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.     

长江与黄河沉积物REE地球化学及示踪作用

长江与黄河沉积物的稀土元素（ＲＥＥ）组成特征不同。长江沉积物ＲＥＥ含量较高,元素含量变化也大于黄河样品;球粒陨石标准化模式表明长江沉积物的（Ｌａ／Ｌｕ）Ｎ、（Ｌａ／Ｙｂ）Ｎ、（Ｇｄ／Ｙｂ）Ｎ的值也相应地比黄河沉积物中的高１０％左右,分布曲线均呈明显的石倾状,轻重稀土分馏明显,相对富集ＬＲＥＥ。且长江样品比黄河样品更富集ＬＲＥＥ,但Ｅｕ亏损不及黄河样品;两者的北美页岩标准化曲线均呈平坦稍右倾状,具有     

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.     

Sources of stream sediments in the granulite terrain of the Walawe Ganga Basin,Sri Lanka,indicated by rare earth element geochemistry

Thirty-eight samples of stream sediments draining high-grade metamorphic rocks in the Walawe Ganga (river) Basin, Sri Lanka, were analysed for their REE contents, together with samples of metamorphic suites from the source region. The metamorphic rocks are enriched in light REE (LREE) compared to heavy REE (HREE) and are characterised by high La/Lu ratios and negative Eu anomalies. The chondrite-normalised patterns for these granulite-grade rocks are similar to that of the average post-Archaean upper crust, but they are slightly enriched with La and Ce. The REE contents of the <63-μm fraction of the stream sediments are similar to the probable source rocks, but the other grain size fractions show more enriched patterns. The <63-μm stream sediments fraction contains lower total REE, more pronouncd negative Eu anomalies, higher Eu_N/Sm_N and lower La _N/Lu_N ratios relative to other fractions. The lower La _N/Lu_N ratio is related to the depletion of heavy minerals in the <63-μm fraction. The 63–125-μm and 125–177-μm grain size fractions of sediments are particularly enriched in LREE (average ΣLREE=2990 μg/g and 3410 μg/g, respectively). The total HREE contents are surprisingly uniform in all size fractions. However, the REE contents in the Walawe Ganga sediments are not comparable with those of the granulite-grade rocks from the source region of the sediments. The enrichment of REE is accounted for by the presence of REE containing accessory mineral phases such as zircon, monazite, apatite and garnet. These minerals are derived from an unknown source, presumably from scattered bodies of granitic pegmatites.     

REE Geochemical Characteristics of Apatite,Sphene and Zircon from Alkaline Rocks

The accessory minerals apatite and sphene are the main carriers of REE in alkaline rocks.Their chondrite-normalized REE patterns decline sharply to the right as those of the host rocks,In the patterns an obvious negative Eu anomaly and a positive Ce anomaly can be seen in apatite and sphene,respectively.Zircon from alkaline rocks is different in REE pattern,I,e,. a nearly symmetric“V“-shaped pattern with a maximum negative Eu anomaly.Compared with the equivalents from granites,apatite,sphene and zircon from alkaline rocks are all characterized by higher (La/Yb)N ratio and less Eu depletion,As to the relative contents of REE in minerals,apatite,sphene and zircon are enriched in LREE,MREE and HREE respectively,depending on their crystallochemical properties.     

Bacterial dissolution of fluorapatite as a possible source of elevated dissolved phosphate in the environment

In order to understand the contribution of geogenic phosphorus to lake eutrophication, we have investigated the rate and extent of fluorapatite dissolution in the presence of two common soil bacteria (Pantoea agglomerans and Bacillus megaterium) at T = 25 °C for 26 days. The release of calcium (Ca), phosphorus (P), and rare earth elements (REE) under biotic and abiotic conditions was compared to investigate the effect of microorganism on apatite dissolution. The release of Ca and P was enhanced under the influence of bacteria. Apatite dissolution rates obtained from solution Ca concentration in the biotic reactors increased above error compared with abiotic controls. Chemical analysis of biomass showed that bacteria scavenged Ca, P, and REE during their growth, which lowered their fluid concentrations, leading to apparent lower release rates. The temporal evolution of pH in the reactors reflected the balance of apatite weathering, solution reactions, bacterial metabolism, and potentially secondary precipitation, which was implied in the variety of REE patterns in the biotic and abiotic reactors. Light rare earth elements (LREE) were preferentially adsorbed to cell surfaces, whereas heavy rare earth elements (HREE) were retained in the fluid phase. Decoupling of LREE and HREE could possibly be due to preferential release of HREE from apatite or selective secondary precipitation of LREE enriched phosphates, especially in the presence of bacteria. When corrected for intracellular concentrations, both biotic reactors showed high P and REE release compared with the abiotic control. We speculate that lack of this correction explains the conflicting findings about the role of bacteria in mineral weathering rates. The observation that bacteria enhance the release rates of P and REE from apatite could account for some of the phosphorus burden and metal pollution in aquatic environments.     

Rare Earth Element Patterns in the Karst Terrains of Guizhou Province, China: Implication for Water/Particle Interaction

The authors determine the concentrations of dissolved (<0.22 μm) rare earth elements (REE) and suspended particulate matter (SPM) of typical karst rivers in Guizhou Province, China during the high-flow period. The concentrations of acid-soluble REE extracted from SPM using diluted hydrochloric acid are also obtained to investigate water/particle interaction in the river water. The dissolved REE contents in the river water are extremely low in the rivers of the study. The dissolved REE distribution patterns normalized by the Post Archean Australia Shale (PAAS) in the karst rivers are not flat, show slight enrichment of heavy REE to light REE, and also have significant negative Ce and Eu anomalies. The acid-soluble REE appears to have similar distribution patterns as characterized by MREE enrichment and slight LREE depletion, with unremarkable Ce and Eu anomalies. The PAAS-normalized REE distribution patterns of SPM are flat with negative Eu anomalies. The contents and distribution patterns of REE in the SPM are closely related to the lithological character of the source rocks. The SPM contains almost all the REE produced in the process of surficial weathering. This demonstrates that particle-hosted REE are the most important form of REE occurrence. REE fractionation, which takes place during weathering and transport, leads to an obvious HREE enrichment in the dissolved loads relative to the SPM. Y/Ho ratio can be used to shed light on REE behaviors during water/particle interaction.     

Scale and timing of Rare Earth Element redistribution in the Taconian foreland of New England

Clastic sedimentary rocks, deposited on eastern North America in response to the Taconian Orogeny, commonly have Sm/Nd isotope relationships indicating substantial isotope disturbance near or subsequent to the time of sedimentation that may be associated with severe depletion in light rare earth elements (LREE). Affected units [Normanskill Formation (Austin Glen and Pawlet Members), Frankfort Formation and Perry Mountain Formation] are widely separated both geographically (western New York to western Maine) and stratigraphically (Middle Ordovician to Silurian). A model is proposed for the most likely explanation of the observed REE and Sm/Nd isotope relationships involving a two‐stage process. In the first stage, REE are redistributed on a mineralogical scale (dissolution/precipitation on a sample scale) often with the involvement of REE‐enriched trace phases such as apatite and monazite. This stage typically takes place during diagenesis but may also take place later during metamorphism and/or recent weathering, and results in isotope re‐equilibration on a sample scale. The second stage occurs when one or more of these phases is redissolved and REE are transported on large advective scales. Where LREE‐enriched phases are involved, this gives rise to LREE depletion in whole rocks. The timing of this second stage cannot be constrained from Sm/Nd isotope data and may take place at any time subsequent to the isotope re‐equilibration. Such complex histories of REE redistribution may result in serious errors in estimating Nd model ages but not in estimating the Nd isotope composition at the age of sedimentation. Thus, Sm/Nd ratios even of unmetamorphosed sedimentary rocks have to be carefully evaluated before the calculation of depleted mantle model ages for the provenance.     

Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China: Their mobilization,redistribution, and fractionation

In this study, the mobilization, redistribution, and fractionation of trace and rare earth elements (REE) during chemical weathering in mid-ridge (A), near mountaintop (B), and valley (C) profiles (weak, weak to moderate, and moderate to intense chemical weathering stage, respectively), are characterized. Among the trace elements, U and V were depleted in the regolith in all three profiles, Sr, Nb, Ta, Zr, and Hf displayed slight gains or losses, and Th, Rb, Cs, and Sc remained immobile. Mn, Ba, Zn, Cu, and Cr were enriched at the regolith in profiles A and B, but depleted in profile C. Mn, Pb, and Co were also depleted in the saprock and fractured shale zones in profiles A and B and enriched in profile C. REEs were enriched in the regolith and depleted at the saprock zone in profiles A and B and depleted along profile C. Mobility of trace and REEs increased with increasing weathering intensity. Normalized REE patterns based on the parent shale revealed light REE (LREE) enrichment, middle REE (MREE), and heavy REE (HREE) depletion patterns. LREEs were less mobile compared with MREEs and HREEs, and this differentiation increased with increasing weathering degree. Positive Ce anomalies were higher in profile C than in profiles A and B. The Ce fractionated from other REE showed that Ce changed from trivalent to tetravalent (as CeO₂) under oxidizing conditions. Minimal REE fractionation was observed in the saprock zone in profiles A and B. In contrast, more intense weathering in profile C resulted in preferential retention of LREE (especially Ce), leading to considerable LREE/MREE and LREE/HREE fractionation. (La/Yb)_N and (La/Sm)_N ratios displayed maximum values in the saprock zone within low pH values. Findings demonstrate that acidic solutions can mobilize REEs and result in leaching of REEs out of the highly acidic portions of the saprock material and transport downward into fractured shale. The overall behavior of elements in the three profiles suggests that solution pH, as well as the presence of primary and secondary minerals, play important roles in the mobilization and redistribution of trace elements and REEs during black shale chemical weathering.     

Rare earth element transport and fractionation in small streams of a mixed basaltic–granitic catchment basin (Massif Central, France)

We present dissolved load (< 0.45 μm) rare earth element (REE) patterns of small streams from a catchment basin in the Massif Central in order to characterize the individual fractionation stages for the dissolved REE from the source to the catchment outlet. The upper part of the catchment is located on a basalt plateau, followed downstream by deep and narrow valleys with granitic and orthogneissic bedrock. Stream water has basalt-like REE patterns on the basaltic plateau close to the source, followed by a continuous depletion in light REE (La-Sm, LREE) downstream. Strontium and neodymium isotope ratios of stream water demonstrate that the dissolved REE are essentially of basaltic origin, even in the lower, granitic and gneissic part of the catchment. Mixing with gneiss or granite derived REE thus cannot explain the observed evolution of the REE patterns. There seems also to be no link with the calculated speciation of the dissolved REE. In contrast, a correlation between saturation indexes for hematite and La/Yb ratios suggests that REE fractionation is mainly controlled by precipitation of Fe-oxide particles that preferentially remove LREE from solution.     

The impact of water-rock interaction and vegetation on calcium isotope fractionation in soil- and stream waters of a small, forested catchment (the Strengbach case)

This study aims to constrain the factors controlling the calcium isotopic compositions in surface waters, especially the respective role of vegetation and water-rock interactions on Ca isotope fractionation in a continental forested ecosystem. The approach is to follow changes in space and time of the isotopic composition and concentration of Ca along its pathway through the hydro-geochemical reservoirs from atmospheric deposits to the outlet of the watershed via throughfalls, percolating soil solutions and springs. The study is focused on the Strengbach catchment, a small forested watershed located in the northeast of France in the Vosges mountains. The δ^44/40Ca values of springs, brooks and stream waters from the catchment are comparable to those of continental rivers and fluctuate between 0.17 and 0.87‰. Soil solutions, however, are significantly depleted in lighter isotopes (δ^44/40Ca: 1.00-1.47‰), whereas vegetation is strongly enriched (δ^44/40Ca: −0.48‰ to +0.19‰). These results highlight that vegetation is a major factor controlling the calcium isotopic composition of soil solutions, with depletion in “light” calcium in the soil solutions from deeper parts of the soil compartments due to preferential ⁴⁰Ca uptake by the plants rootsystem. However, mass balance calculations require the contribution of an additional Ca flux into the soil solutions most probably associated with water-rock interactions. The stream waters are marked by a seasonal variation of their δ^44/40Ca, with low δ^44/40Ca in winter and high δ^44/40Ca in spring, summer and autumn. For some springs, nourishing the streamlet, a decrease of the δ^44/40Ca value is observed when the discharge of the spring increases, with, in addition, a clear covariation between the δ^44/40Ca and corresponding H₄SiO₄ concentrations: high δ^44/40Ca values and low H₄SiO₄ concentrations at high discharge; low δ^44/40Ca values and high H₄SiO₄ concentrations at low discharge. These data imply that during dry periods and low water flow rate the source waters carry a Ca isotopic signature from alteration of soil minerals, whereas during wet periods and high flow rates admixture of significant quantities of ⁴⁰Ca depleted waters (vegetation induced signal) from uppermost soil horizons controls the isotopic composition of the source waters. This study clearly emphasizes the potential of Ca isotopes as tracers of biogeochemical processes at the water-rock-vegetation interface in a small forested catchment.     

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。     

Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A,northern equatorial Pacific

The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies.The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source.     

藏南沙拉岗锑矿稀土和微量元素地球化学示踪及成矿物质来源

藏南沙拉岗锑矿赋存于下白垩统甲不拉组碳质板岩、泥质粉砂岩、硅质岩及燕山期辉绿岩和喜山期辉长岩中,受近东西向层间破碎带和近南北向构造破碎带控制。围岩蚀变较弱,围绕矿体呈对称性的面状、带状分布。稀土和微量元素测试结果表明碳质板岩和硅质岩具有与上地壳和太古宙后页岩非常相似的稀土配分模式。喜山期辉长岩以轻稀土相对亏损、重稀土相对富集和Eu轻度亏损的平坦型稀土配分模式有别于以轻稀土轻度富集、Eu无异常的稀土配分模式为特征的藏南燕山期辉绿岩。锑矿石具有轻稀土强烈富集、分馏程度高、Eu中度亏损、Ce强烈亏损的配分模式,与洋中脊黑烟囱-白烟囱中热液流体和喷流沉积物的Eu强正异常、海水的Ce中等负异常和重稀土富集的稀土配分模式及沃西Sedex型W-Sb-Au矿的稀土配分模式明显不同,但与喜山期辉长岩的稀土配分模式具有明显的互补关系。此外,锑矿石以其强Nb负异常及Ce和Ba正异常的微量元素特征,展示出与喜山期辉长岩的弱Nb负异常和强Rb正异常及碳质板岩-硅质岩的Nb、Ba负异常和轻度Ce、Rb、Th正异常的异同点,矿石δ³⁴S除个别样品为10.3‰和-41.6‰外,均分布在-2.6‰~-4.1‰区间,反映成矿物质主要来源于岩浆的特点。前人测定的流体包裹体氢、氧同位素值分别为δD=-151‰~-166‰,δ¹⁸O=9.4‰~12.3‰,显示岩浆水和地下水的混合性质。因此沙拉岗锑矿是形成于中新世、与藏南拆离系有关的浅成低温热液型矿床,成矿物质主要来源于喜山期辉长岩岩浆,少量来源于围岩,成矿流体部分来源于岩浆期后热液,部分来源于地下水。     

Rare earth elements (REE) of dissolved and suspended loads in the Xijiang River, South China

The Xijiang River is the main channel of the Zhujiang (Pearl River), the second largest river in China in terms of water discharge, and flows through one of the largest carbonate provinces in the world. The rare earth element (REE) concentrations of the dissolved load and the suspended particulate matter (SPM) load were measured in the Xijiang River system during the high-flow season. The low dissolved REE concentration in the Xijiang River is attributed to the interaction of high pH and low DOC concentration. The PAAS-normalized REE patterns for the dissolved load show some common features: negative Ce anomaly, progressively heavy REE (HREE) enrichment relative to light REE (LREE). Similar to the world’s major rivers the absolute concentration of the dissolved REE in the Xijiang River are mainly pH controlled. The degree of REE partitioning between the dissolved load and SPM load is also strongly pH dependent. The negative Ce anomaly is progressively developed with increasing pH, being consistent with the oxidation of Ce (III) to Ce (IV) in the alkaline river waters, and the lack of Ce anomalies in several DOC-rich waters is presumably due to both Ce (III) and Ce (IV) being strongly bound by organic matter. The PAAS-normalized REE patterns for the dissolved load and the SPM load in rivers draining the carbonate rock area exhibit middle REE (MREE) enrichment and a distinct maximum at Eu, indicating the preferential dissolution of phosphatic minerals during weathering of host lithologies. Compared to the Xijiang River waters, the MREE enrichment with a maximum at Eu disappeared and light REE were more depleted in the South China Sea (SCS) waters, suggesting that the REE sourced from the Xijiang River must be further fractionated and modified on entering the SCS. The river fluxes of individual dissolved REE introduced by the Xijiang River into the SCS vary from 0.04 to 4.36 × 10⁴ mol a⁻¹.     

Rare earth elements in apatite and magnetite in Kiruna-type iron ores and some other iron ore types

An investigation of the content and distribution of REE in apatite and magnetite in the iron ores of Kiruna type and some other iron ores is presented. REE in apatite and magnetite in different ore types show characteristic patterns which are related to different modes of formation of the ores.The magnetite-apatite iron ores of the world can be divided into two types: (a) Kiruna iron ores proper which occur in volcanic rocks, and (b) iron ores connected with deuteric processes and/or related to intrusive rocks. Apatite of the Kiruna ores proper in Fennoscandia (e.g. Kiirunavaara, Malmberget and Grängesberg) shows a common pattern with 2000–7000 ppm REE, a weak to moderate LREE/HREE fractionation and negative Eu anomalies. In the Kiruna area, apatite of the main, P-poor ores and of the later, hydrothermal-exhalative P-rich ores, have the same REE distribution which indicates a common source. There is a similar REE distribution in magnetite-apatite trachytic-rhyodacitic host rock which confirms a close magmatic relationship. Apatite in phosphorites (such as the Paleoproterozoic Påläng deposit in northern Sweden) has a different composition (< 1000 ppm REE with Ce depletion) which excludes a sedimentary origin of the Kiruna apatite.Apatite in other volcanogenic magnetite-apatite ores outside Fennoscandia differ by a stronger LREE/HREE fractionation and by a medium to large Eu depletion, partly indicating a relationship to alkaline intrusions. The Avnik apatite, Turkey, shows a weak differentiation in combination with a pronounced negative Eu anomaly, indicating provenance from silicic magmatic sources.The REE pattern of apatite in the deuteric-hydrothermal apatite-bearing iron ores is in general similar to that of apatite in the Kiruna iron ores proper. The similarity indicates a common process of formation for both ore types.The apatite-iron ores of the Kiruna type proper were formed by a late-magmatic differentiation. The ores of the Kiruna area are, in similarity with some other magnetite-apatite ores, emplaced along regional fracture-fault lines and close to an older basement. In general the REE pattern of apatite in the different deposits shows an affinity to alkaline or sub-alkaline magmas, indicating a rifting environment. The alkaline, trachytic volcanics hosting the Kiruna ores in northern Sweden are clearly related to an extensional setting where rifting was important. A probable source for this large-scale ore-forming process was partial melting of deep-seated rocks. The ores evolved in an intracontinental setting with magma generation caused by underplating of older crust.The process giving rise to magnetite-apatite ores of the Kiruna type has occurred during the time span from Paleoproterozoic to Tertiary. The Proterozoic ores occur mainly in cratonized areas, whereas the younger ones occur in fold belts. The amount of ore formed in post-Proterozoic time is as large as that formed in Proterozoic time.     

冀北赤城退变榴辉岩的岩石地球化学及原岩恢复

冀北赤城退变榴辉岩主元素特征显示所有样品均属拉斑玄武岩系列,可分出三种不同的REE配分型式。在MORB标准化微量元素配分图中,LREE亏损型与REE平坦型样品的HFSE与MORB相似,LREE富集型样品则具有较高的Zr、Hf和Y值,Nb和Ta明显富集,显示出陆壳物质混染的特征。这些特征表明,冀北赤城退变榴辉岩的原岩可能为兼具洋中脊和岛孤地球化学属性的洋壳拉斑玄武岩类,在后期俯冲消减过程中,发生榴辉岩相高压变质作用,并混入了部分陆壳物质。     

碳酸盐(岩)的稀土元素特征及其古环境指示意义

稀土元素主要通过交代碳酸盐矿物的Ca^{2+0进入碳酸盐格架,所以沉积碳酸盐(岩}的稀土元素特征能够很好的指示沉积流体来源和古环境。常用的稀土元素指标包括稀土元素总量(ΣREE)、稀土元素配分型式、以及La、Ce、Eu、Gd和Y等元素的异常指数。碳酸盐(岩)的稀土元素含量可能受到硅酸盐矿物、Fe-Mn氧化物/氢氧化物和磷酸盐等非碳酸盐组分以及成岩蚀变作用的影响。因此,在分析过程中,我们只有排除这些影响因素,才能用碳酸盐(岩)的稀土元素指标来探讨流体来源和古环境。这要求我们采集新鲜剖面上的样品,并用适当浓度的弱酸进行分步溶样,提取适当的组分,避免样品中的非碳酸盐组分干扰原始沉积组分的稀土元素特征。不同的沉积水体和沉积相下形成的碳酸盐(岩)具有不同的稀土元素特征:从太古宙到全新世的海相碳酸盐(岩)记录了LREE亏损、La正异常和高Y/Ho值的稀土元素特征;海底孔隙水的稀土元素特征则受氧化-还原条件、离子络合形式、孔隙流体来源的制约;热液流体具有LREE富集、Eu正异常的稀土元素特征;河水和湖泊有相对平坦的稀土元素特征。因此,碳酸盐(岩)的稀土元素特征具有重要的古环境指示意义。     

Hydrogeochemistry in soils and sediments in the area of the Lagoa Campestre lake (Salitre,MG, Brazil): chemical balances of major and trace elements and dynamics of rare earth elements

Study of the sediments filling the Lagoa Campestre peaty lake (Minas Gerais, Brazil) showed a high rare earth elements (REE) content, especially in phosphatic bottom beds (authigenic phosphates), whose fluctuations could be related to variations in the erosion conditions and the nature of the plant cover. In order to understand better the mode of complexation and transport of trace elements in this environment, a geochemical survey was undertaken of the waters of the area, both in surface streams and at the water table.The concentration of the main cations decreases from the top of the slope down towards the lake. This is especially true during the rainy season and could be related to a more active leaching in this period. The chondrite-normalized REE pattern in the soil sequence is very similar to the pattern found for the local bedrock and is characterized by a depletion in heavy REE (HREE). For the groundwaters, the REE abundance normalized to average REE values of soils shows an enrichment in HREE as well as downslope, near the lake, and in the upper part of the sequence. At the outlet of the lake, the water of the stream has an alkaline pH and high values for numerous elements, contrasting with the low contents in the water table and in the lake. Thus it seems that the water of the outlet could be at least partly related to an apatite rich and carbonatitic formation, more abundant in this area. This is confirmed by positive Sm and Eu anomalies. Waters were also collected in 2 types of lysimeters. The cylindrical collectors gave higher REE contents than the plate collectors, a feature that might result from adsorption by the metabolic activity at the rhyzosphere.The geochemical data acquired in the groundwaters, in the lake and at the outlet of the Lagoa Campestre allow a better understanding of the dynamics of the basin. During the rainy season, leaching is active on the slopes; it enhances dissolution of residual minerals in the latosolic cover and induces mobilization of relatively high quantities of REE in the groundwaters. The stream at the outlet is probably mainly fed by deeper waters circulating through apatite rich rocks, except during the rainy season when the lake also partly contributes to its supply. This means that most of the material leached on the slopes of the basin accumulates in the central part of the depression.     

Dissolved rare earth elements in river waters draining karst terrains in Guizhou Province,China

Winter seasonal concentrations of dissolved rare earth elements (REE) of two major river systems (the Wujiang River system and the Yuanjiang River system) in karst-dominated regions in winter were measured by using a method involving solvent extraction and back-extraction and subsequent ICP-MS measurements. The dissolved REE concentrations in the rivers and their tributaries are lower than those in most of the large rivers in the world. High pH and high cation (i.e., Na⁺ + Ca²⁺) concentrations of the rivers are the most important factors controlling the concentrations of dissolved REE in the river water. The dissolved load (<0.22 μm) REE distribution patterns of high-pH river waters are very different from those of low-pH river waters. The shale (PAAS)-normalized REE patterns for the dissolved loads are characterized by light REE-enrichment and heavy REE-enrichment. Water in the upper reaches of the Wujiang River generally shows light REE-enriched patterns, while that in the middle and lower reaches generally shows heavy REE-enriched patterns. The Yuanjiang River is heavy REE enriched with respect to the light REE in the same samples. Water of the Wuyanghe River draining dolomite-dominated terrains has the highest heavy REE-enrichment. Most river water samples show the shale-normalized REE patterns with negative Ce and Eu anomalies, especially water from Wuyanghe River. Y/Ho ratios show that the water/particle interaction might have played an important role in fractionation between HREE and LREE.