The geochemical characteristics of aqueous rare-earth elements in shallow karst groundwater in Guiyang City,China

Fifty-seven shallow groundwater samples were collected from Guiyang karst basin, China, to analyze the aqueous rare-earth elements in low-water seasons and it is shown that the total amount of rare-earth elements (ΣREE) in karst groundwater is exceedingly low compared with that in carbonate rocks or weathering crusts of carbonate rocks, and ranges from 0.01 to 0.43, from 0.03 to 0.27, from 0.03 to 0.19 and from 0.05 to 1.38 μg·L-1 for dolomite, dolomitic & limestone, limestone and clastic rock aquifer, respectively. Both distributions and contents of rare-earth elements (REE) in karst groundwater reflect the lithology of host rocks or weathering crusts of carbonate rocks through which groundwater flows. The chondrite-normalized patterns show a non-flat profile with higher enrichment of slightly light rare-earth elements (LREE) than heavy rare-earth elements (HREE), prominent fractionation between LREE and HREE, negative Ce anomalies and negative or positive Eu anomalies. There is more obvious fractionation between LREE and HREE in groundwater than that in carbonate rocks and their weathering crusts due to high contents of HCO3? and PH in groundwater. In shallow karst groundwater, REE(CO3)n2n-3 (n=1 and 2) is the main inorganic species of REE. But for a clastic rock aquifer, both REESO4+ and REECO3+ are the main inorganic species of REE. Species of REE in groundwater is closely associated with the hydrochemical type of groundwater which is predominated by the lithology of host rocks, groundwater-rock interaction and weathering-pedogenesis of carbonate rocks.     

Hydrothermal Redistribution of Rare—Earth Elements in Pingxiang Dacite,Guangxi

Distribution of the rare-earth elements (REE) in dacite has been studied so as to get a better understanding of the migration behavior of REE during alteration. Both unaltered and altered samples were collected in an unpolluted area of Guangxi Zhuang Autonomous Region, southwest China. The REE concentrations were analyzed by ICP-MS. It is concluded that the REE were enriched during dacite alteration in varying degrees. The chondrite-normalized REE patterns of altered samples approximately maintain the characteristics of unaltered samples. However, if we normalize the REE concentrations of altered samples with unaltered dacite, fractionation of REE will appear. The LREE are more enriched than HREE in all altered samples with the LREE possibly precipitated as carbonate minerals. Both positive and negative Eu anomalies exist. Enrichment, immobility and depletion are noticed for the element Lu. Heavy mineral alteration, difference in stability constant between carbonate LREE and HREE complexes, downward migration of weathering fluid and microenvironment change may be responsible for the fractionation of REE in the altered dacite.     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.     

Compositional characteristics of wolframite in tin deposits,Dupangling, Guangxi

Statistical data on major, trace and rare-earth elements in wolframite from the quartz vein-and greisen-type tin deposits in the Dupangling orefield reveal: (1) The components in wolframite can be divided into two relatively independent groups: the WO₃-Nb-Ta-Sc-REE group, in which WO₃ is negatively correlated with the others and the FeO-MnO-Sn group, in which MnO is negatively correlated with the other two; (2) In general, REE fractionation is not significant, reflected mainly by the separation of Eu from other REE’s. LREE and HREE increase or decrease simultaneously, with HREE being more variable; (3) Nb, Ta, Sc, REE substitute for W, and Sn may enter into wolframite lattice accompanied by Fe-Mn substitution; (4) In contrast to wolframite in quartz veins, which is poor in REE, Nb, Ta and Sc and has highδ Eu values and LREE / HREE and Nb/Ta ratios, wolframite in greisen is rich in REE, Nb, Ta, Sc and has lowδ Eu values and LREE/HREE and Nb/Ta ratios; and (5) The contents and ratios of trace elements and REE partitioning parameters of wolframite can be used as guide for prospecting.     

姑婆山花岗岩主岩体的稀土元素赋存状态研究

稀土元素在姑婆山花岗岩主岩体过渡相中,主要以稀土矿物和类质同象两种形式存在,并以稀土矿物形式为主,其中稀土元素含量占全岩含量的64％以上。轻稀土元素主要赋存于褐帘石和独居石中,重稀土元素主要赋存于褐钇铌矿等矿物中。岩石中至少有65％以上的稀土元素赋存于抗风化能力小的矿物中,为花岗岩风化壳离子吸附型稀土矿床提供了物质来源。     

Characterization and migration of atmospheric REE in soils and surface waters

Rainwater and snow collected from three different sites in France (Vosges Mountains, French Alps and Strasbourg) show more or less similar shapes of their REE distribution patterns. Rainwater from Strasbourg is the most REE enriched sample, whereas precipitations from the two mountainous, less polluted catchments are less REE enriched and have concentrations close to seawater. They are all strongly LREE depleted.Different water samples from an Alpine watershed comprising snow, interstitial, puddle and streamwater show similar REE distributions with LREE enrichment (rainwater normalized) but MREE and HREE depletion. In this environment, where water transfer from the soil to the river is very quick due to the low thickness of the soils, it appears that REE in streamwater mainly originate from atmospheric inputs. Different is the behaviour of the REE in the spring- and streamwaters from the Vosges Mountains. These waters of long residence time in the deep soil horizons react with soil and bedrock REE carrying minerals and show especially significant negative Eu anomalies compared to atmospheric inputs. Their Sr and Nd isotopic data suggest that most of the Sr and Nd originate from apatite leaching or dissolution. Soil solutions and soil leachates from the upper soil horizons due to alteration processes strongly depleted in REE carrying minerals, have REE distribution patterns close to those of lichens and throughfall. Throughfall is slightly more enriched especially in light REE than filtered rainwater probably due to leaching of atmospheric particles deposited on the foliage and also to leaf excretion.Data suggest that Sr and Nd isotopes of the soil solutions in the upper soil horizons originate from two different sources: 1) An atmospheric source with fertilizer, dust and seawater components and 2) A source mainly determined by mineral dissolution in the soil. These two different sources are also recognizable in the Sr and Nd isotopic composition of the tree’s throughfall solution. The atmospheric contributions of Sr and Nd to throughfall and soil solution are of 20 to 70 and 20%, respectively. In springwater, however, the atmospheric Sr and REE contribution is not detectable.     

赣南峰山离子型稀土矿床成矿机理探讨

以赣南大埠岩体西部峰山钻孔风化壳剖面为研究对象,在风化壳剖面各层地质特征研究的基础上,对风化壳剖面各层中含稀土矿物开展了扫描电镜和电子探针分析,探讨了风化壳剖面各层主、微量（包括稀土）元素和离子相稀土元素特征。研究表明,风化壳中稀土元素呈“弓背式”分布,矿体位于风化壳剖面2~9 m,w(REE)平均为516.8×10^-6,离子相稀土元素浸出率为51%~84%,离子相与全项稀土元素总量分布特征一致。风化壳中稀土元素主要以离子吸附态形式和独立矿物（次生方铈矿和风化残余的磷钇矿、褐钇铌矿）形式存在,以离子吸附态形式为主。峰山风化壳离子吸附型稀土矿为轻、重稀土元素共生型稀土矿,以重稀土元素占主导,矿体上部相对富集轻稀土元素,下部相对富集重稀土元素。风化壳剖面中稀土元素的富集分异主要受轻重稀土元素地球化学行为的差异性、风化程度和黏土矿物含量联合控制。     

Experimental determination of REE fractionation between liquid and vapour in the systems NaCl–H2O and CaCl2–H2O up to 450 °C

Fractionation of selected REE between brine and vapour was experimentally determined using a large-volume rocking Ti-autoclave that allowed quasi-isobaric sampling of liquid-vapour pairs. Samples were extracted along the 350, 400 and 450 °C-isotherms of the H₂O-NaCl system, and along the 400 °C isotherm of the CaCl₂ system. Total salt concentrations were either 6.6 and 10 wt% NaCl or CaCl₂, respectively, and total REE concentrations were about 2 ppm of each REE. Starting pH at room temperature was 1.8, added as HCl. In another series of experiments, REEs were added in amounts of 312 ppm. Here, the starting pH at room temperature was 0.5, added as HNO₃:HCl=1:2. Liquid-vapour pairs (L-V) were analysed for REE by ICP-MS methods. L-V-partitioning of REE along a particular isotherm follows broadly the partitioning of the main salt components, NaCl or CaCl₂. D_REE=REE^V/REE^L decrease rapidly from the critical point with decreasing pressure (equivalent to increasing salinity of the liquid) as the solvus opens. This is independent of the total amount of the added REE. Log D_REE values show approximately linear correlations with decreasing pressure from the critical point to salt-saturated conditions where the L-V curve meets the liquid + vapour + solid boundary. At given P and T, we found a systematic variation of D_REE along the La-Lu suite. HREE are enriched in the vapour phase relative to LREE. Fractionation coefficients K_D=(HREE^V/HREE^L)/(LREE^V/LREE^L) increase linearly with (P=P_crit-P along a particular isotherm. At the 450 °C isotherm, K_D (Lu/La) at the critical point (425 bar and 10 wt% NaCl) is 1; about 2.5 at 350 bar (33 wt% NaCl in the liquid); and about 5 if extrapolated to salt-saturation (250 bar and 52 wt% NaCl in the liquid). The REE fractionation behaviour is similar along the CaCl₂-H₂O solvus boundaries. Existing equations of state and thermodynamic databases of REE species cannot predict this behaviour at L-V-equilibrium conditions. That HREE are preferentially fractionated over LREE into the vapour phase has important petrogenetic consequences. In boiling hydrothermal systems, brines will be depleted in HREE relative to LREE. Isobaric cooling is ineffective for fractionation because the solvus closes and the system eventually shifts into the one-phase field. Fractionation is most effective in systems undergoing isothermal or adiabatic decompression. In an open system, where vapour may escape through cavities, fractionation is probably controlled by a Rayleigh fractionation process, resulting in larger overall fractionation effects. Similar fractionations probably occur during magma degassing at very shallow intrusion levels.     

“寨背式”离子吸附型稀土矿床多类型稀土矿化及其成因

赣南寨背离子吸附型稀土矿床产于寨背复式花岗岩体的风化壳中,自20世纪80年代发现以来一直以轻稀土型开采,近年在轻稀土型花岗岩风化壳中发现了重稀土矿。为了探讨轻稀土型花岗岩风化过程中重稀土元素的迁移、分馏和富集机制,本文选择了区内三个具有代表性的风化壳钻孔(ZK1、ZK2和ZK4)对其进行了全相和离子交换相稀土元素地球化学研究。结果显示：钻孔ZK4中离子交换相稀土含量介于14.90×10^-6～835.8×10^-6之间,并富集轻稀土(LREE/HREE=2.28～10.78);钻孔ZK1中离子交换相稀土含量达1470×10^-6(9件样品均值),具有从轻稀土型向重稀土型过渡的配分特征(LREE/HREE=1.30～1.65),并且剖面自上而下显示轻、重稀土逐渐富集的趋势;钻孔ZK2中离子交换相稀土含量为492.4×10^-6(8件样品均值),自上而下稀土配分类型从轻稀土型过渡至重稀土型(LREE/HREE=0.43～2.25),且轻稀土富集在全风化层上部而重稀土则富集在下部。三个钻孔的Nb/Ta和Zr/Hf...     

The Mobility of Rare—Earth Elements During Hydrothermal Activity：A Review

The mobility of the rare-earth elements(REE)during hydrothermal activities is increasingly documented.Geological and experimental evidence suggests that REE may be mobile in solutions rich in F^-,Cl^-,HCO3^-,CO^2- 3,HPO4^2-,PO4^3-,or in combinations of the above ligands,even though little has been known about which ligand or which combination is most effective in mobilizing REE. The fractionation of REE resulting from hydrothermal activities is inconsistent.One set of field data implies the prererential mobility of the light rare-earth elements(LREE).whereas another set of field observations indicates the dominant mobilization of the heavy rare earth elements(HREE),and some theoretical prediction is comtradictory to the field evidence.The Eu anomalies due to hydrothermal activities are complex and plausible explanation is not available.The existing experimental approaches dealing with REE are not adequate for explanation ofREE behaviour in aqueous solutions.Systematic experimental approaches are suggested.     

The Behaviour of Rare—Earth Elements（REE） During Weathering of Granites in Southern Guangxi,China

The behaviour of the rare-earth elements(REE)during the weathering of granites was studied in southern Guangxi,China.Based on the study of the weathering profiles,the soil,weathered and sub-weatereb zones are identified with different REE geochemical behaviours throug the weathering profiles of granite.The Ce anomalies of the weathering profiles cover a large range of values with most falling between 1.02 and 1.43in the soil zone and 0.16and 0.40in the weathered and sub-weathered zones.Light rare-earth elements(LREE) and heavy rare-earth elements(HREE)are enriched to varying degree in the weathering profiles as compared to host granites.In the soil zone,more HREEs are leached than LREEs,and HREEs are more enriched than LREE in the weathered and sub-weathered zones.It is considered that infiltration and adsorption on clays are two processes controlling the enrichment and formation of REE deposits in the weathering profiles of granite.     

西藏尕尔勤铜矿床花岗闪长斑岩地球化学特征及成矿作用研究

对尕尔勤铜矿床花岗闪长斑岩及其锆石的稀土元素进行了分析,并对其成矿作用进行了研究。结果表明,花岗闪长斑岩稀土元素总含量变化范围不大（ΣREE=48.64×10-6~78.12×10-6）,LREE/HREE=8.67~11.68,所有样品都呈轻稀土元素相对富集、重稀土元素亏损的右倾型分配模式;δEu由弱负异常→弱正异常演化,这是因为地幔底辟作用引发地壳部分重熔形成长英质岩浆的过程中,逐步消弱了结晶分异导致的负Eu异常进而出现弱的正Eu异常。锆石具有典型的振荡环带,稀土总量较高（ΣREE=735.78×10-6~6792.10×10-6）,相对亏损轻稀土,富集重稀土,正Ce异常明显,并呈现弱的负Eu异常,这是因为在地幔流体作用下,重稀土元素及Ce较其它轻稀土元素更容易进入锆石晶格所致,Eu呈弱的负异常则是成岩后期岩体受氧化淋滤所致。综合分析,揭示出地幔流体作用导致花岗闪长斑岩具有壳幔混染甚至成矿特征,同时还能透过岩浆与围岩发生物质和能量的交换,导致变质砂岩成矿的成因机制。      

珠江三角洲晚第四纪风化层稀土元素地球化学特征*

珠江三角洲地区上更新统与全新统之间广泛发育1层杂色黏土,其成因多认为主要是由上更新统沉积物在末次冰盛期暴露于地表风化而成。对取自珠江三角洲3条钻孔（PRD09、PRD16和PRD17）的岩心样品分析表明,受风化作用的影响,其稀土元素含量和分异特征发生了较明显的变化。杂色黏土层的稀土总量大大低于下伏沉积物,而在邻近风化层的下伏沉积物中稀土元素却表现为明显富集,尤其是重稀土元素的富集。风化作用强度较大的PRD09孔和PRD17孔下伏沉积物中的稀土富集程度高于风化作用强度相对较小的PRD16孔。珠江三角洲在末次冰盛期时普遍发育的酸性介质条件,促进了风化层的稀土元素发生溶解和迁移。在风化过程中,由于轻、重稀土元素具有不同的溶解迁移能力和吸附能力,导致杂色黏土层的REE指标值（LREE/HREE、(La/Gd)_N和(La/Yb)_N）高于下伏沉积物。风化过程对Ce、Eu异常有一定的影响,但不十分明显,杂色黏土层的Ce、Eu异常值仅略低于下伏沉积物。     

Rare earth elements in modern coral sands: an environmental proxy

The concentration rare earth elements and Yttrium (REE + Y) were determined in coral sands from Kavaratti Island, Arabian Sea, India. Chondrite-normalized REE + Y patterns show: (1) high REE concentration particularly light REE (LREE) enrichment; (2) consistent negative Ce anomaly; (3) nearly chondritic Y/Ho ratios. All these features are consistent with the geochemistry of well oxygenated seawater with significant terrestrial contribution. The seawater composition of Nd/Yb ratio inferred from the coral record point to the dominance of LREE more than the heavy REE (HREE). The high terrestrial input rich in LREE and property of adsorption/scavenging processes of LREE than that of HREE may be the cause. Terrigenous contributions were detected on the basis of co-occurring trace element concentrations (Sc, Hf and Th) and Y/Ho ratio. Except for La, the REE distribution coefficients, KD(REE)s, are between 100 and 300. KDs are high comparing to the other elements in biogenic calcite which is attributed to detrital contamination during elemental incorporation. This study may not reflect original seawater chemistry but it can be a good proxy to indicate proximity of corals to terrigenous input sources.     

灰岩含水层中稀土元素在地下水与围岩间的分异:以皖北任楼煤矿太原组灰岩含水层为例

采取了皖北任楼煤矿太原组灰岩和灰岩水样品进行稀土元素测试分析,结果显示灰岩样品稀土总量较低,平均为36.947×10-6,灰岩样品稀土配分模式表现为轻稀土富集、重稀土亏损型;灰岩水样品稀土总量平均为0.052 6×10-6,灰岩水样品轻、重稀土均富集,轻、重稀土之间分异明显。对灰岩含水层水岩相互作用进行研究,结果表明:轻稀土表现稳定,重稀土分异明显,尤其在Y处有一个明显的峰值;Y元素与Ca元素呈正相关关系,相比石灰岩,灰岩水的Y/Ho、Y/Dy分异更为明显。研究认为,灰岩水中Y元素的峰值效应也可作为灰岩水源识别的依据。     

贵州锦屏地区新元古代下江群地球化学特征及构造环境研究

对贵州锦屏新元古代下江群地层剖面常量元素及稀土元素系统分析结果表明,该区下江群地层常量元素具有中等Si O2含量,介于57.54%~88.91%之间,平均68.32%,较低的Ca O含量(一般1%),较高的K2O/Na2O,Al2O3/Ti O2比值及较低的TFe2O3+Mg O含量。稀土总量ΣREE介于46.5×10-6~306.3×10-6之间,平均值为152.5×10-6,ΣLREE/ΣHREE为8.73~21.6,平均12.96,表明轻稀土相对富集,重稀土相对亏损;下江群各组段δEu在0.7~0.8之间,为弱负异常。稀土配分模式总体为右倾,而轻稀土分馏中等,重稀土分馏较低,表现在稀土配分曲线为轻稀土斜率较大,重稀土趋于平坦。通过各组段地球化学特征参数与参数投点可得:番召组与清水江组、平略组与隆里组具有相似地球化学特征,表明其构造环境相似且呈过渡变化,初步认为番召组与清水江组形成于活动大陆边缘的弧后盆地沉积,而平略组与隆里组为大陆边缘的边缘海沉积。     

四川盆地北部早白垩世剑门关组泥质岩地球化学特征及其地质意义

早白垩世剑门关组是研究四川盆地北部沉积环境演化的良好地层,对该地层开展系统的地球化学研究,对探讨四川盆地北部早白垩世剑门关组物源区性质、构造背景、古风化作用及古环境具有重要意义。系统分析了剑门关组泥质岩主量、微量和稀土元素地球化学特征,发现早白垩世剑门关组泥质岩富CaO、MgO,贫Al_2O_3、Fe_2O_3、K_2O、Na_2O、TiO_2、P_2O_5、MnO,富Cr、Cs、V,贫Sr、Nb、U、Hf,稀土元素总量为(164.96～234.35)×10^-6,轻、重稀土元素比值为11.77～15.87,轻、重稀土元素分馏程度高,轻稀土元素相对富集,具弱的正Eu异常。综合分析认为:剑门关组为同一物源的近物源再旋回沉积岩;源岩为沉积岩,可能富含斜长石、重晶石等富Eu矿物;源岩在沉积前经历了中等程度的化学风化作用,并发生了钾交代作用;剑门关组沉积期为温暖、湿润的气候,物源区具有由活动大陆边缘向大陆岛弧转化的特征。     

辽西阜新-彰武地区新生代火山岩的岩石地球化学特征及成因分析

辽西阜新-彰武地区新生代有两个火山旋回,即古近纪古新世那立闪旋回和新近纪中新世船底山旋回.通过1∶25万区域地质调查修测项目,根据野外岩石学、岩石地球化学、火山旋回、区域对比并结合前人资料进行了深入细致的研究和厘定.各旋回火山熔岩总体从基性→中基性演化,具有钠、硅、铝增高,铁、镁降低的特点.该时期火山岩各岩石过渡元素分配型式曲线基本协调一致,呈明显的“V”型,表明为同源岩浆分异产物.偏碱性岩石为富稀土岩石,正常岩石为贫稀土岩石,LREE/HREE值为8.2~18.84.各岩石均具轻稀土富集、分馏较好,重稀土亏损、分馏较弱的特点.Sm/Nd值在0.12~0.21之间,Eu/Sm值为0.28~0.86,反映该时期火山岩浆主要来源于地幔.     

河流稀土元素地球化学研究进展

河流系统中,稀土元素(REE)受区域地质背景、风化作用、溶液化学以及水与颗粒物相互作用等因素的影响发生分异。河流悬浮物显示轻稀土(LREE)适度富集;河水显示重稀土(HREE)富集,或在HREE富集的基础上又有适度的中稀土(MREE)富集;与其它微量元素相比,REE在河水与颗粒物之间有较小的分配系数(K≈10-6);河流沉积物多显示平坦的REE配分模式。     

Zoning and sectoriality of the florencite and xenotime group minerals from quartz veins,the Subpolar Urals

A detailed study of the florencite and xenotime assemblage from quartz veins of Au-REE occurrences in the Subpolar Urals allowed the REE fractionation and distribution of REE mixtures in the crystal structure to be characterized. In minerals of selective composition, isomorphic mixtures of LREE and HREE are divided into lanthanum La_sg (La-Pr) and samarium Sm_sg (Nd-Eu) subgroups in florencite and gadolinium Gd_sg (Gd-Dy) and ytterbium Yb_sg (Ho-Lu) subgroups in xenotime. Concentrations of elements from these subgroups are inversely proportional to each other. Each florencite or xenotime crystal is characterized by several mineral varieties: xenotime-(Y) and Gd-bearing xenotime-(Y), florencite-(Sm), -(Nd), and -(Ce); they are selectively distributed by growth zones and pyramids of the crystal with formation of direct and inverse zoning. In both cases, cores of the crystals are enriched in HREE. The correlation between REEs, Y, and such trace elements as As, S, Ca, Sr, U, and Sc is established. REE deportment is considered in minerals formed as products of primary crystallization and hydrothermal redeposition. The REE fractionation is interpreted in terms of quantum mechanics.