The aqueous geochemistry of the rare-earth elements: Critical stability constants for complexes with simple car☐ylic acids at 25°C and 1 bar and their application to nuclear waste management

The mobility of the rare-earth elements (REE) is relevant to nuclear waste management in that REE are produced during radioactive decay in high-level waste and they are good chemical analogues for some of the trivalent actinides (e.g., Am³⁺ and Cm³⁺). Car☐ylic acids are present naturally in many geologic fluids and also have been disposed of along with radionuclides; such complexing agents may increase the mobility of the REE (actinides) and need to be considered in geochemical models of the transport of these metals into the far-field environment. In this study, available stability constants for the formation of REE complexes with the organic ligands acetate, adipate, benzoate, citrate, ETDA, formate, fumarate, glutarate, glycolate, -hydroxyisobutyrate, isobutyrate, lactate, maleate, malonate, -mercaptoacetate, oxalate, m-phthalate, o-phthalate, propionate, salicylate and succinate have been critically evaluated. Those stability constants considered most reliable were, where necessary, corrected to 25°C using published enthalpy data and, where possible, corrected to infinite dilution using a model based on the Pitzer equations. These data provide the basis for future geochemical modelling of the behavior of the REE in nuclear waste disposal sites. Some simple geochemical calculations presented in this paper suggest that monodentate ligands such as acetate are unlikely to contribute significantly to REE (actinide) mobility in most nuclear waste disposal environments. However, ligands capable of chelating in a multi-dentate manner, e.g., oxalate, malonate, succinate, EDTA, etc., may increase the mobility of trivalent lanthanides and actinides significantly, even though their concentrations are lower than monodentate ligands in most natural environments. However, the effectiveness of any of these organic ligands depends on the concentrations of competing ions, such as Ca²⁺, Mg²⁺, etc., being low relative to the total ligand concentration.     

低温热液成矿作用中铊有机络合物搬运形式的研究

文章依据等库伦反应外推原理,计算了铊的醋酸(TlAc0)、柠檬酸(TlCit2-)、苹果酸(TlMal-)、草酸(TlOx-)及琥珀酸(TlSuc-)络合物在25～100℃之间的稳定常数。将这些稳定常数输入EQ3/6的DATA0.SUP热力学数据库后,在75℃和100℃温度条件下,对铊的诸物种于低温热液中在不同pH值条件下的分配进行了计算。计算表明,在中性及偏碱性条件下,在75℃还原环境中,自由铊离子(Tl+)所占比例约为55%,TlHS0约占10%,而其余则为铊的有机络合物,并以铊的柠檬酸络合物占绝对优势。在75℃氧化环境中,自由铊离子约占55%,而铊的有机络合物则为45%左右。在100℃还原环境中,自由铊离子所占比例约为20%,TlHS0约占20%,其余则为铊的有机络合物。在100℃氧化环境中,自由铊离子所占比例约为30%,其余则为铊的有机络合物。因而笔者认为,铊的有机络合物,尤其是铊的柠檬酸络合物,在低温热液中对于铊的溶解及搬运起着重要的作用。     

Prediction of the thermodynamic properties of metal–chromate aqueous complexes to high temperatures and pressures and implications for the speciation of hexavalent chromium in some natural waters

Log–log correlation plots between the dissociation constants of known metal–chromate complexes and those of corresponding metal–sulfate complexes at 25 °C, 1 bar were used to derive the standard partial molal Gibbs free energies of formation of unknown metal–chromate complexes involving either (i) monovalent cations, divalent cations, and trivalent lanthanides or (ii) trivalent cations (excluding those of rare earth elements, REE) and tetravalent cations. For each of these two classes of ionic associations, empirical relationships between the standard partial molal volumes, isobaric heat capacities and entropies of known metal–chromate complexes and the corresponding thermodynamic properties of metal ions have been found. These data were utilized to evaluate the solute-characteristic parameters of the revised Helgeson–Kirkham–Flowers equation of state and to compute the thermodynamic properties of the dissociation reactions of metal–chromate complexes at high temperatures and pressures.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Do organic ligands affect forsterite dissolution rates?

Far-from equilibrium, steady state forsterite dissolution rates were measured at pH ∼3 and 25 °C in aqueous solutions containing 0.1 m/kg NaCl and up to 0.1 mol/kg of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those common in Earth surface environments and those considered as potential catalysts for use in CO₂ sequestration efforts: acetate, oxalate, citrate, EDTA⁴⁻, glutamate, gluconate, malonate, aspartate, tartrate, malate, alginate, salycilate and humate. The presence of up to 0.1 mol/kg of each organic ligand altered forsterite dissolution rates less than 0.2 log units, which is the estimated uncertainty of the measured rates. Results obtained in this study, therefore, suggest that the presence of aqueous organic anions negligibly affects forsterite far-from equilibrium dissolution rates in most natural environments, and indicate that forsterite carbonation may not be appreciably accelerated by organic ligand catalysis.     

A study of differentiation pattern and rare earth elements migration in geochemical and hydrogeochemical environments of Airekan and Cheshmeh Shotori areas (Central Iran)

The Airekan and Cheshmeh Shotori areas are located about 60 km northeast of Khour, in Isfahan province from Central Iran. Research on characteristics and rare earth elements (REE) pattern in hydrogeochemical environments of these areas suggests the same origin for the elements dissolved in groundwater in these areas. Investigation of migration pattern of REE in hydrogeochemical environments shows that the migration and transportation of REE has occurred through chloride complexes. REEs, leached by water/rock interaction from the Airekan granite, are transported by groundwater and then precipitated in the Cheshmeh Shotori area. Study of the Cheshmeh Shotori sediments shows the presence of a sequence of red oxidized and dark layers. Geochemical characteristics of these sediments reveal that their REE characteristics are mainly inherited from the Airekan granite. Changes in the REE pattern of these sediments with depth show that changes in oxidation and reduction process have not played a significant role in controlling their behavior. It is crucial to note that adsorption of REEs dissolved in water by hydrosilicate increases these elements in depth. The REE behavior shows water/rock interaction between the granitic rocks and groundwater as the main factor of solution, migration and precipitation of REEs in the Cheshmeh Shotori area.     

煤矸石中稀土元素的提取富集工艺

用盐酸浸取煤矸石粉末样品, 选择性溶解其中稀土元素(REE) 、Fe、Al和Ti等元素; 用氢氧化铁共沉淀法有效地分离富集稀土元素(REE) , 继而用草酸盐沉淀将稀土元素与Fe定量分离。实验表明: 稀土元素的提取率为88.25% ～92.86% , 稀土氧化物纯度达到99.00%。本方法具有操作简单、富集效率较高等特点。     

The mobility of the rare earth elements: Evidence and implications from selected terrains affected by burial metamorphism

The mobility of the rare earth element (REE) during hydrous burial metamorphism is described from three localities. Comparison of REE abundances in relict domains and metadomains from flood lavas in the Maddina Volcanics, Fortescue Group, Western Australia shows that, relative to the relict domains, REE may be strongly depleted in certain metadomains. Strong variations in La/Yb, La/Sm and Eu may also occur due to postcrystallization secondary processes. Similar comparisons in flood lavas from Mamainse Point in the Canadian Keweenawan Series show that REE are mobile and increase in abundance in metadomains. Spilites from U.S. Virgin Islands also show evidence for REE mobility during low grade burial metamorphism. In this case light REE (LREE) have been preferentially mobilized with heavy REE (HREE) remaining parallel or sub-parallel on chondrite normalized plots.REE analyses from these locations together with an evaluation of published work suggests that the mobility of REE can be described by: 1. gross REE and selective LREE enrichment; 2. REE movement around a primary mean; 3. gross REE depletion; 4. selective REE mobility. Failure to take into account REE mobility may lead to incorrect conclusions concerning petrogenetic models based on altered basic sequences. The coherence of REE with other key trace elements during alteration is also discussed.     

滇西陇川营盘山离子吸附型稀土矿稀土元素分布特征

滇西陇川地区广泛分布着白垩纪至古近纪中酸性花岗岩,以邦棍尖山为代表的岩体花岗岩稀土含量较高,经复杂的风化淋滤作用,岩体中的稀土元素在风化壳中迁移、富集成矿,陇川营盘山稀土矿即为近年新发现的该类型矿产地之一。为研究新发现的营盘山稀土矿稀土元素分布特征、富集规律及稀土配分特征,利用电感耦合等离子体质谱仪(ICP-MS)分析成矿母岩及其风化壳不同风化程度样品稀土分量,结果表明:风化壳各层位稀土元素分布特征相比母岩具有明显的继承性,随风化程度升高,轻重稀土分馏程度升高,轻稀土在全风化层上部相对富集,且随风化程度升高轻稀土富集程度升高,而重稀土的富集程度则逐渐减弱,Gd是风化壳富集能力最强的元素,Dy富集能力最弱,Ce富集在近地表,重稀土具有更强的向下迁移能力。同时,研究发现该稀土矿床的稀土配分特征为低钇、铕,富镧、铈、钕。     

Organic/ Inorganic Occurrence of Metallic Elements of the Black Shale-Hosted Baiguoyuan Silver-Vanadium Deposit in Xingshan, Hubei

By means of kerogen purification, the proton induced X-ray emission (PIXE) and instrumental neutron activation analysis (INAA), the authors have studied the organic/inorganic occurrence modes of the metallic elements of the Baiguoyuan silver-vanadium deposit hosted in black shale in Hubei Province, China. The result shows that Au, Hg and Ta have a strong tendency to occur organically, with more than 70% of these elements being associated organically. Se, Ga, Ag and Hf are partly associated with organic matter, with more than 20% of them occurring organically. Compared with the above elements, Zn, Cu, As and Sb are weakly associated organically, and tend to be enriched in kerogen. However, Mn, Th, U, V, Co, Cr, Al, Fe and Sc usually occur inorganically. Of the rare earth elements (REE), La, Ce, Tb, Dy, Yb and Lu have stronger ability to be associated with organic matter than Sm and Eu.     

内蒙古大石寨地区稀土元素的区域分布特征

总结了内蒙古大石寨地区1∶25万区域地球化学调查获得的1点/4km2的水系沉积物组合样品中的La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y等15种稀土元素的区域地球化学分布特征。稀土元素分布与研究区中部的黑云母花岗岩密切相关,轻稀土主要分布在该岩体外围的二叠系地层中,重稀土主要分布在该岩体上方。该岩体上方和外围地层的稀土元素分布、稀土元素总量、轻重稀土比及δCe、δEu、(La/Sm)N、(La/Tb)N、(La/Lu)N、(Ce/Yb)N、(Gd/Lu)N等稀土元素分馏特征的差异明显。利用区域地球化学调查水系沉积物样品中的稀土元素含量,可获得研究区可靠的稀土元素区域地球化学分布特征,也可反映研究区地质特点,并为区域地球化学异常解译提供参考资料。     

The distribution of rare earth elements between monzogranitic melt and the aqueous volatile phase in experimental investigations at 800 °C and 200 MPa

The partitioning of the rare earth elements between a peraluminous monzogranitic melt and a chloride-bearing, sulfur- and carbon dioxide-free, aqueous volatile phase was examined experimentally as a function of chloride and major element concentrations at 800 °C and 200 MPa. The light rare earth elements (e.g. La, Ce) partition into the aqueous volatile phase to a greater extent than the heavy rare earth elements (e.g. Yb, Lu). Distribution of the rare earth elements and the major elements H, Na, K, Ca, and Al between the melt phase (mp) and aqueous volatile phase (aq) is a function of the chlorine concentration in the system, and our data are consistent with the rare earth and major elements occurring as chloride complexes in the aqueous volatile phase. Apparent equilibrium constants for experiments at 800 °C and 200 MPa, K ^′ _REE,Na ^aq/mp , expressed as the ratio of the concentration of a given rare earth element in the aqueous volatile phase to the concentration of the same element in the melt phase, divided by the cubed ratio of sodium in the aqueous volatile phase to the concentration of sodium in the melt phase, decrease systematically with increasing atomic number from K ^′ _La,Na ^aq/mp = 0.41(±0.03) to K ^′ _Lu,Na ^aq/mp =0.11(±0.01), except for Eu. These experimentally derived apparent equilibrium constants for the rare earth elements can be used in a numerical simulation of magmatic volatile exsolution. The simulation gave results consistent with the elemental distribution in the potassic alteration zone of a deep porphyry copper deposit, but higher concentrations of heavy rare earth elements are released into the magmatic aqueous solution than are captured in the secondary mineralization. Received: 1 November 1999 / Accepted: 7 June 2000     

离子吸附型稀土监控样定值研究

离子吸附型稀土矿是中国极其重要、世界罕见的矿床类型,是中国的优势矿产资源。目前现有的稀土标样全部为稀土矿石成分分析标样,稀土元素以氧化物形式稳定存在,无法淋滤浸取,不能对离子吸附型稀土淋滤过程进行监控。为进一步满足离子吸附型稀土资源勘查和评价需要,本文按照导则《标准物质定值的通用原则及统计学原理》（JJF 1343—2012）,制备了三种岩性共9个离子吸附型稀土监控样。样品采自南岭地区典型富轻稀土（HREE）离子吸附型稀土风化壳,经干燥、球磨至200目后混合机混匀,以硫酸铵淋滤、电感耦合等离子体质谱法（ICP-MS）测试离子相稀土元素含量,检验样品均匀性,结果表明F值小于临界值F_{0.05（19,20）},样品均匀性良好。在两年内对样品进行4次稳定性检验,在95%置信度时│β₁│<t_0.05×s（β₁）,未发现明显不稳定变化,表明稳定性良好。由8家技术权威的实验室进行协作定值,经过统计计算给出各离子相稀土元素含量的加权平均值和扩展不确定度,定值结果涵盖除Sc以外的15种稀土元素。该系列监控样的研制能够为离子吸附型稀土矿产资源评价和有效利用等工作提供计量支撑。     

Rare Earth Element and Trace Element Features of Gold-bearing Pyrite in the Jinshan Gold Deposit, Jiangxi Province

<正>Jinshan gold deposit is located in northeastern Jiangxi,South China,which is related to the ductile shear zone.It has a gold reserve of more than 200 tons,with 80%of gold occurring in pyrite. The LREE of gold-bearing pyrite is as higher as 171.664 ppm on average,with relatively higher light rare earth elements(LREE;159.556 ppm) and lower HREE(12.108 ppm).TheΣLREE/ΣHREE ratio is 12.612 and(La/Yb)_N is 11.765.These indicate that pyrite is rich in LREE.The(La/Sm)_N ratio is 3.758 and that of(Gd/Yb)_N is 1.695.These are obvious LREE fractionations.The rare earth element(REE) distribution patterns show obvious Eu anomaly with averageδEu values of 0.664,andδCe anomalies of 1.044.REE characteristics are similar to those of wall rocks(regional metamorphic rocks),but different from those of the Dexing granodiorite porphyry and Damaoshan biotite granite.These features indicate that the ore-forming materials in the Jinshan gold deposit derived from the wall rocks, and the ore-forming fluids derived from metamorphic water.The Co/Ni ratio(average value 0.38) of pyrite suggests that the Jinshan gold deposit formed under a medium-low temperature.It is inferred from the values of high-field strength elements,LREE,Hf/Sm,Nb/La,and Th/La of the pyrite that the ore-forming fluids of the Jinshan gold deposit derived from metamorphic water with ClF.     

Do organic ligands affect calcite dissolution rates?

Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO₂ sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA⁴⁻, succinate, d-glucosaminate, l-glutamate, d-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of <0.05 mol/kg of these organic anions changes calcite dissolution rates by less than a factor of 2.5 with the exception of citrate and EDTA⁴⁻. The presence of 0.05 mol/kg citrate and EDTA⁴⁻ increases calcite dissolution rates by as much as a factor of 35 and 500, respectively, compared to rates in organic anion-free solutions. Further calcite dissolution experiments were performed in the presence of organic polymers similar to bacterial exudates, cell exopolysaccharides, and analogs of microbial cell envelopes: alginate, lichen extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.     

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。     

Rare Earth and High Field‐Strength Elements in the Multani Mitti Clay: A Study Using INAA

Instrumental neutron activation analysis was used to determine nine rare earth elements (REE), Sc and five high field‐strength elements (HFSE) in the Multani Mitti (MM) clay. Chondrite‐normalised rare earth element patterns for the MM clay compared with those for the Post‐Archaean Australian Shale (PAAS), Upper Continental Crust (UCC) and North American Shale Composite (NASC) showed enrichment of light REEs and depletion of heavy REEs with a slight negative Eu anomaly. The Multani Mitti clay showed close resemblance to PAAS and NASC in its average REE and HFSE contents. Positive correlations between La/Ce, La/Sm, La/Yb, Zr/Hf, Th/U and Th/Ta ratios predict enrichment of LREEs, Zr and Th and depletion of HREEs. A parent source of felsic origin for the MM clay is also endorsed through the high La/Th and low Th/Sc ratios observed.     

Dissolution kinetics and biodurability of tremolite particles in mimicked lung fluids: Effect of citrate and oxalate

The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble’s solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L⁻¹ of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from −13.00 (pH 4) to −13.35 (pH 7.4) mol g⁻¹ s⁻¹ and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L⁻¹ citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L⁻¹) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers.     

Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.     

云南红河州超大规模离子吸附型稀土矿的发现及其意义

围绕国家战略性产业发展对稀土资源的需求, 特别是紧缺的重稀土资源, 如何快速有效地发现富含重稀土矿床找矿靶区是勘查地球化学急需解决的问题。“化学地球”大科学计划获得全国地球化学基准数据, 圈定稀土异常超常富集区9处, 其中新发现的滇南红河州蒙自—中越边境地区稀土富集区轻重稀土比值(LREE/HREE)为3.5, 与华南富含重稀土的离子吸附型稀土矿异常LREE/HREE比值一致。结合地质背景、成矿母岩、气候和地形地貌特点等初步判断具有寻找类似华南富含重稀土的离子吸附型稀土矿资源潜力。因此, 对这一异常的核心区, 开展了1:25万、1:5万地球化学调查和风化剖面测量, 并经29个钻孔验证, 初步发现马鞍底潜在超大型富含重稀土离子吸附型稀土矿。富矿区分布于坡度较缓的坡脚处, 风化母岩为印支期和燕山期花岗岩、元古界斜长片麻岩和变粒岩。风化剖面厚度最深可达25 m左右, 富矿层位位于全风化层, 一般在2~13 m深度, 矿体平均厚度6~13 m, 最厚可达21 m, 平均品位0.14%。根据29个钻孔和84个风化壳剖面测量, 初步估算稀土潜在矿石量约9.46亿吨、稀土氧化物潜在资源约100万吨。这是我国首次在滇南地区发现潜在超大型离子吸附型稀土矿。该离子吸附型稀土矿同时富含轻稀土(镧、铈、镨、钕)和重稀土(钆、铽、镝、钇), 具有重大经济价值和科学意义。这一发现表明开展从极低密度、低密度到高密度地球化学调查, 获得全部16个稀土元素高质量数据是发现离子吸附型稀土矿的快速有效方法。