东沟坝多金属矿床矿质来源的稀土元素地球化学限制

对东沟坝矿床矿石及赋矿火山岩的稀土组成研究表明：矿石普遍发育显著的Eu正异常和弱的Ce负异常,说明成矿热液为温度较高(250℃以上)、相对还原的热流体。Eu正异常和弱Ce负异常同时在矿石中发育。说明矿石沉淀时较高温度的热流体与少量的海水发生了对流混合。除Eu、Ce之外矿石稀土配分模式总体与赋矿的火山岩接近,说明成矿金属主要来自豆坝群火山岩。根据矿石中大量发育重晶石和矿石普遍具有的LREE富集、明显的Eu正异常和弱Ce负异常的事实,推断成矿流体中SO4^2-的大量出现与岩浆脱气组分贡献有关。     

从稀土元素判别早前寒武纪岩石物质来源评价中条山铀、铜区域成矿远景

稀土元素已被公认为是判断岩石物质来源的有效地球化学指示剂:而物源,尤其是含矿层的物源(有时包括成矿组分的来源)对区域成矿远景评价具有很重要的意义。本文主要从稀土元素地球化学角度研究了中条山上太古界涑水杂岩、下元古界绛县群、含矿层中条群篦子沟组代表性岩石的物质来源,并从物源(矿源)对含矿层的成铀、成铜远景进行了评价。指出了铀、铜成矿的有利地段。     

川东南二叠系区域盖层沥青来源稀土元素示踪

二叠系区域性盖层中沥青的稀土元素特征和配分模式与寒武系沥青相同,而与志留系烃源岩显著不同,说明区域性盖层中的沥青来自于下伏寒武系牛蹄塘组烃源岩.     

熊耳山上宫金矿稀土元素特征及对金矿物质来源的指示意义

上宫金矿矿化样品与熊耳群安山岩、燕山期花岗岩有着相似的稀土元素特征,其物源关系更为密切.不同类型矿石的稀土总质量分数存在较大差别,总体呈现出矿化程度越强稀土总量越低的特征.大部分金矿石与铅锌(银金)矿石均表现出弱的Eu、Ce异常,其中 δEu金矿石均值(0.84)>δEu铅锌矿石均值(0.75),δCe金矿石均值(0.88)<δCe铅锌矿石均值(0.96),造成这种现象的原因可能是热液交代或成矿热液为富Cl–的还原性流体.(Sm/Eu)样品/(Sm/Eu)球粒陨石-(Sm/Eu)样品图解显示,上宫金矿各类样品能近似拟合成一条直线,说明了岩浆热液为成矿提供了最初的热源和物源,而安山岩和片麻岩的接触交代可能对成矿提供了部分物源.矿石样品和蚀变岩样品中均出现不同程度的Tb、Tm元素正异常,说明成矿物质来源可能受到了地壳岩石的影响.上宫金矿田δEu-Au相关图解显示,成矿过程中,随着Au元素的富集,Eu元素也出现相对富集.     

贵州盘县架底金矿稀土元素和同位素特征及成矿物质来源探讨

架底金矿位于贵州西部峨眉山玄武岩分布区,首次在该区发现产于峨眉山玄武岩组第二段中部的以蚀变火山角砾岩为主的层间破碎带中的原生金矿体,赋矿围岩主要为玄武岩和凝灰岩,容矿岩石主要为蚀变火山角砾岩,其下层矿产于中二叠统茅口组与上二叠统峨眉山玄武岩组间的不整合界面附近的构造蚀变体中。本文通过稀土元素和氢、氧、硫同位素来探讨架底金矿体与围岩的关系及成矿物质来源,矿体ΣREE值的变化范围为151.11×10~(-6)~321.52×10~(-6),平均值为221.21×10~(-6),明显小于围岩,LREE/HREE值的变化范围为2.9~8.53,平均值为6.84,La_N/Yb_N值的变化范围为5.55~12.33,平均值为9.13,略小于围岩。除了个别矿体样品的δEu值小于1,其他样品基本远大于1,暗示与成矿作用相关的流体可能经历过高温和还原的深部环境,矿体继承了围岩稀土配分曲线的部分特征,说明部分成矿物质可能来自围岩。辉锑矿δ34S值的变化范围为-0.80‰~-0.90‰,极差为0.1‰,平均值为-0.85‰,数据变化范围较窄,均一化程度较高,主要在0‰附近,指示成矿相关矿物辉锑矿的硫可能主要来源于深部。石英氢氧同位素的δD_(V-SMOW)值的变化范围为-70‰~-56‰,δ~(18)O_(V-SMOW)值的变化范围为23.20‰~23.60‰,按200℃作为本区金矿的成矿温度,根据石英-水在自然体系中的分馏方程式,可计算得出石英中与之相平衡的水的δ~(18)O_(H_2O)值变化范围为11.49‰~11.89‰,投图的结果说明与成矿作用相关的流体均落在岩浆水和变质水之间,显示两者相混合的特征,但研究区基本没有变质作用的发生,并且4件石英样品的δD_(V-SMOW)均落在正常岩浆水范围内,指示架底金矿中成矿流体来源具有岩浆水的特点。     

黔东北地区金亮萤石矿床稀土元素地球化学特征与成矿物质来源

黔东北-渝东南一带分布有大量的萤石矿床(点),这些矿床(点)主要分布在北东向区域性断裂两盘的奥陶系下统桐梓组和红花园组灰岩中NW、NNW向张性断裂内,矿体呈脉状或透镜状产出,深部至奥陶系下统桐梓组逐渐尖灭,关于该区萤石矿成因及物质来源长期存在较大争议。金亮萤石矿床是黔东北沿河地区代表性小型萤石矿床,本文对该矿床中萤石开展稀土元素地球化学研究。结果表明,萤石ΣREE为67.4×10^-6～90.55×10^-6,LREE/HREE值为43.98～78.78,δEu值为77.07～94.71,δCe值为0.39～0.42。矿床萤石稀土分布模式呈明显右倾曲线,为轻稀土相对富集型,以Eu正异常和Ce负异常明显为特征。结合矿床地质特征,认为该萤石矿床为热液成因的产物,萤石为同源同期热液流体在氧化环境成矿。萤石成矿作用与沉积岩关系密切,其中成矿物质Ca主要来源于下奥陶统红花园组灰岩,可能部分来源于深部碳酸盐岩,而成矿物质F主要来源于深部上震旦统陡山沱组至下寒武统明心寺组高氟地层。     

辽东湾东南部海域柱状沉积物稀土元素地球化学特征与物源识别

对辽东湾东南部海域LDC30孔沉积物稀土元素（REE）、粒度等指标进行了分析,研究了其沉积物中稀土元素组成特征及其控制因素,并对其物质来源进行了探讨。结果表明,LDC30孔沉积物ΣREE平均值为149.49 μg/g,略高于黄海和东海,但是低于渤海和南海,并且低于全球沉积物ΣREE的平均值。研究区沉积物REE配分模式表现为明显的轻稀土富集、重稀土相对亏损;δEu的平均值为0.71,为中度亏损,δCe无异常;轻稀土与重稀土之间的分异作用较强,且轻重稀土内部分异明显。根据沉积物REE垂向变化特征,可将LDC30岩芯以51cm为界划分为两段,上段（0~51 cm）ΣREE含量随着深度的减小而呈增加的趋势,下段（51~99 cm）ΣREE含量在垂向上没有明显的波动变化,并且上段较下段稀土分异明显。δCe整体上比较稳定,但是在上段（0~51 cm）呈现下降的趋势。δEu垂向上也相对稳定的趋势。该孔沉积物REE参数与粒度之间无明显的相关性,REE组成不受粒度的控制,但重矿物对REE的组成和分布状况有重要的影响。LDC30孔沉积物物质来源比较稳定,并且具有强烈的陆源特征,其沉积物主要来源于辽东湾北部河流（大辽河、小凌河、双台子河等）,同时辽东湾西部河流滦河可能对LDC30孔上段沉积物有一定贡献。     

贵州老万场金矿成矿物质来源的研究

硅酸盐成分研究表明老万场红土化过程经历了粘土化、铝土矿化、铁化三种化学风化作用;风化中化学蚀变较强，K2O、Na2O、CaO相对于Al2O3的淋失量很高。在红土剖面上成矿元素的含量变化很大。相关性分析表明，红土化过程中，Au、As的富集与脱硅富铝化程度关系不大，而与铁的富集有明显的关系；Au、As的富集与相对还原的环境有关，而Sb则在相对氧化的环境中易于聚集。可能反映了红土剖面中潜水面下部附近相对还原的环境Au、As易于富集。大厂层样品和老万场红土剖面样品在成矿元素(Au、As、Sb)含量、稀土元素含量、轻重稀土比值、配分曲线上以及微量元素特征包括大离子亲石元素、不相容元素上的较大差异，显示了红土层的发育与大厂层岩石有较大的差别，暗示它们物质来源上的一定差异性。     

鲜水河断裂带富硼地热水中稀土元素分布特征及其对硼来源的指示意义

高温地热系统地热水中普遍富含高浓度的硼,其来源的研究一直是地热地质学者关注的热点问题。尽管众多的学者对地热水中硼形成机理开展了广泛的研究,但富硼地热水中稀土元素的分布特征及其迁移规律能否指示热水中硼的来源尚不清楚。本研究以鲜水河断裂带富硼地热水为研究对象,通过野外调查取样、室内测试分析、水文地球化学模拟和综合研究等技术手段和方法,探究断裂带地热水中硼和稀土元素的分布特征和迁移规律。研究结果显示：鲜水河断裂带地热水中硼含量90%超过我国饮用水标准规定值0.5 mg/L（地热水中硼含量最大值为10.50 mg/L）;地热水中稀土元素含量为0.08～3.49 μg/L,且主要以LnCO₃⁺和Ln(CO₃)₂⁻的络合物形态存在。地热水稀土元素PAAS归一化模式表现为重稀土元素相对于轻稀土元素富集（(Nd/Yb)_SN均值为0.41）,且具有较显著的Eu（均值为0.34）和Ce（均值为0.07）正异常特征。地热水中硼和稀土元素的迁移均受到赋热含水层长英质和碳酸盐岩类矿物溶解过程的影响,且地热水中稀土元素的地球化学特征一定程度上可以指示地热水中硼的富集过程。研究成果拓展了稀土元素在富硼地热水研究中的应用,能为揭示富硼地热水成因研究提供依据。

     

准噶尔盆地表层沉积物的稀土元素特征与物源指示

准噶尔盆地的新生代沉积的物质来源对认识中亚地区乃至全球气候环境演变、亚洲内陆干旱化以及粉尘输送路径等关键科学问题都具有重要的意义,但目前对盆地内沉积物的物质来源的研究还比较粗略。文章以准噶尔盆地内不同类型的表层沉积物为研究对象,通过对稀土元素特征的研究进一步探讨盆地内不同沉积的物质来源与相互联系。研究结果表明：准噶尔盆地不同区域表层沉积物的稀土元素含量（不含Y元素）变化较大,变化范围为55.54~194.44 μg/g;大部分样品的δCe值在0.95~1.05之间,未见明显的Ce异常,指示了盆地内整体干旱环境下较弱的风化成壤作用,而Eu异常和UCC标准化配分模式表现出的复杂变化,可能指示了准噶尔盆地表层沉积物物质来源的多源性。根据盆地内表层沉积物的稀土元素总量、配分模式以及δEu值表现出的不同特征,结合了盆地内的区域地形和盛行风向等要素,认为盆地东部的戈壁砂和周围山地的基岩碎屑物之间存在着一定的物源继承,同时强劲的西北风也为该地带来了来自盆地北部和中部的物质来源;北部的阿尔泰山碎屑物质是盆地北部戈壁砂和沙漠砂的主要物质来源,但戈壁砂表现出的Eu中度亏损和较高的ΣREE值可能代表着该区域还存在更为广阔的物源;盆地西部各类沉积物之间表现出的稀土元素特征的相似性表明该地缺乏外界物质的参与,物源具有明显的局域性;盆地南缘的沙漠砂和河流表层沉积物主要来源于天山碎屑物质经冰川磨蚀及寒冻风化等作用形成的粉砂粒级物质,但是该地的黄土在地形和风向的影响下表现出了复杂的物质来源,盆地中的沙漠、天山碎屑物质、盆地东部的戈壁砂,甚至于中亚广大荒漠区的粉尘都为黄土提供了部分物源。

     

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.     

长江沉积物稀土元素的粒度效应研究

依据Stokes定律,将小于63μm的长江沉积物分成小于2、2～4、4～8、8～16、16～32、32～63μm6个粒级,采用ICP-MS法分别测试了分粒级沉积物的REE含量,结果显示:长江沉积物REE的丰度遵循元素的"粒度控制律",即随粒度变细,∑REE含量依次增高;北美页岩标准化分布曲线均呈右倾的近"W"型,轻、重稀土分馏明显,相对富集LREE,明显的Ce负异常和弱Eu亏损。对长江沉积物不同粒级样品进行X射线衍射分析和体视镜下观测,结果表明:长江沉积物随粒度增大石英和长石含量逐步增加,碳酸盐和重矿物在各个粒级中含量甚微并且随粒级变化不大;长江沉积物REE随粒度变细逐渐增加的特征主要受控于沉积物随粒度变化而变化的矿物成分,黏土粒级及细粉砂中较高的∑REE主要是黏土矿物吸附作用的结果,粗粉砂中较低的∑REE主要为长石和石英的稀释作用结果,而碳酸盐和重矿物因其较低的含量对稀土元素含量影响较小。     

Geochemistry of dissolved rare earth elements in the Equatorial Pacific Ocean

Seawater samples were collected from four locations in the Equatorial Pacific Ocean during the MR02-K06 cruise of the R/V Mirai and analyzed for dissolved rare earth elements (REEs) using inductively coupled plasma mass spectrometry. According to variations of REE concentrations and Yb/La ratios, the results show that the river input of the Papua New Guinea islands may affect the compositions of REEs in the Equatorial Pacific surface water. The Yb/La values and the REE concentrations in the waters deeper than 3,000 m in the western South Pacific and the Equatorial Pacific Oceans, which represent the characteristics of Antarctic Bottom Water (AABW), demonstrate similar variation trend with depth. This result also indicates that the REEs which originated from the South Pacific Ocean have entered the North Pacific Ocean across the equator with AABW intrusion.     

The rare earth element (REE) mineralisation potential of highly fractionated rhyolites: A potential low-grade,bulk tonnage source of critical metals

The rare earth elements (REE) have become crucial for modern industry, technology and medicine, with the increase in demand for these elements over the past few years currently being met by relatively few well-known mineral deposits. This lack of a secure supply of the REE has led to increased research into potential alternative sources of these in demand elements. The primary fractionation processes involved in the petrogenesis of highly fractionated high-silica rhyolites can cause the magmas that form these units to become preferentially enriched in the REE, especially in the more valuable heavy REE (HREE), although this is dependent on the mineral assemblages fractionated by the system in question, a factor that is in turn a function of the source and tectonic setting of a given magmatic event. The mineralogy of the REE is also important, with volatile exsolution and vapour-phase activity within highly evolved rhyolite systems potentially having a key role in concentrating the REE and other elements into concentrations (and more importantly potentially acid leachable and therefore processable minerals) that may be economically viable to extract. This, combined with the fact these rhyolites are often enriched in other critical and/or economically important metals (e.g., Y, Nb, Ta, Be, Li, F, Sn, Rb, Th, and U) means that these volcanic units should be considered as potential sources of these critical metals. In addition, the large volume nature of these rhyolites combined with the fact they frequently crop out at the Earth’s surface makes them ideally suited for more economical bulk open pit extraction. This suggests that these high-silica REE-enriched rhyolites should be considered potential REE analogues of bulk-tonnage, low-grade porphyry Cu deposits, warranting further investigation to determine whether these rhyolites are a viable new source of the REE (especially the HREE) and are potential targets for future mineral exploration.     

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.     

Geochemical behavior of rare earth elements in hydrothermally altered rocks of the Kuroko mining area,Japan

In this study we analyzed the chemical composition of hydrothermally altered dacite and basalt from the Kuroko mining area, northeastern Honshu, Japan, by REE (rare earth element). Features of rare earth element analyses include: (1) altered footwall dacite exhibits a negative Eu anomaly compared with fresh dacite, suggesting preferential removal of Eu²⁺ from the altered dacite via hydrothermal solutions, (2) altered hangingwall dacite and basalt and dacite and basalt adjacent to ore deposits exhibit positive Eu anomalies compared with fresh dacite and basalt, suggesting addition of Eu²⁺ from hydrothermal solutions, (3) LREE ratio (∑LREE/∑REE) from altered dacite of chlorite–sericite zone and K-feldspar zone show a negative relationship with δ¹⁸O, and La/Sm ratios show a positive correlation with the K₂O index. These trends indicate the addition of light rare earth elements such as La to the altered dacite from hydrothermal solution and/or leaching of heavy rare earth elements such as Sm and Yb, (4) Principal component analysis (PCA) indicates that light rare earth elements enrichment is related to the formation of sericite zone near the Kuroko deposits but not to the formations of chlorite and K-feldspar zones, and (5) The correlations among REE features (LREE ratio, MREE ratio, HREE ratio, Eu/Eu?), δ¹⁸O and K₂O index are not found for montmorillonite zone, mixed layer clay mineral zone and mordenite zone. Therefore, it is inferred that sericite, chlorite and K-feldspar alterations are related to the Kuroko and vein-type mineralization, but montmorillonite and mordenite alterations are not related to the mineralizations, and probably they formed at the post-mineralization stage.     

Geochemistry of rare earth elements in a marine influenced coal and its organic solvent extracts from the Antaibao mining district, Shanxi, China

Twenty-six samples including roof, bottom and coal plies of a marine influenced coal bed were collected from the Antaibao mining district, Shanxi, China. The rare earth elements (REEs) were determined in solids and organic solvent extracts. The distribution pattern showed three distinct patterns: shale-like, LREE-rich and HREE-rich. This is attributed to the variable microenvironment of peat-forming swamp, the degree of marine influences and different REE sources. REEs in the coal are mainly controlled by detrital minerals but also affected by seawater. The chondrite-normalized REE patterns of the organic solvent extracts are distinctly different from those of corresponding original coal samples, which show a negative Eu anomaly, a depletion of middle REEs and an enrichment of HREEs. The LREEs in coal extracts are likely adsorbed by hydrogen-containing functional groups, and HREEs are likely bonded to carbon atoms.     

煤及其燃烧产物飞灰和底灰中稀土元素地球化学特征及集散规律

采用ICP—MS法测试了褐煤、肥煤和无烟煤以及在不同燃烧条件下获取的飞灰、底灰等29个样品的稀土元素含量;分析了稀土元素地球化学特征。结果表明,不同煤种的稀土元素含量不同,相同煤种在不同燃烧条件下获取的飞灰、底灰中的稀土元素含量也不同;褐煤、肥煤、无烟煤及其燃煤产物飞灰、底灰的稀土元素分布模式呈左高右低的宽缓的“V”型曲线;Eu存在明显负异常。研究了燃煤过程中稀土元素的分布及集散规律,稀土元素在飞灰、底灰中的含量比原煤有明显提高,其增加幅度为几倍至20多倍不等,表明煤炭燃烧后稀土元素在飞灰、底灰中进一步聚集;飞灰和底灰中稀土元素含量、飞灰和底灰对煤的稀土元素含量比和富集因子以及飞灰对底灰的稀土元素含量比和富集因子等,不仅与原煤中稀土元素有直接关系,而且还受锅炉燃烧方式、燃烧温度(炉温)等人为因素的影响。     

相山铀矿田成矿流体特征:来自微量、稀土元素地球化学证据

相山铀矿田的成矿流体性质和来源存在争议,为进一步探讨相山铀矿田成矿流体的性质和来源,本文对相山铀矿田西部的居隆庵铀矿床和北部的沙洲铀矿床中的新鲜围岩、蚀变围岩及矿石的微量、稀土元素含量及其变化进行了研究。结果显示:在含较多热液成因萤石的居隆庵铀矿床中,从新鲜围岩到蚀变围岩到矿石,Zr、Hf含量先降低再升高;而在含少量热液萤石的沙洲铀矿床中,新鲜围岩、蚀变围岩和矿石的Zr、Hf含量基本一致。鉴于富F流体易汲取岩石中的Zr、Hf,因此,这两个矿床中不同类型样品Zr、Hf含量的不同变化趋势,可能与居隆庵铀矿床的成矿流体富F、而沙洲铀矿床的成矿流体相对贫F有关。这两个铀矿床中矿石的稀土配分曲线与其各自的新鲜及蚀变围岩的稀土配分曲线形态相似但又存在差异,说明每个矿床的新鲜围岩、蚀变围岩和矿石之间的稀土元素既具有继承性、又受到不同性质的流体的影响。居隆庵铀矿床中矿石显示Eu负异常,可能主要是继承了围岩的Eu负异常;沙洲铀矿床中矿石Eu显示弱负异常至弱正异常的特征,可能与围岩中斜长石因热液蚀变作用而释放出的Eu的进入流体有关。基于新鲜围岩、蚀变围岩及矿石的U和REE研究,推断居隆庵铀矿床成矿流体中U和REE均以F的络合物形式迁移;但沙洲铀矿床中铀矿石品位较低,可能是与流体中相对贫F有关。     

Pb and rare earth element diffusion in xenotime

Diffusion of Pb and the rare earth elements Sm, Dy and Yb have been characterized in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na₂CO₃–MoO₃ flux method. The sources of diffusant for the rare earth diffusion experiments were REE phosphate powders, with experiments run using sources containing a single REE. For Pb, the source consisted a mixture of YPO₄ and PbTiO₃. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from 30 min to several weeks, at temperatures from 1000 to 1500 °C. The REE and Pb distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS).The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101):

Diffusivities among the REE do not differ greatly in xenotime over the investigated temperature range, in contrast to findings for the REE in zircon [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.], where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they likely substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE^+ 3 → Y^+ 3 exchange, without charge compensation as needed for REE^+ 3 → Zr^+ 4 exchange in zircon. This latter factor may also contribute to the large activation energies for diffusion of the REE in zircon (i.e., 691–841 kJ mol^− 1, [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.]), in comparison with those for xenotime.For Pb, the following Arrhenius relation is obtained (also normal to (101)):

These measurements suggest that Pb diffusion in xenotime is quite slow, even slower than Pb diffusion in monazite and zircon, and considerably slower than diffusion of the REE in xenotime. Xenotime may therefore be even more retentive of Pb isotope signatures than either monazite or zircon in cases where Pb isotopes are altered solely by volume diffusion. However, because the activation energy for Pb diffusion in xenotime is lower than those for monazite and zircon, Pb diffusion may be somewhat faster at many temperatures of geologic interest in xenotime than in monazite or zircon.