(La/Yb)Shale、(La/Ce)Shale和∑REE与细粒沉积物沉积环境的关系以及(La/Ce)Shale—Al2O3/(Al2O3 +Fe2O3)图解等说明研究区硅质岩沉积环境为大陆边缘的中下部。Th/U和Ceanom指示了硅质岩形成于氧化环境。      

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.     

Geochemistry of ferromanganese nodule–sediment pairs from Central Indian Ocean Basin

Fourteen ferromanganese nodule–sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule–sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo – (307, 273), Ni – (71, 125), Mn – (64, 87), Cu – (43, 80), Co – (23, 75), Pb – (15, 24), Zn – (9, 11) and V – (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation (r ? 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.     

川东地区二叠系结核状、条带状及团块状硅岩成因

川东地区二叠系结核状、条带状和团块状硅岩发育,主要分布于茅口组上段及吴家坪组,夹于石灰岩层间或层内。通过野外露头观察、室内薄片鉴定以及主量元素、微量元素和稀土元素分析,对广元长江沟、旺苍双汇、宣汉立石河和巫溪尖山的二叠系硅岩进行了岩石学及地球化学研究,重点分析了硅质来源,并对其成因机制进行了探讨。结果表明,研究区硅岩形态多样、分布不均,硅岩中见残余的石灰岩;硅质成分主要为玉髓及微晶石英、灰质硅岩中玉髓"侵入"方解石、相邻石灰岩中少量生屑被硅化。硅岩的化学成分以SiO2为主(52.79%～99.21%,平均为85.18%),Fe/Ti值、(Fe+Mn)/Ti值及Al/(Al+Fe+Mn)值反映其形成与热水活动有关;硅岩的部分微量元素含量与地壳中该元素的平均含量差异明显,Co/Ni值与Th/U值较低;稀土元素总量低,Ce负异常,LREE/HREE值低,δEu值相对较高。综合分析认为研究区二叠系硅岩为交代成因,硅质以热水来源为主,玄武岩淋滤及上升流提供了部分硅质。复合来源的硅质通过同生断裂、表层淋滤及上升流进入碳酸盐沉积物中,在不同的成岩阶段交代碳酸盐沉积物(岩),形成了顺层面或层内分布的结核状、条带状及团块状硅岩。     

Geochemistry and Origin of Layers in Single Manganese Nodule from the Philippine Sea and Manganese Nodules from Offshore Minami-Torishima,Western Pacific

Layers from one manganese nodule dredged from the Philippine Sea(16°56'N, 129°48'E; water depth, 5700 m) and 45 bulk nodules from offshore Minami-Torishima Island, Japan(23°3'N, 153°22'E; water depth, 1200 m) were analyzed chemically and their origin is discussed based on geochemical constraints. In general, Cu, Ni, Zn and Mo tend to increase with increasing Mn content, while Co, Pb, Ba, V, Sc, Th, and the rare earth elements(REEs) show less variation with increasing Mn content. Nodule 42 H from the Philippine Sea has an average Mn/Fe ratio close to 1 and shows a positive Ce anomaly, suggesting a predominant hydrogenous origin. Profiles of 230Th230 ex and Thex/232 Th ratios in the outer ~0.3 mm of nodule 42 H indicate a steady growth rate of ~1.7 mm/Myr. Nodule E30 from offshore Minami-Torishima is characterized by lower Mn, Fe, Mn/Fe(0.53) and Mo/V(0.2) ratios but higher P and Cu/Ni(0.31) ratio relative to other nodules from that area. The Ce content of E30 is unusually low(82 ppm) when compared with other nodules from the area and it is the only nodule analyzed with a negative Ce anomaly(-0.64). Based on the geochemical data we suggest that most nodules from offshore Minami-Torishima are primarily of hydrogenous origin except E30, which is dominated by hydrothermal input, and E45, which has about a 35% hydrothermal contribution.     

山东蓬莱史家沟西山火山碎屑岩风化壳元素地球化学特征

以山东蓬莱城西史家沟的西山火山碎屑岩风化壳为研究对象,系统采集样品,并测试了微量元素、主量元素、稀土元素以及黏土矿物等指标,揭示了西山火山碎屑岩风化壳的元素地球化学特征,讨论了风化壳的形成年代及其气候条件。史家沟火山碎屑岩风化壳源自基性-超基性玻屑凝灰岩母岩,CIA平均值为92.3,总体上处于为强度风化水平,K、Na、Ca和Mg等元素淋失殆尽,出现了脱硅富铝铁现象,为轻稀土富集型风化壳。西山火山碎屑岩风化壳可分为两个喷发旋回,大致以200 cm为界限,在此以下第一旋回,以上为第二旋回。第一旋回的CIA介于94.0~97.2之间,V、Rb、Sb、Mo、Li和Ga等微量元素出现淋失,在213 cm处并出现了?REE、?LREE和?HREE的峰值、Ce的负异常,蒙脱石化彻底,风化壳呈现灰白色。第二旋回的CIA在86.3~89.2之间,风化程度较第一旋回稍低,微量元素和稀土元素垂直变化较小,蒙脱石化并不完全彻底,仍残留长石、赤铁矿和石英等原生矿物,因而仍然呈现红色或淡红色。西山火山碎屑岩风化壳形成于中新世末到上新世,为温暖湿润的亚热带环境;中新世后的气候趋冷造成了两个旋回风化程度和元素地球化学特征的差异。