中国南方红壤中稀土元素分布的研究

中国南方红壤中稀土元素总量主要集中在１５０￣２００μｇ／ｇ范围内,且土壤剖面层的底土层含量较高;稀土元素分布模式表明,红壤中轻稀土元素间略有分异,而轻,重稀土元素间以及重稀土元素间没有明显分异,稀土元素含量与红壤中有机质,粘粒含量及阳离子交换量间的相关性很弱,而与红壤中铁锰氧化物及磷酸岩呈显著的正相关关系。     

Effect of simulated acid rain on soil acidification and rare earth elements leaching loss in soils of rare earth mining area in southern Jiangxi Province of China

Acid rain has long been a great concern because of environmental and ecological problems; however, the effect of acid rain on soil acidification, loss of rare earth elements (REEs) via the leaching process, and transformation are rarely reported in rare earth mining areas. Through a simulated acid rain leaching experience, the effect of acid rain was studied on soil acidification and REEs leaching loss. The results showed that the tested soil had certain buffering capacity against nearly neutral rainwater. However, simulated acid rain of low and very low pH (pH ≤ 3.5) had a greater impact on soil acidification. After eluviating by simulated acid rain of pH 3.5 for 36 h, the pH of tailings, garden soil, paddy soil, and alluvial soil decreased by 20.41, 32.03, 13.60, 16.88, and 15.83 %, respectively, from the original values. For simulated acid rain of pH 2.5, it was 31.89, 44.76, 31.26, 29.87, and 29.15 %, respectively. After simulated acid rain eluviations of low and very low pH (pH ≤ 3.5), the order of the leaching rate of REEs in the tested soil was as follows: garden soil > tailings > paddy soil > alluvial soil. For nearly neutral rainwater (pH 4.5 simulated acid rain and pH 5.6 deionized water), the order was tailings > garden soil > paddy soil > alluvial soil. For simulated acid rain of the same pH, the leaching amounts of REEs in tailings and garden soil were higher than those in paddy soil and alluvial soil. After leaching by low and very low pH-simulated acid rain (pH ≤ 3.5), the peak value of the leaching amount of REEs in all tested soil appeared at 2 h, and then gradually reduced and reached a stable leaching state 20 h after leaching. On leaching by simulated acid rain of pH 2.5, the maximum REEs contents of leachate in tailings, garden soil, paddy soil, and alluvial soil were 156.35, 145.82, 99.88, and 85.97 mg/L, respectively. For pH 3.5 of simulated acid rain, it was 130.49, 110.49, 80.57, and 62.73 mg/L, respectively. On leaching by simulated acid rain of pH 4.5, the maximum contents of REEs in the leachate were 53.46 and 29.82 mg/L, respectively, which were observed after leaching for 6 h in tailings and garden soil that became stable 12 h after leaching. The contents of leached REEs in paddy soil and alluvial soil were always in a lower and stable state. After eluviations with deionized water of pH 5.6, the contents of leached REEs in other soils were lower, except for the slight fluctuations in tailings. The maximum content in the leachate of REEs was in the water-soluble and exchangeable fraction. When bound to carbonate fractions, REEs were not detected in the leachate. REEs bound to iron-manganese (Fe–Mn) oxides fraction and to organic matter fraction in the leachate possibly came from the tested soil or from the REEs transformation during the migration process. The content of residual fraction REEs in the leachate was very low.     

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.     

Effects of antecedent soil moisture on losses of rare earth elements and phosphorus in runoff

The effects of antecedent soil moisture on losses of rare earth elements (REEs) and phosphorus (P) in runoff were evaluated through a simulated rainfall experiment at the rate of 83?mm?h^?1. The results revealed that antecedent moisture was a significant factor affecting the amounts of REE and P losses. It was observed that most REEs and P transported with sediments in the runoff. There was a significant correlation between the total amounts of REE losses and those of P losses in the runoff. The optimal antecedent moisture for minimization of losses for REEs ranged from 10.19 to 11.17% and it was 10.91% for P.     

Rare earth elements in Quaternary clays of the Numedal area, southern Norway

Rare earth elements (REE) in the clay fraction (< 2μ) of the Quaternary deposits in the Numedal area, southern Norway, have been determined by a spark source mass spectrometric method. The REE content was studied in relation to weathering and sedimentological factors.

The total REE content varies from 100 to 1300 ppm. An average of the similar fraction of 16 non-marine clays, mostly tillitic, gave 527 ppm REE. An average of 38 glacial and postglacial marine clays from the lower part of the Numedal valley gave 335 ppm REE (max. 781 ppm). After removal of adsorbed ions the average total REE content of morainian and marine clays decreased to 186 ppm.

The content and distribution of the REE in the Numedal clays are strongly influenced by environmental factors. Under neutral and alkaline conditions the REE are accumulated by adsorption on clay minerals, and by increasing the hydrogen ion concentration the adsorbed ions are readily removed.     

Concentrations of rare earth elements in topsoil from East China

Fifty topsoil samples collected from 12 different regions of East China have been analyzed for rare earth elements (REEs). The average REE concentrations of the 50 topsoil samples are much higher than world average and are characterized by LREE-enrichment, HREE-depletion, Eu-depletion and Ce-enrichment. However, the REE concentration is not strongly affected by the climate of the sampling site; it is controlled mainly by parent materials. The plot of Ce/Eu against Eu/Sm is proved to be useful to distinguish different parent materials of topsoil. Each element in the 50 topsoil has a good correlation with its neighboring element. Seven of the 13 values are above 0.987.     

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     

Fate characteristics of nitrogen in runoff from a small agricultural watershed on the south of Huaihe River in China

Qualitative and quantitative evolution of the Swarna estuary, during the past 38 years (1967–2005), has been analysed by integrating the results of field surveys, satellite images, hydrodynamic modelling and topographic data in GIS context. Significant changes in erosion/accretion patterns of the estuarine banks, inlet configuration and adjacent spits, and origin, morphology, orientation and areal extent of fifteen braided islands have been estimated. Hydrodynamics of the region is studied through modelling, and probable flow pattern that is responsible for morphological changes is discussed. The simulated flow patterns indicate that current speeds are of the order of 10–20 cm/s inside the estuary and of the order of 40 cm/s at the mouth. The Right bank (Rb) of the estuary is subject to net erosion and the Left bank (Lb) is subject to net accretion. On an average, 20–30% of the area of all braided islands would be flooded, if the water level rises by 0.7 to 1.0 m. Islands of this estuary are morphologically very dynamic (migrating towards north, northeast and southwest directions) and subject to net accretion, whereas only one island (i.e., the Padu) has lost its major portion of landmass. A conceptual inverse distance weighted (IDW) interpolation model has been generated and evaluated possible flooding on the estuarine shoals and braided islands, due to heavy rainfall and/or sea-level rise. The model reveals that the possibility of flooding will be higher for those islands which are located close to the Rb than those close to the Lb.     

长江三峡地区成冰纪-埃迪卡拉纪转换时期微量元素和稀土元素地球化学特征

通过微量元素和稀土元素地球化学分析,对长江三峡地区陡山沱组层型剖面--田家园子剖面成冰系南沱组顶部和埃迪卡拉系陡山沱组下部102个岩石样品进行了地球化学研究。重点分析了氧化还原敏感元素(Zn,Co,U,Mo,Ni,V)的富集特征,并探讨其可能成因机制以及三峡地区成冰纪-埃迪卡拉纪转换时期的水体特征。结果表明:在南沱组顶部仅Zn和Co富集;在盖帽白云岩下部,氧化还原敏感元素均富集,而在盖帽白云岩上部,除Zn和V外,其他氧化还原敏感元素均亏损;在陡山沱组Ⅱ段下部,氧化还原敏感元素由最初的亏损,逐渐变为较稳定的富集。在陡山沱组下部,出现2次明显的富集峰值,分别出现在剖面的0.4m处(盖帽白云岩中间)和6.5m处(陡山沱组Ⅱ段下部)。整个剖面大部分样品具有Eu的轻微正异常(Eu/Eu^*＜1.6), 而在剖面0.4m和6.5m处,Eu具有明显的正异常,结合稀土配分类型、Y/Ho值、La异常、Ce异常等指标,推测这2次异常均可能受到深海热液流的影响,而缺氧海水的上涌造成水体缺氧,导致这些元素出现富集峰值。U/Th、V/(V+Ni)以及稀土元素指标综合指示,三峡地区南沱组顶部冰碛岩应为氧化环境下的沉积物;随着冰川消融,冰融淡水注入古海洋,陡山沱组盖帽碳酸盐的沉积受冰融淡水的影响,深部缺氧海水的上涌使沉积水体经历氧化-缺氧-氧化的转变,海水的分层性较强;而陡山沱组Ⅱ段下部沉积环境以分层性较弱的弱氧化环境为主。     

Dissolved rare earth elements in a seasonally snow-covered, alpine/subalpine watershed, Loch Vale, Colorado

Dissolved rare earth elements (REEs) were determined in a four-year time series at the outlet of Loch Vale. The Loch Vale watershed is a seasonally snow-covered alpine/subalpine basin in Rocky Mountain National Park, USA. The time series was mainly distinguished by an annual early spring peak in the concentrations of all REEs. REE concentrations at this time were as much as 8-fold greater than at other times of the year. This annual peak was coincident with an early spring peak in dissolved organic carbon (DOC) which results from flushing of soils at the beginning of spring snow melting. The REE/DOC peak occurs as discharge starts to increase from wintertime lows but well before the spring peak in discharge. Speciation considerations suggest complexation of the REEs by DOC. The Ce anomaly also increases (i.e., is less fractionated) during the spring flush indicating that the most reducing (or least oxidizing) REE sources in the system are comparatively more important at that time. Mn data and the La/Yb ratio also support this. The behavior of REEs in the Loch Vale system has additionally been compared with metal and DOC behavior in other systems. Hydrologic and climatic differences can be important especially with regard to timing and duration of the spring flush peak. Damping of hydrologic events in the lower floodplain of major rivers may also partially result in the differences observed between Loch Vale and the lower Mississippi River. However, comparison with the Amazon River system additionally suggests that seasonal flooding of wetlands may be an important regulator of REE concentrations. Chemical differences are also important for these systems. This includes pH and suspended matter concentrations which affect the balance between adsorption and complexation. Additionally, the relative complexing ability of DOC in different systems is a factor needing further consideration.     

华北克拉通南缘早白垩世天目山A型花岗岩的锆石稀土元素和岩石地球化学特征

天目山正长花岗岩位于华北克拉通南缘、北秦岭构造带及桐柏—大别造山带构造拼合地区,其岩石成因模型可为秦岭—大别造山带燕山期深部构造演化提供新的限定。它的n(206Pb)/n(238U)加权平均年龄为129. 2±1. 7 Ma,形成于早白垩世。天目山花岗岩锆石稀土元素具有轻稀土亏损、重稀土富集、Ce和Sm正异常及明显Pr、Nd和Eu负异常（δEu值介于0. 01 ~ 0. 19）,锆石的形成温度介于603 ~ 788 ℃之间,天目山锆石/熔体体系中稀土元素分配系数波动特征表明其形成中存在深部岩浆/流体混合作用。天目山花岗岩样品具有富硅、碱和贫钙、镁的特征,在SiO2 —K2O图解中落入高钾钙碱性系列。在微量元素蛛网图中,它们显示了明显的Rb、Th及Zr、Hf的异常峰和Sr、P、Ti的异常谷。它们的稀土总量介于106??10-6~ 139??10-6之间,(La/Yb)N值范围是5. 94 ~ 9. 22,其稀土配分模式具轻稀土富集、中稀土亏损和重稀土略微富集的“V”型（海鸥型）特征,Eu负异常明显（δEu值介于0. 06 ~ 0. 16）。它们的10000Ga/Al值介于3. 38 ~ 4. 15,Nb和Ta的含量分别为63. 5??10-6~ 131??10-6和3. 20??10-6~ 7. 55??10-6（Nb/Ta值介于17. 3 ~ 22. 9）,天目山花岗岩属于A型花岗岩中富Nb的A1亚类。天目山花岗岩部分熔融源区位于角闪岩相,源区残余相主要为角闪石和斜长石且无石榴子石残余。天目山花岗岩形成于板内构造环境,它是早白垩世~130 Ma桐柏山三合店—鸡公山区域岩石圈拆沉作用的岩浆响应,幔源富Nb岩浆/流体因此得以快速释放,上侵途中混合活化壳源岩浆/流体库之后就位固结成岩。     

江西龙源坝地区花岗岩风化壳离子吸附型稀土矿成矿条件与分布特征

对龙源坝地区南西部山间小盆地周围的花岗岩风化壳进行踏勘调查发现,区内山形地势受燕山期NE向良伞寨断裂带和喜山期新构造的双重影响,盆地周缘多为低缓山丘,风化壳厚度大,壳层结构发育完整,是离子型稀土矿理想的赋存场所。基岩岩性主要为燕山早期粗中粒似斑状黑云母花岗岩,次为燕山晚期细粒二云母花岗岩、煌斑岩,是离子型稀土矿的成矿物质来源。研究区处于赣南粤北(稀土矿)成矿亚区,属亚热带气候,温热多雨,利于离子型稀土矿的形成。认为该区具有探寻中―小型花岗岩风化壳离子吸附型稀土矿的找矿潜力。     

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.     

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。     

Water–granite interaction: Clues from strontium,neodymium and rare earth elements in soil and waters

Strontium-, Nd-, and rare-earth-element-isotope data are presented from rock, weathered rock (arene) and saprolite, sediment and soil, shallow and deep groundwater (e.g. mineral-water springs), and surface waters in the Margeride massif, located in the French Massif Central. Granitoid rock and gneiss are the main lithologies encountered in the Margeride, which corresponds to a large and 5-km-deep laccolith. Compared to bedrock, the Sr isotopes in arene, regolith, sediment and soil strongly diverge with a linear increase in the ⁸⁷Sr/⁸⁶Sr and Rb/Sr ratios. Neodymium isotopes fluctuate least between bedrock and the weathering products. In order to characterise the theoretical Sr isotopic signature IRf(Sr) of water interacting with granite, a dissolution model was applied, based on the hypothesis that most of the Sr comes from the dissolution of plagioclase, K-feldspar and biotite. Similar to the Sr model, an approach was developed for modelling the theoretical Nd isotopic signature IRf(Nd) of water interacting with a granite, assuming that most Nd originates from dissolution of the same minerals as those that yield Sr, plus apatite. The IRf(Sr) ratio of water after equilibration with the Sr derived from minerals was calculated for the Margeride granite and compared to values measured in surface- and groundwaters. Comparison of the results shows agreement between the calculated IRf(Sr) and the observed ⁸⁷Sr/⁸⁶Sr ratios. When calculating the IRf(Nd) ratio of water after equilibration with the Nd derived from minerals of the Margeride granite, the results indicated good agreement with surface-water values, whereas mineralised waters analysed within the Margeride hydrosystem could not be directly linked to weathering of the granite alone. Because the recharge area of deep groundwater is located on the Margeride massif, very deep circulation involving interaction with other rocks (e.g. shales) at depths of >5 km must be considered.     

龙感湖稀土元素的地球化学特征

采用液-液萃取法,连续提取法和ICP-MS测试技术,对龙感湖不同季节水和颗粒物中稀土元素进行研究.结果表明,龙感湖的溶解态稀土含量极低,稀土总含量(ΣREE)在3.14～129.81ng/kg之间,且季节性变化明显.龙感湖溶解态稀土元素表现出平坦型的页岩配分模式,这是由于在草型湖泊中溶解态稀土主要以吸附在微细胶体上的形式存在,水粒相互作用在这个过程中起主要控制作用.悬浮物中的稀土含量顺序为:残渣态>>Fe-Mn结合态>>有机态和AEC态,颗粒物中稀土元素主要以残渣态形式存在.Fe-Mn结合态、有机态和AEC态的页岩配分模式为中稀土富集,残渣态的页岩配分模式为平坦型.这说明中稀土与轻重稀土相比具有更强的潜在地球化学活性,但在龙感湖的环境中的迁移能力相对轻重稀土来说较弱.     

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.     

淮南采煤沉陷区表层沉积物稀土元素地球化学特征

稀土元素由于其独特的化学特征被广泛应用于环境地球化学分析过程研究。以淮南采煤沉陷区表层沉积物中稀土元素(REEs)为研究对象,采集研究区潘一、顾桥、谢桥沉陷区的表层沉积物样品共12个,采用ICP-MS对样品的稀土元素含量进行测试分析,探讨了表层沉积物中稀土元素的含量分布特征、控制因素及其物质来源。结果表明:研究区表层沉积物中稀土元素含量为54.63~130.45 μg/g,平均102.60 μg/g;LREE/HREE比值为11.89~20.55,平均14.29,轻稀土呈现明显富集现象;相关性分析结果显示,REEs趋向于黏土组分中富集;研究区养殖和捕捞活动导致表层沉积物中稀土元素含量的降低;球粒陨石标准化结果表明,研究区稀土元素呈现不同程度的La和Gd正异常,其中,Gd正异常主要是受到燃煤的影响,而La正异常主要与燃煤和化肥有关。结合Pearson相关性、球粒陨石标准化和(La/Yb)_N-(La/Sm)_N-(Gd/Yb)_N三元图判别,认为研究区水体表层沉积物中稀土元素与人类活动(燃煤和化肥)有关,研究认识为污染物的源头控制和煤矿区环境的生态治理提供参考依据。      

粉煤灰——稀土元素的潜在来源

稀土是在地壳发现的一系列化学元素,由于其独特的化学性质,稀土元素广泛应用于包括电子产品、计算机、通信系统、交通、医疗、国防等多个领域。随着稀土资源的持续开采、高昂的环境代价,以及新兴领域对稀土需求的日益增长提出对回收稀土加强研究,利用经济可行的方法,寻找更多来源的要求。