The impact of vegetation on REE fractionation in stream waters of a small forested catchment (the Strengbach case)

Previous studies on waters of a streamlet in the Vosges Mountains (Eastern France) have shown that strontium and rare earth elements (REE) mainly originate from preferential dissolution of apatite during weathering. However, stream water REE patterns normalized to apatite are still depleted in the light REE (LREE, La-Sm) pointing to the presence of an additional LREE depleting process. Vegetation samples are strongly enriched in LREE compared to stream water and their Sr and Nd isotopic compositions are comparable with those of apatite and stream water. Thus, the preferential LREE uptake by vegetation might lead to an additional LREE depletion of surface runoff in the forested catchment. Mass balance calculations indicate, that the yearly LREE uptake by vegetation is comparable with the LREE export by the streamlet and, therefore, might be an important factor controlling LREE depletion in river water. This is underlined by the observation that rivers from arctic and boreal regions with sparse vegetation appear to be less depleted in LREE than rivers from tropical environments or boreal environments with a dense vegetation cover.     

The impact of vegetation on fractionation of rare earth elements (REE) during water–rock interaction

Previous studies on waters of a streamlet in the Vosges mountains (eastern France) have shown that Sr and rare earth elements (REE) principally originate from apatite dissolution during weathering. However, stream water REE patterns normalized to apatite are still depleted in light REE (LREE, La–Sm) pointing to the presence of an additional LREE depleting process. Speciation calculations indicate that complexation cannot explain this additional LREE depletion. In contrast, vegetation samples are strongly enriched in LREE compared to water and their Sr and Nd isotopic compositions are comparable with those of apatite and waters. Thus, the preferential LREE uptake by the plants at the root–water–soil (apatite) interface might lead to an additional LREE depletion of the waters in the forested catchment. Mass balance calculations indicate that the yearly LREE uptake by vegetation is comparable with the LREE export by the streamlet and, therefore, might be an important factor controlling the LREE depletion in river waters.     

The source of calcium in wet atmospheric deposits: Ca-Sr isotope evidence

Tracing the origin of calcium in wet atmospheric deposits is important for environmental studies since it is a dominant acid neutralising cation and an essential nutrient. Here we present the first calcium isotope ratio measurements for rain and snow. Samples from northeastern and southern locations (France, Switzerland, Luxembourg, California and Japan) suggest a carbonate origin. Only at a local scale in a forested watershed (Vosges mountains, France) the Ca isotopic compositions of rainwater indicate that the rainwater becomes admixed with throughfall solution, which is a mixing product of Ca from dissolved atmospheric dust particles and leave excretions. If this proves to be widely true, the contribution of Ca from the canopy could be very important for the neutralisation of acid rain and of the corresponding soil system in forested watersheds. In such cases Ca and Sr cycles are decoupled in the lower atmosphere. In contrast to Sr isotopes, Ca isotopes can be applied to tracing processes occurring in the biosphere.     

花岗岩的成岩时代、地球化学特征和成因青海祁漫塔格地区虎头崖矿床Ⅵ矿带

利用 LA ICP MS 锆石 U Pb 法,测得与成矿有关的青海祁漫塔格地区虎头崖矿床Ⅵ矿带花岗岩的成岩年龄为(233.6±1.8)Ma(MSWD=1.2,n=17)。地球化学特征显示：花岗岩属高钾钙碱性、弱过铝质花岗岩;样品的稀土元素组成以总体右倾,轻、重稀土分异明显和具明显的负铕异常为特征;微量元素具有富集 Rb、Th、U、La、Nd 等大离子亲石元素,亏损 Ba、Sr、Nb、P、Ti 等元素的特点。Sr Nd 同位素组成特征显示,花岗岩的源区可能是富集岩石圈地幔。初步研究认为,虎头崖矿床Ⅵ矿带花岗岩可能形成于中、晚三叠世碰撞后碰撞的构造背景下。     

Trace element and isotopic evidence for REE migration and fractionation in salts next to a basalt dyke

Neodymium and Sr isotopic compositions and the rare earth elements (REE) distribution patterns have been determined in salts adjacent to a basaltic dyke along 2 parallel horizontal profiles. The salts, originally consisting of carnallite (KMgCl₃ · 6H₂O), have been transformed during basalt intrusion mainly into halite (NaCl) and sylvite (KCl) by fluids saturated in NaCl. The Sr isotope data suggests that much more fluid penetrated the upper than the lower horizon. The Nd isotope data shows that in the upper horizon, where fluid flow was stronger, Nd is essentially derived from the basalt. In contrast, in the lower horizon a strong salt Nd component is present.The REE data document in both horizons is a strong depletion of Ce, Pr, Nd, Sm and Eu with increasing distance from the basalt. This depletion of the light rare earths (LREE) is stronger in the upper horizon where fluid flow was stronger. The authors suggest that this REE fractionation is more likely due to precipitation of LREE-enriched accessory minerals such as apatite, than to differential REE solubility caused by selective REE complexation. This finding is of interest for REE behaviour in brines in general, and for the behaviour of radioactive REE and actinides in a salt repository for high-level nuclear waste in particular.     

汉诺坝玄武岩中地幔岩捕掳体REE和Sr,Nd同位素地球化学

本文报道汉诺坝玄武岩中地幔岩捕掳体的ＲＥＥ丰度和Ｓｒ、Ｎｄ同位素组成。不同岩石类型的ＲＥＥ配分模式和同位素组成反映地幔部分熔融程度和交代作用过程。二辉橄榄岩亏损轻稀土，是原始地幔经不同程度部分熔融的残留体。方辉橄榄岩具Ｕ型ＲＥＥ配分模式，是强烈亏损的地幔岩被熔体非化学平衡交代的结果。二辉岩脉状体富轻、中稀土，它同与脉状体接触的二辉橄榄岩可达化学平衡或近于化学平衡，而二辉岩脉状体的形成与玄武岩岩浆无成因关系。据对二辉岩脉状体和不含脉状体橄榄岩的Ｓｍ－Ｎｄ同位素定年，这种脉状体形成于３００Ｍａ左右。     

An Ordovician intra-oceanic subduction system influenced by ridge subduction in the West Junggar,Northwest China

We report elemental and Nd–Sr isotopic data for three types of Ordovician volcanic and gabbroic rocks from the Sharburti Mountains in the West Junggar (Xinjiang), Northwest China. Gabbros and Type I lavas occur in the Early Ordovician Hongguleleng ophiolite whereas Type II and III lavas are parts of the Middle Ordovician Bulukeqi Group. Gabbros and Type I lavas are tholeiites with a depleted light rare earth element (LREE) and mid-oceanic ridge basalt (MORB)-like signature with a crystallization sequence of plagioclase–clinopyroxene, suggesting formation at a mid-oceanic ridge. Type II lavas are Nb-enriched basalts (NEBs, Nb = 14–15 ppm), which have E-MORB-like REE patterns and Nb/Yb and Th/Yb ratios. They come from mantle metasomatized by slab melts. Type III lavas are further divided into two sub-types: (1) Type IIIa is tholeiitic to calc-alkaline basalts and andesites, with REE patterns that are flat or slightly LREE enriched, and with a negative Nb anomaly and Th/Yb enrichment, indicating that they were generated above a subduction zone; (2) Type IIIb is calc-alkaline basalts and andesites, which are strongly enriched in LREE with a marked negative Nb anomaly and Th/Yb enrichment, suggesting generation in a normal island-arc setting. The initial ⁸⁷Sr/⁸⁶Sr ratios of Type III lavas range from 0.70443 to 0.70532 and ?Ndt ranges from +1.5 to +4.5, suggesting that these melts were derived from mantle wedge significantly modified by subducted material (enriched mantle I (EMI)) above a subduction zone. Contemporary tholeiitic to calc-alkaline basalt–andesite and NEB association suggest that the NEBs erupted during development of the tholeiitic to calc-alkaline arc. We propose a model of intra-oceanic subduction influenced by ridge subduction for the Ordovician tectono-magmatic evolution of the northern West Junggar.     

大兴安岭中南段中生代中基性火山岩岩石学地球化学研究

大兴安岭中南段中生代火山岩的成因和形成时的构造背景涉及南蒙古-兴蒙造山带的后期构造演化及区内众多的铜、银多金属矿床的形成,因而对其成因的研究具有重要意义。在野外工作基础上,对大兴安岭中南段中生代中基性火山岩进行了较为系统的岩石学和元素地球化学研究。结果表明,火山岩的岩石类型为玄武粗安岩、粗面安山岩、英安岩及粗面岩,属钙碱性岩石系列;玄武粗安岩、粗面安山岩、英安岩及粗面岩的常量元素以富集SiO2,Na2O,K2O和亏损Fe2O3,FeO,MgO,CaO等为特征,微量元素以富集亲石元素和亏损铁族元素及Nb,Ta为特征;火山岩的稀土元素分配模式为轻稀土富集型;(^87Sr／^86Sr)．为0．7045～0．7077,且主要集中在0．7045～0．7055的区间内,εNd(t)多数为正值。火山岩是地幔物质部分熔融的产物,形成于张性构造环境,它们是天山一兴安造山带后造山期软流圈或地幔柱上涌所引起的岩石圈伸展作用、内蒙古-吉黑印支造山带造山期后的伸展作用和蒙古-鄂霍茨克残余洋“剪刀式”闭合所形成的拉张作用等综合效应的响应事件。     

REE Mineralization of Weathered Crust and Clay Sediment on Granitic Rocks in the Sanyo Belt,SW Japan and the Southern Jiangxi Province,China

Rare earth element (REE) geochemistry and mineralogy have been studied in the weathered crusts derived from the Early Yanshanian (Jurassic) biotite granites of Dabu and Dingnan, as well as in the Indosinian (Permian) muscovite–biotite granite of Aigao in southern Jiangxi province, China, and the weathered crusts and clay sediments on biotite granites in the Sanyo belt, SW Japan, that is, Okayama, Tanakami, and Naegi areas. In all of the weathered crusts, biotite and plagioclase commonly tend to decrease toward the upper part of the profile, whereas kaolinite and residual quartz and K‐feldspar increase. The weathered crusts of the Dingnan granites and some Naegi granites, which are characterized by the enrichment in light REE (LREE) in C horizons, have higher total REE (ΣREE) content than the parent REE‐enriched granites. Weathering of LREE‐bearing apatite and fluorocarbonates in the Dingnan granites and allanite and apatite in some Naegi granites may account for the leaching of LREE at the B horizons. The leached LREE must result in subsequent enrichment of LREE in the C horizons. The enrichment is probably associated with mainly adsorption onto kaolinite and partly formation of possible secondary LREE‐bearing minerals. In Japan it was found that REE mineralization occurs not in the weathered granitic crusts but in reworked clay sediments, especially kaolinite‐rich layers, derived mainly from the weathering materials of REE‐enriched granitic rocks. The clay sediments are more enriched in LREE, which likely adsorbed onto kaolinite. Concentration of heavy REE within almost all the weathered crusts and clay sediments, however, may reflect mainly residual REE‐bearing minerals such as zircon, which originated in the parent granitic rocks. The findings of the present study support the three processes for fractionation of the REE during weathering: (i) selective leaching of rocks containing both stable and unstable REE‐bearing minerals; (ii) adsorption onto clay minerals; and (iii) presence of possible secondary LREE‐bearing minerals.     

白银厂矿田早中寒武世火山岩地球化学及成因分析

白银厂矿田早中寒武世火山岩主要为玄武岩－碱性玄武岩－安山岩－玄武安山岩－玄武粗安岩－英安流纹岩－流纹岩。其中基性和中基性岩类为碱性系列和亚碱性系列,碱性玄武岩主要为钾质玄武岩系列。酸性岩类为钙碱性系列。岩石全碱含量平均为５．７６％,Ｋ２Ｏ／,Ｋ２Ｏ／Ｎａ２〈１,Ｆｅ２Ｏ／ＦｅＯ平殚为０．７４;ＴｉＯ２绝大部分样品含量小于１％（在酸性火山岩中含量较低：０．２％～０．８３％,平均为０．５３％;基性和中     

青藏高原岩石圈演化的记录：藏北超钾质及钠质火山岩的岩石学与地球化学特征

藏北鱼鳞山超钾质火山岩为一中等规模的熔岩被, 可分为三期。前两期主要为霞石黝方白榴石响岩、霞石白榴斑岩等, 后期主要为方钠石霓石粗面岩、霓霞粗面岩等。时代为１８～３０ Ｍａ。本区超钾质岩浆 Ｓｉ Ｏ２ 强烈不饱和、强碱性、高度富集 Ｌ Ｒ Ｅ Ｅ及 Ｌ Ｉ Ｌ Ｅ、放射成因 Ｓｒ、 Ｐｂ 及非放射成因 Ｎｄ 同位素 （８６ Ｓｒ／８７ Ｓｒ＝ ０７０８７６６～０７０９１６２, ２０６ Ｐｂ／２０４ Ｐｂ＝ １８８８２８８８～ １９１０４７５１, ２０７ Ｐｂ／２０４ Ｐｂ＝ １５６４２０３７ ～ １５８２８４５８, ２０８ Ｐｂ／２０４ Ｐｂ＝ ３９１３８９２１ ～ ３９６８６８３５ 及１４３ Ｎｄ／１４４ Ｎｄ＝ ０５１２１１６ ～０５１２３４２）,其上述特征指示岩浆源区为受到地壳物质强烈交代的富集 Ｅ Ｍ Ｉ Ｉ型地幔。藏北拉嘎拉钠质碱性橄榄玄武岩为高原面上的剥蚀残丘, 时代为６０ Ｍａ。其岩石学、 Ｒ Ｅ Ｅ、微量元素及 Ｓｒ Ｎｄ Ｐｂ 同位素指示了岩浆源区为受到洋壳俯冲物质交代的轻度富集地幔。本研究结果指示, 羌塘高原南部富集地幔的形成可能是受到印度板块俯冲的影响。     

青海祁漫塔格地区虎头崖矿床Ⅵ矿带花岗岩的成岩时代、地球化学特征和成因

利用LA-ICP-MS锆石U-Pb法,测得与成矿有关的青海祁漫塔格地区虎头崖矿床Ⅵ矿带花岗岩的成岩年龄为(233.6±1.8) Ma(MSWD=1.2,n=17)。地球化学特征显示:花岗岩属高钾钙碱性、弱过铝质花岗岩;样品的稀土元素组成以总体右倾,轻、重稀土分异明显和具明显的负铕异常为特征;微量元素具有富集Rb、Th、U、La、Nd等大离子亲石元素,亏损Ba、Sr、Nb、P、Ti等元素的特点。Sr-Nd同位素组成特征显示,花岗岩的源区可能是富集岩石圈地幔。初步研究认为,虎头崖矿床Ⅵ矿带花岗岩可能形成于中、晚三叠世碰撞后碰撞的构造背景下。     

粤西阳春中生代钾玄质侵入岩及其构造意义：

粤西阳春地区马山二长闪长岩强烈富集K、Sr和LREE，(87Sr／86Sr)；≈0.7046，εNd(t)≈+1；岗尾-轮水岩体较富集K、Rb、Th和LREE，(87Sr／86Sr)：≈0.7063，εNd(t)≈-2；石岩体较富集Sr，K、Rb、Th和LREE相对较低，(87Sr／86Sr);=0.7084～0.7089，εNd(t)≈-6。马山岩体来源于大离子亲石元素(ULE)和LREE富集的交代地幔；岗尾-轮水岩体来自于放射成因Sr、Nd同位素组成略高或交代时间略早的富集交代地幔，并且经历了明显的结晶分异作用；石岩体则很可能是前存下地壳底垫基性岩重熔形成的。从早侏罗世到早白垩世，南岭西部的岩浆成分和源区的规律性变化反映了区域软流圈地幔上涌和岩石圈伸展-拉张-减薄的演化过程。     

Redistribution and fractionation of rare-earth and other elements in a weathering profile

A weathering profile on a uniform Lower Cretaceous volcanogenic sandstone from southern Victoria, Australia is enriched in rare-earth elements (REE), Y and other elements including Ba, Sr and Rb. Enrichments of REE of up to 7 times parent-rock values are associated with Fe-leached members of alteration couplets with little or no enrichment in adjacent Fe-rich members. These alteration couplets are similar in appearance to Liesegang banding. The REE have been fractionated during accumulation, leading to relative enrichment of the light rare earths (LREE).

The formation of an alteration couplet from fresh rock at the weathering front involves redistribution of only Fe (and P) and does not involve redistribution of REE, Y. Ba, Sr and Rb. Breakdown of original minerals in the present soil and degradation of vermiculite in the upper part of the weathering profile releases RE and related elements into solution. This solution moves down and along the profile until it comes into contact with neutral to alkaline conditions at the narrow weathering front. Here REE particularly are absorbed and apparently fixed in vermiculite forming at the expense of biotite and chlorite. (La + Ce + Nd + Y) up to 10.1 wt.% is recorded in degraded biotite grains with similar but lower contents in the degraded diagenetic chlorite cement.

Such accumulation and fractionation have important implications for REE studies involving sedimentary rocks or for that matter outcrop samples of any rock type.     

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.     

念青唐古拉中基性侵入岩年代学、地球化学及岩石成因

念青唐古拉早始新世中基性侵入岩由角闪辉长岩及二长闪长岩组成,其中角闪辉长岩锆石LA-MC-ICPMS U-Pb年龄为(49.92±0.24)Ma。中基性侵入岩属于高钾钙碱系列至钾玄岩系列;稀土总量较高且轻稀土富集;富集大离子亲石元素(Rb,Th,K),亏损高场强元素(Nb,Ta,Ti),具有弧岩浆岩的微量元素特征。中基性侵入岩具有较高的初始锶((87Sr/86Sr)i为0.708 77～0.713 71)、低的εNd值(-6.9～-6.1)、古老的亏损地幔模式年龄(TDM为1 329～1 995Ma),以及εNd、Nb/La与MgO无明显相关性,表明其源区为受古老地壳交代的富集地幔。稀土元素模拟表明中基性侵入岩的成岩过程受地幔中轻程度部分熔融作用所控制。动力学背景分析表明其与新特提斯洋板片的断离及软流圈物质的上涌密切相关。     

Rare-Earth Elements in the Atmospheric Precipitation of the City of Blagoveshchensk

The mineral composition, distribution and fractionation of rare-earth elements in dissolved and suspended forms (solid residue) of atmospheric precipitation were studied by analyzing the snow sampled over urbanized territory by the example of the city of Blagoveschensk. Electron-microscopic studies revealed the own minerals of rare-earth elements in dust aerosols. It is shown that the main sources of the atmospheric pollution by rare-earth elements were emissions of TPP (heat and power plants) and boiler houses. Contrasting geochemical anomalies of rare-earth elements were found in the snow cover of the city. The REE concentrations in the solid phase of snow are few orders of magnitude higher than those of the liquid phase. The snow solid phase provides insight into the REE behavior, because it directly reflects the impact of different anthropogenic sources. The characteristic feature of the REE distribution in the solid residue of snow is their LREE enrichment relative to MREE and HREE. The average HREE content is 10% of total REE. In the snow water–solid phase system, most samples show weak fractionation between LREE and HREE owing to the low total mineralization of the snow liquid phase and the small content of organic matter.     

江苏省海州式磷矿岩石地球化学特征及成矿背景

本文对苏北地区锦屏组磷矿石及地层样品进行了岩相学及地球化学分析,研究了磷矿初始沉积环境和源区特征。磷矿类微量元素富集Ba、Pb、U、Sr,贫Th、Ta、Nb、Ti;REE配分曲线为LREE富集型,Ce负异常,表明成矿环境为陆缘海,且成矿过程受深海热水沉积和生物作用影响。Sr、Nd同位素初始值判断磷灰岩物质来源为年轻的地壳物质。绿片岩类微量元素富集Rb、Th、K,贫Th、U、Ta、Nb、Sr、Ti;REE配分曲线为LREE富集型,判断其原岩为陆源碎屑岩。（混合）片麻岩类微量元素富集Pb、Th、K,亏损Ba、Ta、Nb、Sr、Ti;REE配分曲线为LREE富集型,具地幔源区特征。     

四川木洛稀土矿床碳酸岩地球化学

木洛稀土矿床成因上与碳酸岩-碱性杂岩密切相关。碳酸岩主要由方解石组成,CaO/（CaO＋MgO＋FeO＋Fe2O3＋MnO）比值在95.7%～99.6%,为方解石碳酸岩。碳酸岩相对富集大离子亲石元素Ba、Sr、LREE,亏损高场强元素Nb、Ta、Ti、Zr、P,高Zr/Hf和La/Nb值,低Sm/Nd和Rb/Sr值,暗示岩石来自富集地幔EMI。地质、地球化学研究表明,木洛碳酸岩是在峨眉山地幔柱地幔遗存物经喜马拉雅造山运动再次活化的产物,但碳酸岩熔浆在上侵过程中受到地壳物质混染。碳酸岩-碱性岩熔浆带来大量稀土元素,并在喜马拉雅造山期造山运动派生的局部引张部位成矿。     

Geochemical Records of Mantle Processes in Mantle Xenoliths from Three Cenozoic Basaltic Volcanoes in Eastern China

Rare earth element (REE) contents, and Sr and Nd isotopic compositions were measured for three suites of mantle xenoliths from the Kuandian, Hannuoba and Huinan volcanoes in the north of the Sino-Korean Platform. From the correlations of Yb contents with Al/Si and Ca/Si ratios, the peridotites are considered to be the residues of partial melting of the primitive mantle. The chondrite-normalized REE compositions are diverse, varying from strongly LREE-depleted to LREE-enriched, with various types of REE patterns. Metasomatic alteration by small-volume silicate melts, of mantle peridotites previously variably depleted due to fractional melting in the spinel peridotite field, can account for the diversity of REE patterns. The Sr/ Ba versus La/Ba correlation indicates that the metasomatic agent was enriched in Ba over Sr and La, suggestive of its volatile-rich signature and an origin by fluid-triggered melting in an ancient subduction zone. The Sr and Nd isotopic compositions of these xenoliths, even from