Trace elements in magnetite as petrogenetic indicators

We have characterized the distribution of 25 trace elements in magnetite (Mg, Al, Si, P, Ca, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Sn, Hf, Ta, W, and Pb), using laser ablation ICP-MS and electron microprobe, from a variety of magmatic and hydrothermal ore-forming environments and compared them with data from the literature. We propose a new multielement diagram, normalized to bulk continental crust, designed to emphasize the partitioning behavior of trace elements between magnetite, the melt/fluid, and co-crystallizing phases. The normalized pattern of magnetite reflects the composition of the melt/fluid, which in both magmatic and hydrothermal systems varies with temperature. Thus, it is possible to distinguish magnetite formed at different degrees of crystal fractionation in both silicate and sulfide melts. The crystallization of ilmenite or sulfide before magnetite is recorded as a marked depletion in Ti or Cu, respectively. The chemical signature of hydrothermal magnetite is distinct being depleted in elements that are relatively immobile during alteration and commonly enriched in elements that are highly incompatible into magnetite (e.g., Si and Ca). Magnetite formed from low-temperature fluids has the lowest overall abundance of trace elements due to their lower solubility. Chemical zonation of magnetite is rare but occurs in some hydrothermal deposits where laser mapping reveals oscillatory zoning, which records the changing conditions and composition of the fluid during magnetite growth. This new way of plotting all 25 trace elements on 1 diagram, normalized to bulk continental crust and elements in order of compatibility into magnetite, provides a tool to help understand the processes that control partitioning of a full suit of trace elements in magnetite and aid discrimination of magnetite formed in different environments. It has applications in both petrogenetic and provenance studies, such as in the exploration of ore deposits and in sedimentology.     

Trace elements in groundwater as indicators of anthropogenic impact

The distribution of several minor and trace elements mainly in fresh (dominating TDS 160–400 mg/l) groundwater of Latvia have been investigated by the Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) technique. An evaluation of results of about 700 analyses leads to the conclusion that concentrations of these elements is influenced by: pH–Eh conditions, groundwater residence time and diffuse contamination, whereas the role of water-bearing sediments is of secondary importance. Most trace elements are characterised by low mobility under alkaline and reducing conditions; concentrations in confined aquifers are much smaller than the Maximum Permissible Values for drinking water. The strongest anomalies of REE, Al and P were found in shallow groundwater around the former agrochemical storehouses.     

Pregnanes as molecular indicators for depositional environments of sediments and petroleum source rocks

Steroids with unconventional side chains have increasingly been applied as diagnostic markers for geological source and age assessments. However, one of the most distinctive characteristics, the abnormal abundance of pregnane and homopregnane in ancient sediments and petroleum, remains unresolved. Higher pregnane and homopregnane, as well as C₂₃–C₂₆ 20-n-alkylpregnanes, relative to the regular steranes were observed in samples collected from different petroleum basins in China. These included Precambrian marine carbonate-derived petroleum (NW Sichuan Basin), Lower Paleozoic marine marl derived crude oils (Tarim Basin), and Eocene hypersaline lacustrine carbonate source rocks and associated petroleum (Bohai Bay Basin). However, all of the samples have many common biomarker characteristics, such as pristane/phytane ratios < 1, low amounts of diasteranes and high C₂₉/C₃₀ hopane (∼0.6–1), C₃₅/C₃₄ hopane (mostly ⩾ 1) and dibenzothiophene/phenanthrene (DBT/PHEN, mostly 0.5–1) ratios revealing a contribution from anoxic carbonate/marl source rocks deposited in restricted, clastic-starved settings. We suggest that 5α,l4β,l7β-pregnane and homopregnane, as well as their higher C₂₃–C₂₆ homologues, are geological products derived from steroids bound to the kerogen by a sulfurized side chain. Carbon or carbonate minerals are considered to be natural catalysts for this cracking reaction via preferential cleavage of the bond between C-20 and C-22. Similar distributions occur in the short chain analogues of 4-methylsterane, triaromatic steroid and methyltriaromatic steroid hydrocarbons, providing circumstantial evidence for this proposal. The ratio of pregnane and homopregnane to the total regular steranes and the ratio of C₂₇ diasteranes to cholestanes can be sensitive indicators of sedimentary environments and facies. In general, high diasteranes and low pregnanes (with homologues) indicate an oxic water column or significant input of terrigenous organic matter in clay rich source rocks and some organic lean carbonate rocks. Low diasteranes with high pregnanes implies restricted, sulfur rich conditions, typical of anoxic carbonate source rocks. Furthermore, the two ratios may be useful to assess the variation of mineralogy and openness of source rock depositional settings.     

State of rare earth elements in the rare earth deposits of Northwest Guizhou,China

We studied the states of rare earth elements in ore of the Xianglushan rare earth deposit. Rare earth ore samples were tested and examined by scanning electron microscope, electron probe, and chemical leaching. No independent rare earth minerals were detected by scanning electron microscope. Elements detected by the electronic probe for the in situ micro-zone of the sample included: O, Al, Si, Ca, Mg, Fe, Ti, K, Na, S, Cl, C, Cu, Cr, V, and Pt. Rare earth elements were not detected by electron probe. (NH4)₂SO₄, (NH₄)Cl, NaCl, and H₂SO₄ were used as reagents in chemical leaching experiments that easily leached out rare earth elements under the action of 10% reagent, indicating that the rare earth elements in ore are mainly in the ionic state rather than present as rare earth minerals.     

Geochemical characteristics and provenance implication of rare earth elements in surface sediments from bays along Guangdong Coast, Southeast China

A systematic study of the granulometric properties and the occurrence and distribution of rare earth elements (REE) within surface sediments from ten bays situated along the coast of Southeast China has facilitated a more rigorous understanding of constraints on sediment provenance in the area. The results show that REE concentrations are similar within a single bay, but vary considerably (133.58–251.77 mg/kg) among the bays. The chondrite-normalized distribution patterns show the typical enrichment of light REEs (LREEs: La–Eu) relative to heavy REEs (HREEs: Gd–Lu), and an apparent depletion of Eu, which is diagnostic of a terrigenous sediment source. Obvious enrichments of the middle REEs (MREEs: Sm–Ho) in the PAAS-normalized (Post-Archean Australian Shale) distribution patterns of these bay sediments are similar to results reported from large rivers in China. Comparing the REE composition of the bay sediments with those of adjoining fluvial sediments and with the bedrock of the surrounding drainage basins, the latter are indicated as the dominant sediment source. The uniform REE distribution patterns, and MREE enrichments, prove that the sediments are derived from the material transported by the streams and rivers that discharge into the bays.     

Organic species of lanthanum in natural environments: Implications to mobility of rare earth elements in low temperature environments

Naturally occurring organic ligands, such as acetate, citrate, malonate, oxalate, and succinate, play important roles in mobility and accumulation of La and other rare earth elements in low temperature systems under Earth surface conditions. However, a comprehensive and consistent thermodynamic database covering the complexes of rare earth elements with those naturally occurring organic ligands is lacking. In this study, thermodynamic data of organic species of rare earth elements (REE) represented by La, with an emphasis on their aqueous complexes with organic ligands, are critically reviewed. The organic ligands covered by this study include acetate, citrate, malonate, oxalate and succinate. In this critical review, the Specific Interaction Theory (SIT) model is adopted for extrapolation to infinite dilution. This model is a reliable activity coefficient model valid for a wide range of ionic strengths. These critically reviewed data, including complex formation constants, SIT interaction coefficients and solubility product constants, would enable accurate modeling of the speciation and solubility of REE in various environments including high ionic strength environments, providing insight into mobility and enrichment of REE in various environments.     

Trace fossils as diagnostic indicators of deep-marine environments, Middle Eocene Ainsa-Jaca basin, Spanish Pyrenees

A quantitative study of trace fossil abundance in the Middle Eocene deep-marine clastic systems, Ainsa-Jaca basin, Spanish Pyrenees, shows that they are powerful discriminators of submarine fan and related environments. Sixteen fan and related environments are recognized from upper-slope gully to the distal basin-floor. For each environment, the degree of bioturbation (density), trace-fossil diversity, number of pre-depositional and post-depositional trace fossils, as well as the number of graphoglyptid ichnospecies were quantified. In the more laterally confined and channel-dominated Ainsa basin, there is a trend of increasing bioturbation intensity and trace-fossil diversity away from channel-axis to off-axis environments. In the more unconfined and distal Jaca basin, there is a trend of increasing trace-fossil diversity and number of pre-depositional trace fossils including graphoglyptids from the channel-lobe transition to the fan-fringe. The trace-fossil assemblages of the Ainsa-Jaca basin are characteristic of a number of sub-ichnofacies of the Nereites ichnofacies. In the distal Jaca basin, the Paleodictyon sub-ichnofacies occurs in the lobe-fringe and fan-fringe, whereas the distal basin-floor has a trace-fossil assemblage typical of the Paleodictyon sub-ichnofacies, but with a high proportion of post-depositional fodinichnia . Trace-fossil assemblages of proximal basin, axial, environments are characteristic of the Ophiomorpha rudis sub-ichnofacies, whilst proximal off-axis environments, have a mixed Paleodictyon-Ophiomorpha rudis sub-ichnofacies trace-fossil assemblage.     

南黄海NT1孔沉积物稀土元素组成与物源判别

为研究黄河、长江以及韩国河流输运的大陆物质对南黄海沉积的贡献,对南黄海中部泥质区NT1孔沉积物做了稀土元素分析和物源判别。研究发现,南黄海NT1孔沉积物物源主要为长江源和黄河源,NT1孔上部0—7．70m沉积物以长江源为主,中部7．70．16．60m和40．00～50．70m沉积物以黄河源为主,其间夹近24m厚的沉积物则以长江源为主,底部50．70～69．76m沉积物以长江源为主。结果表明,长江从晚更新世早期到现代对南黄海中部泥质区沉积起着主要作用,而黄河则在晚更新世晚期的早玉木冰期时已开始对南黄海陆架沉积作用有明显影响。     

Fertiliser characterisation: Major,trace and rare earth elements

In recent years, there has been increasing concern regarding the chemical impact of agricultural activities on the environment so it is necessary to identify contaminants, and/or characterise the sources of contamination. In this study, a comprehensive chemical characterisation of 27 fertilisers of different types used in Spain has been conducted; major, minor and trace elements were determined, including rare earth elements. Results show that compound fertilisers used for fertigation or foliar application have low content of heavy metals, whereas fertilisers used for basal and top dressing have the highest content of both REE and other heavy metals. REE patterns of fertilisers have been determined in order for them to be used as tracers of fertilisers in future environmental studies. Furthermore in this work REE patterns of fertilisers are used as tracers of the source of phosphate in compound fertilisers, distinguishing between phosphorite and carbonatite derived fertilisers. Fertilisers from carbonatites have higher contents of REE, Sr, Ba and Th whereas fertilisers from phosphorites have higher contents of metals of environmental concern, such as Cd, U and As; and the sum of the heavy metals is higher. Some of the analysed fertilisers have Cd concentrations that exceed maximum values established in some countries and can be expected to produce long-term soil accumulation. Furthermore, other elements such as U, As and Cr are 10–50 times higher in concentration than those of Cd, but there is no legislation regarding them, therefore it is necessary to regulate fertiliser compositions in order to achieve environmental protection of soils and waters.     

Geochemistry of the Eocene limestones of the Jaisalmer basin,Rajasthan, India: Implications on depositional conditions and sources of rare earth elements

Major, trace and rare earth elements (REE) concentration of the Eocene limestones, Jaisalmer Basin, Rajasthan, India are analysed to reconstruct the depositional conditions and to identify sources of REEs. Among the major oxides, CaO is the dominant oxide followed by SiO₂ in the studied limestones. Trace element Ba dominates over the other trace elements and it shows negative correlation with CaO. The Sr, occurring in small concentration, shows positive correlation with CaO. Other trace elements such as V, Zr, Sc, Y, Rb, Ni, Pb Co, Cu, U occur in small concentrations. The studied limestones show a positive correlation of ΣREE with Fe₂O₃, Ni, Th, Sc, and Y. These limestones possess sea-water like shale-normalized REE + Y pattern with light REE depletion, slight Gd enrichment, slightly positive La anomaly, positive Y anomaly, positive Eu anomaly, negative Ce anomaly and superchondritic Y/Ho ratio from 23.12 to 28.57. The dominance of CaO and low percentage of MgO suggest that mineral phase is calcite and there is absence of dolomitization. The occurrence of SiO₂ and Al₂O₃ in appreciable percentages may be because of the siliciclastic input during the limestone precipiatetion. The low concentration of Uranium (0.4-3.7) and authigenic Uranium (Average Total U-Th/3 value = 0.74) indicate that the studied limestones were precipitated in oxic condition from seawater. The depletion of LREE suggests that the limestones were precipitated from the seawater. The positive correlation of ΣREE with Al₂O₃ Fe₂O₃, Ni, Th, Sc, and Y and negative correlation with CaO suggest an input of siliciclastic sediments from the land during limestone precipitation. The negative Ce anomaly, slightly positive La anomaly, slight Gd enrichment, positive Y anomaly, and positive Eu anomaly also suggest that the limestone was precipitated from the seawater with some siliciclastic input from continent. The low values of the Y/Ho ratio (23.12 to 28.57) in the studied limestones suggest some modification of the seawater by the input of freshwater in a coastal environment. The REEs of the studied limestones are correlable with the shallow sea water REEs with exception of a few elements. We envisage a coastal/shallow marine depositional environment where mixing of the continental material in sea water appears feasible.     

深海稀土分布规律与成矿作用

深海稀土是近年发现的一种富集中-重稀土的新型海洋矿产资源,其资源量远超陆地稀土储量,具有重要的潜在应用价值。中国是继日本之后在国际上第二个开展深海稀土调查研究的国家,2011年以来,先后在中印度洋海盆、东南太平洋和西太平洋深海盆地发现了大面积富稀土沉积区,在全球大洋中初步划分出4个深海稀土成矿带：西太平洋深海稀土成矿带、中—东太平洋深海稀土成矿带、东南太平洋深海稀土成矿带和中印度洋海盆-沃顿海盆深海稀土成矿带。深海富稀土沉积主要发育在深海盆地的沸石粘土和远洋粘土中,属于自生成因;部分发育在洋中脊附近的盆地中,受到热液作用的影响。研究发现,深海粘土中稀土元素主要赋存于生物磷灰石中,海水是稀土元素的主要来源;在早期成岩阶段,稀土元素在深海沉积物中发生转移和重新分配,并最终富集于生物磷灰石中;大水深（CCD面之下）、低沉积速率和强底流活动是深海稀土大规模成矿的主要控制因素。今后需要继续加大深海稀土基础调查,加强深海稀土调查探测技术研发,并开展海陆稀土成矿作用对比研究,揭示深海稀土成矿机制和规律。     

Geochemistry of rare earth elements in oceanic phillipsites

The behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southern Basin of the Pacific. The REE concentrations were determined in the >50-μm-fraction phillipsite samples by the ICP-MS method. The composition of separate phillipsite accretions was studied using the electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite-only samples are related to the admixture of ferrocalcium hydroxophosphates. The analysis of separate phillipsite accretions reveals low (<0.1–18.1 ppm) REE (III) concentrations. The Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE (III) are present as an admixture of iron oxyhydroxides in separate phillipsite accretions. Based on the REE (III) concentration in iron oxyhydroxides, we can identify two generations of phillipsite accretions. Massive rounded accretions (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) accretions are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of the volcaniclastic material and oceanic deep water. Hence, the REE distribution in phillipsites does not depend on the sedimentation rate and host sediment composition.     

Improved provenance tracing of Asian dust sources using rare earth elements and selected trace elements for palaeomonsoon studies on the eastern Tibetan Plateau

The Asian Monsoon forms an important part of the earth’s climate system, yet our understanding of the past interactions between its different sub-systems, the East Asian and Indian monsoons, and between monsoonal winds and other prevailing wind currents such as the Westerly jet, is limited, particularly in central Asia. This in turn affects our ability to develop climate models capable of accurately predicting future changes in atmospheric circulation patterns and monsoon intensities in Asia. Provenance studies of mineral dust deposited in terrestrial settings such as peat bogs can address this problem directly, by offering the possibility to examine past deposition rates and wind direction, and hence reconstruct past atmospheric circulation patterns. However, such studies are challenged by several issues, most importantly the identification of proxies that unambiguously distinguish between the different potential dust sources and that are independent of particle size. In addition, a single analytical method that is suitable for sample preparation of both dust source (i.e. desert sand, soil) and receptor (i.e. dust archive such as peat or soil profiles) material is desirable in order to minimize error propagation derived from the experimental and analytical work. Here, an improved geochemical framework of provenance tracers to study atmospheric circulation patterns and palaeomonsoon variability in central Asia is provided, by combining for the first time mineralogical as well as major and trace elemental (Sc, Y, Th and the rare earth elements) information on Chinese (central Chinese loess plateau, northern Qaidam basin and Taklamakan, Badain Juran and Tengger deserts), Indian (Thar desert) and Tibetan (eastern Qinghai-Tibetan Plateau) dust sources.Quartz, feldspars and clay minerals are the major constituents of all studied sources, with highly variable calcite contents reflected in the CaO concentrations. Chinese and Tibetan dust sources are enriched in middle REE relative to the upper continental crust and average shale but the Thar desert has a REE signature distinctly different from all other dust sources. There are significant differences in major, trace and REE compositions between the coarse and fine fractions of the surface sands, with the finest <4 μm fraction enriched in Al₂O₃, Fe₂O₃, MnO, MgO and K₂O and the <32 μm fractions in Sc, Y, Th and the REE relative to the coarse fractions. The <4 μm fraction best represents the bulk REE geochemistry of the samples. The provenance tracers Y/∑REE, La/Er, La/Gd, Gd/Er, La/Yb, Y/Tb, Y/La, Y/Nd and to a certain extent the europium anomaly Eu/Eu^∗ (all REE normalized to post-Archean Australian shale, PAAS) are particle size-independent tracers, of which combinations of Y/∑REE, La/Yb, Y/Tb, Y/La and Eu/Eu^∗ can be used to distinguish the Thar desert, the Chinese deserts, the Chinese loess plateau and the Tibetan soils. Their independence upon grain size means that these tracers can be applied to the long-range provenance tracing of Asian dust even when only bulk samples are available in the source region. Combinations of La/Th, Y/Tb, Y/∑REE, Sc/La and Y/Er distinguish the Tibetan soils from the Chinese loess plateau and the Chinese deserts. La/Th and notably Th/∑REE isolate the signature of the Badain Juran desert and the combination of Sc/La and Y/Er that of the Taklamakan desert. The similarity in all trace and REE-based provenance tracers between the northern Qaidam basin and Tengger desert suggests that these two deposits may have a common aeolian source.     

铝土矿中伴生三稀元素研究进展

近年来国内外铝土矿中伴生三稀元素的研究表明,众多铝土矿及赤泥中的三稀元素具有巨大的综合利用潜力,部分矿床甚至已到达了工业生产的要求.三稀元素通常以类质同相形式进入矿物晶格和离子态吸附于矿物表面两种形式产出,但在很多铝土矿中均发现有少量稀土独立矿物的存在.影响铝土矿床中三稀元素富集因素复杂,包括成矿原岩、pH值、氧化还原环境和赋存矿物等.目前,电解铝的尾矿-赤泥中三稀元素的回收工艺也日渐成熟,酸浸-萃取(离子交换)是主要提取方法.由于铝土矿中矿物组成细小且复杂,其中三稀元素种类众多,含量相对较低,因此,未来分辨率和精度更高的显微测试技术的应用将推动三稀元素在铝土矿分布、赋存形式和富集机理研究深入.     

Sedimentary facies, depositional environments and palaeogeographic evolution of the Neogene Denizli Basin, SW Anatolia, Turkey

The Denizli Basin (southwestern Anatolia, Turkey) contains a record of environmental changes dating since the Early Miocene. Detailed facies analysis of the Neogene formations in this half-graben enables us to document successive depositional regimes and palaeogeographic settings. Sedimentation commenced in the Early Miocene with the deposition of alluvial-fan and fluvial facies (K?z?lburun Formation). At this stage, alluvial fans sourced from elevated areas to the south prograded towards the basin centre. The Middle Miocene time saw the establishment of marginal lacustrine and wetland environments followed by the development of a shallow lake (Sazak Formation). The uppermost part of this unit consists of evaporitic saline lake and saline mudflat facies that grade upward into brackish lacustrine deposits of Late Miocene-Pliocene age (Kolankaya Formation). The lake became shallower at the end of the Pliocene time, as is indicated by expansion shoreface/foreshore facies. In the Early Quaternary, the Denizli Basin was transformed into a graben by the activation of ESE-trending normal faults. Alluvial fans were active at the basin margins, whereas a meandering river system occupied the basin central part.Oxygen isotope data from carbonates in the successive formations show an alternation of wetter climatic periods, when fresh water settings predominated, and very arid periods, when the basin hosted brackish to hypersaline lakes. The Neogene sedimentation was controlled by an active, ESE-trending major normal fault along the basin's southern margin and by climatically induced lake-level changes. The deposition was more or less continuous from the Early Miocene to Late Pliocene time, with local unconformities developed only in the uppermost part of the basin-fill succession. The unconformable base of the overlying Quaternary deposits reflects the basin's transformation from a half-graben into a graben system.     

香花岭花岗岩稀土元素演化

香花岭地区花岗岩中的稀土元素呈逆向演化 ,其演化过程受花岗岩体系中的岩浆主成分、熔体结构相及流体组分变化等影响。花岗岩造岩矿物中稀土元素与各自岩石变化的一致性 ,可能暗示稀土元素的演化受岩浆的制约 ;稀土元素总量随岩浆演化而下降 ,与岩浆体系降温矿物的晶出、熔体相的相对减少、流体相的增加及射气分异作用的发生等有关 ,而轻稀土富集则是由于岩浆体系向碱性增强方向演化的结果。对于连续演化的花岗岩而言 ,稀土元素的分布样式或许可作为岩浆演化酸碱环境的指向 ;负铕异常的减小除与岩浆主成分的变化有关外 ,还与氧化 还原环境的变化有关     

Stabilisation of divalent rare earth elements in natural fluorite

Summary ?The occurrence of divalent rare earth elements (Sm²⁺, Yb²⁺, Tm²⁺, and Ho²⁺) in natural fluorite is evaluated using a suite of 37 samples deriving mainly from Sn–W deposits in the Erzgebirge (Germany), Central Kazakhstan, and the Mongolian Altai. Trace element composition was determined by ICP-AES and ICP-MS. The defect structure of the samples was studied by cathodoluminescence (CL), electron paramagnetic resonance (EPR), and optical absorption spectroscopy. Reduction of cubic Sm³⁺, Yb³⁺, Tm³⁺, and Ho³⁺ under radioactive irradiation produces the corresponding divalent centres. Our data suggest a preferable formation of Sm²⁺ and Yb²⁺ under thorium and of Tm²⁺ and Ho²⁺ under uranium irradiation. Irradiation (indicated by intense brownish (thorium) and deep purple (uranium) coloration of fluorite) gives rise to a population of divalent centres in equilibrium with their decay. However, sporadic radioactive irradiation and stabilisation of the divalent state of the REE by other electron defects were found in most cases. Three models of stabilisation of Sm²⁺, Yb²⁺, Tm²⁺, and Ho²⁺ are discussed. The most effective mechanism for Sm, Yb, Tm, and Ho is coupling with Fe³⁺ centres (REE³⁺+Fe²⁺ → REE²⁺+Fe³⁺). Accordingly, the occurrence of Fe³⁺ centres in natural fluorite is regarded to indicate not an oxidising, but rather a reducing environment during fluorite precipitation. Originally incorporated in the divalent form, Fe²⁺ was converted to Fe³⁺ by radioactive irradiation. Such a conclusion is in agreement with the finding of high contents of interstitial fluorine providing tetragonal local compensation of trivalent REE centres in crystals with high Fe³⁺. If Fe is not present, compensation of divalent Sm, Yb, and Tm is achieved by radiogenic oxidation of Ce(Pr, Tb)³⁺ accompanied by charge transfer (REE³⁺+Ce(Pr, Tb)³⁺ → REE²⁺+ Ce(Pr, Tb)⁴⁺). Ho²⁺ is sometimes stabilised by a hole trapped by an electron localised on a F vacancy (Ho³⁺+e⁻ on □_F → REE²⁺+ self-trapped exciton). Because Sm²⁺ is optically active, the stabilisation by Fe³⁺ (stable up to temperatures above 350 °C) or Ce(Pr, Tb)⁴⁺ (unstable even under visible light) in samples may be determined by careful observations in the field. Institut für Geotechnik, ETH Zürich, ETH-H?nggerberg, Zürich, Switzerland Stanford Linear Accelerator Center, Menlo Park, CA, USA Received January 8, 2002; revised version accepted June 10, 2002     

巴尔哲超大型稀有稀土矿床成矿机制研究

巴尔哲矿床中的矿化和非矿化碱性花岗岩主要造岩矿物均为微斜长石、石英、钠闪石和钠长石,但其相对含量及颗粒大小明显不同,且两类岩石中包裹体的组成特征及锆石的结晶习性也有显著差异.主量元素分析显示,矿化与非矿化碱性花岗岩均以富硅、富碱、贫镁和钙为特征,为较典型的非造山A型花岗岩.尽管矿化碱性花岗岩中K_2O和Na_2O的含量均没有明显的增加,但其Na+K/Al、Na_2O+K_2O/CaO、FeO~*/MgO及K_2O/MgO等岩石化学参数与非矿化碱性花岗岩明显不同.在矿化碱性花岗岩中除了矿化的稀土元素及Nb、Zr强烈富集外,U、Th及Y也明显富集,而Ba、Sr、P、Eu和Ti表现为强烈的亏损.在非矿化碱性花岗岩中除了大离子亲石元素Rb略有富集外,稀土元素、Nb、Zr、U、Th、Ta及Y并无明显富集,虽然Sr、P、Eu和Ti也表现为亏损,但与矿化碱性花岗岩相比其亏损程度明显降低.岩相学、岩石化学及微量元素地球化学特征显示,矿化碱性花岗岩不可能是非矿化碱性花岗岩硅化和钠长石化作用的产物,二者应是同一岩浆体系不同演化阶段熔体固结的产物.K/Rb、Rb/Sr及δEu等地球化学参数显示,矿化碱性花岗岩是高演化A型花岗质熔体固结的产物;而岩石学、包裹体及地球化学特征则显示,这种高演化的A型花岗质熔体已经进入了岩浆一热液过渡阶段.巴尔哲矿床稀有稀土元素的超常富集和成矿与A型花岗岩的高演化过程密切相关.     

巢湖的稀土元素地球化学特征

采用液-液萃取法和ICP-MS测试技术对巢湖的溶解态稀土元素进行了分析。结果表明,巢湖的溶解态稀土的含量与世界淡水相当,丰水期的样品含量高于其他季节。pH值和悬浮物、胶体是控制巢湖水体中溶解态稀土含量的主要因素。巢湖的溶解态稀土的分布模式以平坦型为主,少数呈现重稀土富集。丰水期和枯水期的溶解态稀土的(La/Yb)N值从西半湖区到东半湖区呈现有规律性的逐渐增大,并且丰水期的(La/Yb)N值低于枯水期。在富营养化湖泊中,胶体和水生生物可能是造成这一现象的主要原因。     

陈家山矿煤中微量元素和稀土元素地球化学特征

通过对陈家山煤矿中下侏罗统延安组4^#主采煤层中微量元素和稀土元素的测试分析,发现煤中富集亲花岗岩的钨钼族元素W、Mo、Bi、Sn、Ba、Sr和Li,说明该区煤系形成期间的陆源碎屑主要来自花岗岩和花岗片麻岩等中、酸性岩石。4^#煤中ΣREE平均值为98.2×10^-6,稀土元素分布模式十分相似,呈左高右低的宽缓“V”型曲线,Eu负异常明显,反映出稀土元素与陆源碎屑岩关系密切,成煤期间稀土元素来源一致,陆源物质的供应相对稳定。