太平洋富钴结壳中稀土元素的赋存状态

采用化学提取方法对采自太平洋国际海域的板状和结核状富钴结壳的稀土元素进行了分级提取 ,并利用等离子质谱仪 (ICP MS)测定了稀土元素的质量分数。结果表明 ,结壳中稀土元素在不同结合态中的富集顺序为 :残渣态 >有机结合态 >锰氧化物结合态 >碳酸盐结合态 >吸附态。稀土总质量分数的 5 6 %以上集中在残渣态中 ,并主要赋存于非晶态FeOOH物相中 ,说明FeOOH的形成对稀土元素的富集具有重要作用。水羟锰矿占结壳中X衍射结晶矿物的 95 %以上 ,但其稀土质量分数仅占稀土总质量分数的 1 6 %左右。呈有机结合态的稀土元素含量约占结壳稀土总质量分数的 2 0 % ,表明有机质对于结壳的形成及稀土元素的富集具有显著影响     

内蒙古拜仁达坝铅锌矿矿集区土壤中成矿元素分布及其赋存形态研究

对拜仁达坝铅锌矿矿集区3个多金属矿区的3个土壤粒级样品中Zn、Pb、Cu、Ag 4种主要成矿元素的7种赋存形式(水溶态、离子交换态、碳酸盐结合态、有机质结合态、铁锰氧化物结合态、硫化物结合态和残渣态)进行了测定。研究结果表明:1银都矿区土壤中Zn、Pb和Ag浓度最高,而道伦达坝矿区土壤中Cu的浓度最高;2拜仁达坝矿集区土壤中Zn、Pb和Cu主要以残渣态形式赋存,而Ag主要以铁锰氧化物结合态和硫化物结合态形式赋存;3拜仁达坝矿集区Zn、Pb和Cu元素在3个土壤粒级中的各个赋存形式所占的比例略有差别,但总体上大致相同,而Ag元素的赋存状态在3个土壤粒级的差异较大;4 3个矿区土壤中水溶态、离子交换态、碳酸盐结合态和有机质结合态的Zn和Pb差别不大;铁锰氧化物结合态、硫化物结合态和残渣态的Zn和Pb,以及Cu和Ag的7个赋存状态在3个矿区的差别较大。     

土壤样品中镉的形态分析研究

采用改进的Tessier连续提取法对武汉地区的土壤样品中镉的形态进行了分析,结果表明土壤中镉主要以离子交换态形式存在,总体看其顺序为离子交换态(包含水溶态)>碳酸盐结合态>铁锰氧化物结合态>腐殖酸结合态>残渣态>强有机结合态,说明土壤中镉较活泼,易于迁移转化,对植物的可给性大,是环境中的重要污染元素.     

红壤中稀土元素结合形态的分布及分配

红壤剖面中稀土元素结合形态的分布研究表明,稀土元素的各种结合形态中以残渣态为主,其次为铁锰氧化物结合态,大部分稀土元素的可交换态、碳酸盐结合态、有机质结合态及酸溶态含量较为接近。稀土元素结合形态在剖面层中的分布大致可分为两类,一类以表层含量较高,如有机质结合态;另一类以深层含量较高,如可交换态、碳酸盐结合态、残渣态（大部分稀土元素表现为C层＞A层＞B层）和酸溶态（主要表现为C层＞B层＞A层）,而铁锰氧化物结合态变化较复杂,但主要集中在深层。不同母质对不同稀土元素各种结合形态的分布有一定的制约作用．表现为某些稀土元素的一些结合形态在一种或几种母质的红壤中占主导地位。稀土元素结合形态的分配研究表明,元素Pr、Tb、Tm、Yb、Lu的分异普遍比较显著,在不同结合形态中呈现富集或亏损,而Ce、Sm、Eu等元素则主要在某一种结合形态中发生分异。从稀土元素的各种结合形态与红壤的硅酸盐成分及其有机质含量、pH值间的相关分析认识到结合形态与红壤本身成分间的密切关系。     

淮南煤田潘三矿煤中钡、锰、镍的含量及其赋存状态

采用电感耦合等离子体原子发射光谱仪(ICP-AES)和逐级化学提取法对淮南煤田潘三矿某钻孔煤中Ba、Mn和Ni的含量及其赋存状态进行了研究。结果表明:潘三矿煤样中Ba含量较其他地区煤明显偏高,Mn含量较其他地区明显偏低,而Ni元素含量则相差不大;Ba主要以离子交换态存在,也较少以有机结合态、碳酸盐结合态和硅酸盐结合态形式赋存;Mn主要以离子交换态或碳酸盐结合态存在;Ni主要以有机结合态的形式存在,也存在碳酸盐结合态、硫化物结合态和硅酸盐结合态的Ni。     

呼和浩特市大气降尘中镉赋存形态分析

采用Tessier连续提取法对呼和浩特市不同区域的9个大气降尘样品中镉的赋存形态进行了研究。结果表明,各形态含量在总镉中所占比例由大到小排列顺序依次是:铁锰氧化物结合态>残渣态>碳酸盐结合态>强有机结合态>可交换态。大气降尘中镉的5种形态占总镉的平均质量分数由大到小为:铁锰氧化物结合态31.80%,残渣态24.42%,碳酸盐结合态19.04%,强有机结合态14.61%,可交换态10.13%;铁锰氧化物结合态是主要存在形态;铁锰氧化物结合态镉、有机结合态镉、残留态镉这三种形态镉生物有效性很低,但当环境改变时可能发生镉释放,应予以关注。汽油和煤的燃烧以及工厂排放镉能加大城市大气降尘中的镉含量。     

石煤中稀土元素地球化学研究

在全面收集石煤中稀土元素含量资料的基础上,探讨了石煤中稀土元素的赋存状态,剖析了石煤中稀土元素的富集成因。结果表明：不同地区石煤中稀土元素含量的差异较大,但均高于中国煤和世界煤中稀土元素的背景值,稀土元素相对富集。石煤中稀土元素的赋存状态多样,但以无机结合态或残渣态为主,部分石煤中稀土元素与有机质有关,部分兼具有机态和无机态。石煤中稀土元素富集的主要因素包括海相沉积环境、沉积物源区供给、热液流体（酸性、碱性、高温岩浆热液和海底喷流等）的侵入和地下水淋滤作用等。L/H、LaN/YbN、δCe、δEu等地球化学参数和稀土元素配分模式可推断石煤形成的物质来源和成矿条件等信息,具重要的地学示踪理论意义。     

贵州平坝白云岩风化壳稀土超常富集层中稀土赋存状态的研究

以平坝白云岩风化壳剖面为例,主要利用化学连续提取的方法,结合透射电镜的分析,对碳酸盐岩风化壳岩-土界面附近的稀土超常富集层中REE的赋存状态进行了研究,获得了REE在水溶态及可交换态(相态Ⅰ)、碳酸盐结合态及专性吸附态(相态Ⅱ)、非晶质氧化铁锰结合态(相态Ⅲ)、晶质氧化铁锰结合态(相态Ⅳ)、有机质及硫化物结合态(相态Ⅴ)和残渣态(相态Ⅵ)等6种相态的含量及变化规律.结果表明,REE在富集层中主要以专性吸附态、残渣态和有机态为主.风化前缘可溶态稀土所占比例较高,为稀土在风化壳中的迁移、转化提供可能;基岩中原生含磷稀土矿物的风化产生的稀土磷酸盐矿物的聚集导致了残渣态稀土大量存在于风化前缘;此外,由于风化淋溶的不断进行,可溶态的REE在高的pH值条件与剖面中的有机质、铁锰氧化物和粘土矿物共同作用下沉淀、富集,也导致了风化前缘稀土的超常富集.     

煤中微量元素赋存状态的逐提试验研究

首次通过逐级化学提取试验对高级煤中10余个微量元素的赋存状态（水溶态及可交换态，碳酸盐铁锰氧化物结合态，有机质结合态，进入晶格或呈单矿物态）进行研究，结果表明：绝大多数元素具有一种以上的赋存状态；不同沉积环境条件下，元素的赋存态可以发生改变；元素的赋存状态不同，其入侵环境及对环境的危害程度不同。     

湖北古城锰矿的沉淀形式及其古环境意义

古城锰矿是扬子地台北缘典型的“大塘坡”式锰矿,赋存于南华系大塘坡组含锰黑色岩系中,含锰矿物主要为菱锰矿.古城锰矿稀土总量高、类似现代海底铁锰结核的“帽式”稀土元素配分模式和Ce的正异常等地球化学指标指示古城锰矿Mn是以锰氧化物或氢氧化物形式沉淀,锰碳酸盐是后期转化而成.Fe/Mn比值低,较低的V、U含量和中等程度的Mo富集以及氧化还原敏感元素对Th/U、V/Cr、V/(V+Ni)比值等地球化学指标指示古城锰矿沉积环境为一种氧化一次氧化的状态,与锰是以锰氧化物或氢氧化物形式沉淀的结论一致.综合认为,古城锰矿成矿机制包括沉淀和转化两个过程,在氧化还原分层的海洋系统中,Mn在上部氧化性的水体中以氧化物或氢氧化物形式沉淀,之后下沉被掩埋在缺氧带之下,在成岩过程中和有机物质相互作用,锰氧化物或氢氧化物被还原释放出的Mn2+和有机碳被氧化释放出的CO32-结合形成锰碳酸盐,其转化可以方程2MnO2+CH2O+HCO3-=2MnCO3+H2O+OH-简单表示.     

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element.We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases.Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO₂, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO₂.Thermodynamic calculations indicate that Te occurs predominantly as H₅TeO₆⁻ in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO₂ in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.     

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean

The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules. Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).     

Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements(REE) composition of the polymetallic crusts and nodules obtained from the South China Sea(SCS) were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances(∑REE) of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE(LREE), the markedly positive Ce anomaly(δCe), and the non-or weakly positive Eu anomaly(δEu), suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event(sea-level change) during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.     

西太平洋海山富钴结壳的稀土和铂族元素特征及其意义

为了探讨富钴结壳的稀土和铂族元素是否有相似的形成机制,对西太平洋海山富钴结壳稀土和铂族元素进行了类比研究.结果表明:富钴结壳的∑REY范围为1 433.7×10-6~2 888.0×10-6,其中Ce占到近50%,北美页岩标准化后显示较平坦的稀土模式和显著的Ce正异常特征.根据稀土配分模式及已有的Nd同位素结果,富钴结壳具有亲陆壳属性.富钴结壳具有极高的Pt (115.5×10-9~1 132.0×10-9)、(Pt/Pd)_N和 (Pt/Os)_N值,Ir与Pt及Rh与Pt显示良好相关性.经球粒陨石标准化后显示较一致PGE (platinum-group elements) 配分模式,从Os到Pt逐渐富集,Pd元素强烈亏损.已有的Os同位素研究结果显示物源在地质历史时期从幔源属性向陆源属性变化,但富钴结壳PGE元素内部相对含量仍在一定程度上保持稳定.研究认为:富钴结壳对海水中的稀土清扫具有选择性,Ce的正异常恰恰是结壳对海水稀土中Ce的优先选择造成的,从而导致海水亏损Ce.然而海水中Ce的亏损并未改变新形成富钴结壳的稀土模式,原因是在海洋中存在适量的具有亏损Ce特征的磷酸盐等组分,理论上只需要氧化物类稀土与磷酸盐类稀土消耗的稀土与海水中的补给平衡即可.只是在相关过程中,海洋中氧化物类对稀土的选择更具有主动性,而磷酸盐类表现更多的继承关系.尽管Os同位素显示物源供给发生变化,然而富钴结壳PGE模式相对稳定.因此富钴结壳PGE模式同样可以用富钴结壳对PGE的选择性吸收解释,因富钴结壳优先选择Pt与Ir以及相对排斥Pd和Os,形成了现有独特的PGE模式.      

麦哲伦海山群MK海山富钴结壳稀土元素的赋存相态

利用ICP-OES和ICP-MS,分析了麦哲伦海山群西北端MK海山2 170 m水深的MKD23B-3号富钴结壳样品,获得了其剖面上主元素、稀土元素（REE）和Y含量数据,并基于元素含量间的线性相关关系,研究了REE和Y的赋存相态。结果显示:该样品剖面从基岩到表面可划分为5层,第Ⅰ、Ⅱ层为磷酸盐化壳层,第Ⅲ、Ⅳ、Ⅴ层为未磷酸盐化壳层。在未磷酸盐化壳层中,REE和Y主要赋存在δ-MnO₂相中;而在磷酸盐化壳层中,REE和Y除了赋存在Fe、Mn氧化物相中外,主要赋存在独立于碳氟磷灰石（CFA）的矿物相态中,可能为稀土的磷酸盐。并提出利用磷酸盐中REE/Y 估算富钴结壳磷酸盐化壳层次生稀土的方法,据此估算了MK海山富钴结壳磷酸盐化壳层次生稀土的量。在该样品中,次生稀土占稀土总量的42%~88%,近一半以上的稀土是次生的,磷酸盐化作用对于REE和Y的次生富集具有显著的贡献;因此解读磷酸盐化富钴结壳的稀土元素（特别是Nd同位素）古海洋记录必须排除次生稀土元素的干扰。     

Geochemical and mineralogical evidence of tectonic and sedimentary factors controlling the origin of ferromanganese crusts associated to stratigraphic discontinuities (Betic Cordilleras, SE of Spain)

Ferromanganese crusts were found in carbonates of tectonostratigraphic units located in the northern and southern areas of the eastern External Subbetic of the Betic Cordilleras (SE Spain). The crusts are associated with four stratigraphic discontinuities of the Jurassic pelagic swells sequences: D1 (Late Carixian-Early Domerian), D2 (Middle Toarcian-Early Bajocian), D3 (Middle Bathonian-Middle Oxfordian), D4 (Early Tithonian-Late Albian). Two main textural types of crusts are distinguished. Type I crusts are thin and characterized by the presence of goethite, quartz, albite and phyllosilicates. Moreover, they show Si, Al, Mg, Na, Ti and K contents close to the European Shale Composite contents and Fe/Mn ratios (>350) higher than type II crusts. Type II crusts occur as thicker banded laminae and/or macrooncoids. They consist mainly of goethite and Mn-oxyhydroxides, which are enriched in REE, Co, Ni and Cu and show a strong Ce positive anomaly. After stratigraphical, mineralogical and geochemical data, the crust formation would be produced by the exposition of bottom sediments during long periods to a thin layer of oxidizing sea and porewater enriched in metallic elements. The textural and compositional variations between crusts can be explained by taking into account the bathymetric conditions. In shallower swells, the precipitation of a thick layer of banded type II crusts and in deeper areas, thin type I crusts were formed. Organic influence was only important in crusts from D3 of the northern area where textural evidence indicates the existence of seasonal periodically alternation between organism accretion and fine sedimentation. These were preceded and followed by phases in which the inorganic precipitation of oxides prevailed together with the fine sedimentation.     

A geochemical comparison of manganese oxide deposits of the Hawaiian Archipelago and the Deep Sea

Data are presented on the composition of manganese crusts collected within the Hawaiian Exclusive Economic Zone (HEEZ). These crusts were obtained in 80% of the dredge hauls between 800 and 3000 m. Although the chemistries of crusts on the Cenozoic Hawaiian Ridge and an older Cretaceous seamounts south and north of the ridge are quite similar, there are marked differences, both in composition and in mineralogical organization, between shallow and deep crusts. Shallow crusts (<1500 m) are composed of five distinct phases (i.e. silicate, apatite, iron oxide, manganese oxide, and non-associated copper), whereas the deep crusts display no obvious inter-elemental organization based on dendrograms. The mean composition of HEEZ crusts differs from that of Eastern Tropical Pacific nodules in that crusts are comparatively rich in As, Pb, Co, Ce, Fe, and Ti, whereas nodules have comparatively more Cu, Ni, and Sr. Compositional differences between shallow crusts and nodules are discussed in terms of (1) element source; (2) Mn-oxide mineralogy; and (3) redox conditions in the adjacent seawater. It is concluded that the major differences between crust and nodules is due to metal sources; water column for crusts, sediments for nodules. Advective processes within the O₂ minimum also affect the HEEZ crusts.     

Geochemistry of rare earth elements in the mainstream of the Yangtze River,China

Water, suspended matter, and sediment samples were taken from 8 locations along the Yangtze River in 1992. The concentration and speciation (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual forms) of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) were determined by instrumental neutron activation analysis (INAA).The contents of the soluble fraction of REEs in the river are low, and REEs mainly reside in particulate form. In the particles, the chondrite-normalized distribution patterns show significant LREE enrichment and Eu-depletion. While normalized to shales, both sediments and suspended matter samples show relative LREE enrichment and HREE depletion. REEs are relatively enriched in fine-grained fractions of the sediments.The speciation characteristics of REEs in the sediments and suspended matter are very similar. The amount of the five forms follows the order: residual>>bound to organic matter∼bound to Fe–Mn oxides>bound to carbonates>>exchangeable. About 65 to 85% of REEs in the particles exist in the residual form, and the exchangeable form is very low. High proportions of residual REEs reveal that REEs in sediments and suspended matter are controlled by their abundances in the earth's crust. Carbonate, Fe–Mn oxide and organic fractions of REEs in sediments account for 2.4–6.9%, 5.2–11.1%, and 7.3–14.0% of the total contents respectively. They are similar to those in the suspended matter. This shows that carbonates, Fe–Mn oxides and organic matter play important roles during the particle-water interaction processes. By normalization to shales, the 3 forms of REEs follow convex shapes according to atomic number with middle REE (Sm, Eu, and Tb) enrichment, while light REE and heavy REE are depleted.     

太平洋多金属结核和富钴结壳稀土元素地球化学对比及其地质意义

多金属结核和富钴结壳是大洋两类典型的铁锰产物。为探讨不同海区多金属结核和富钴结壳之间稀土元素特点及其揭示的地质意义,利用近年中国在太平洋获取的样品进行对比,采用ICP-AES对稀土元素测试。结果表明,结壳具有正Ce异常明显、LREE富集、∑REE高的特点,而结核表现为HREE相对富集、∑REE相对较低,因成因类型不同,Ce异常或表现为正异常、负异常或异常不明显。结核形成后受到成岩作用的影响,而结壳则为水成作用形成;结核和结壳中REE的存在形式比较复杂,不同海区各不相同,中太平洋东部产出的结壳和位于东太平洋的结核中REE可能主要赋存于铁矿物相,而西太平洋结壳REE可能主要赋存于锰矿物相;结核和结壳REE可能分别来自海水和海山蚀变玄武岩,热液作用影响有限。