Lithium distribution and isotopic fractionation during chemical weathering and soil formation in a loess profile

Lithium (Li) is a fluid-mobile element and δ⁷Li in secondary deposits represents an excellent proxy for silicate weathering and authigenic mineral formation. The soil samples from 1205 to 1295 cm in the Weinan profile, one of the best developed loess-paleosol sequences covering the last glacial–interglacial climatic cycle, were collected and chemically separated into detritus and carbonate fractions for subsequent analyses of Li, δ⁷Li, major and trace elements. Other desert specimens (i.e., Qaidam Desert, Tengger Desert, Badain Juran Desert and Taklimakan Desert) near the Chinese Loess Plateau (CLP) and various standard clays were analyzed for assisting provenance determination. The Li and δ⁷Li distributions in the detritus are rather homogeneous, 1.4–2.0 μg/g and +2.5‰ to +4.7‰, respectively, compared with the carbonate fraction. The detrital δ⁷Li varies systematically with magnetic susceptibility and grain size changes, reflecting significant Li isotopic variation associated with sources and mineralogy of detrital material. On the other hand, Li and δ⁷Li in carbonates show large changes, 781–963 ng/g and −4.1‰ to +10.2‰, respectively. These carbonate δ⁷Li correlated well with the estimated index of chemical weathering, as a result of Li mobilization and soil formation during chemical weathering.     

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.     

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.     

华北平原高氟地下水中稀土元素分布和分异特征

高氟地下水是世界各国研究者广泛关注的重大环境问题。尽管对高氟地下水的化学特征、形成机理和扩散机制等已有不少研究,但其稀土元素(REE)的含量和分异特征以及这些特征能否反映高氟地下水的形成和分布尚不清楚,这在一定程度上限制了REE在高氟地下水中的运用。本研究以地下水氟离子异常严重地区——华北平原为研究区,沿地下水流向采集浅层和深层地下水样,研究分析了水中氟离子和REE的地球化学特征。浓度分析结果表明地下水氟离子浓度介于0.28 mg/L和9.33 mg/L之间,其中55%超出我国饮用水标准规定值1.0 mg/L;PHREEQC计算结果反映地下水中氟以NaF、CaF⁺、MgF⁺和自由态F^-形式存在,其中自由态F^-含量占主导(85.42%99.39%);高氟地下水主要分布于中部冲积湖积平原以及东部冲积海积平原,60%高氟地下水样分布在180 m深度以下;水化学图件分析结果指示浅层高氟地下水的形成主要受蒸发浓缩作用的控制,而深层高氟地下水是水岩相互作用下的矿物溶解和离子竞争吸附共同作用的结果。研究区地下水REE含量处于pmol/L至nmol/L级别,PHREEQC模拟计算结果表明REE主要以碳酸络合物( {\mathrm{REECO}}_3^{+}和$REE(CO_{3})_{2}^{-})$的形式存在,与氟离子络合的稀土元素(REEF²⁺和 {\mathrm{REEF}}_2^{+})占01.18%;上陆壳(UCC)标准化结果显示,所有地下水均呈重REE(HREE)和中REE(MREE)相对于轻REE(LREE)富集的模式,且具有显著Ce负异常(0.11* = Ce_UCC/(La_UCC×Pr_UCC)^0.5<2.29)特性;地下水富HREE主要归因于HREE比LREE优先与碳酸根络合,并且形成更加稳定的碳酸络合物。沿地下水流向,深层地下水中总REE含量与地下水中氟浓度均呈现不断上升的变化趋势,同时高氟地下水比低氟地下水更易富集重稀土元素,说明稀土元素对深层含水层富氟行为具有一定的指示作用。     

Pyritization of fossil mollusk shells and some problems of supergene sulfide formation

The study of specific features of the pyritization of mollusk fossil shells has provided new evidence of the relationship between the generation of hydrosulfides during the bacterial reduction of sulfates and the composition of organic matter (OM) exploited by bacteria in processes of metabolism. The OM is represented by conchiolin of the ammonite shell frustule. Interaction between the bacterial H₂S and Fe²⁺ fosters the pseudomorphous replacement of conchiolin by the colloidal iron monosulfide that is subsequently transformed into pyrite. Hydrogen sulfide and/or monosulfide migrate into diagenetic cracks and cavities formed in the clayey—carbonate matrix that fills up the interior cavity of a shell. We believe that the data reported in this communication should be taken into consideration in the study of formation constraints of vein and disseminated sulfide mineralization in sedimentary rocks during the early diagenesis and related problems of ore formation.     

黔东南煌斑岩类风化壳中稀土元素富集特征及找矿意义

以往研究认为煌斑岩类及其风化壳因规模小且稀土元素难以高度富集,不易形成稀土元素矿床。然而,本文通过对黔东南麻江隆昌、龙山、大塘、石板寨及和尚坟地区20件风化煌斑岩类中稀土元素进行测试分析发现,风化煌斑岩类中稀土元素含量普遍偏高,ΣREE+Y介于558. 78×10-6~2409.94×10-6(平均1461.21×10-6),其中LREE平均1346.44×10-6,HREE平均53.52×10-6,稀土元素具有高度富集甚至成矿的潜力。其中石板寨、和尚坟煌斑岩风化程度较强,稀土元素富集程度较高,隆昌、龙山等地煌斑岩风化程度相对较弱,稀土元素富集程度相对较低。煌斑岩类风化壳中高度富集轻稀土元素,且以La、Ce、Nd、Pr相对富集为特征。电子探针分析表明,风化煌斑岩类中稀土元素多以稀土独立矿物形式存在,其中以独居石为主。     

深海稀土分布规律与成矿作用

深海稀土是近年发现的一种富集中-重稀土的新型海洋矿产资源,其资源量远超陆地稀土储量,具有重要的潜在应用价值。中国是继日本之后在国际上第二个开展深海稀土调查研究的国家,2011年以来,先后在中印度洋海盆、东南太平洋和西太平洋深海盆地发现了大面积富稀土沉积区,在全球大洋中初步划分出4个深海稀土成矿带：西太平洋深海稀土成矿带、中—东太平洋深海稀土成矿带、东南太平洋深海稀土成矿带和中印度洋海盆-沃顿海盆深海稀土成矿带。深海富稀土沉积主要发育在深海盆地的沸石粘土和远洋粘土中,属于自生成因;部分发育在洋中脊附近的盆地中,受到热液作用的影响。研究发现,深海粘土中稀土元素主要赋存于生物磷灰石中,海水是稀土元素的主要来源;在早期成岩阶段,稀土元素在深海沉积物中发生转移和重新分配,并最终富集于生物磷灰石中;大水深（CCD面之下）、低沉积速率和强底流活动是深海稀土大规模成矿的主要控制因素。今后需要继续加大深海稀土基础调查,加强深海稀土调查探测技术研发,并开展海陆稀土成矿作用对比研究,揭示深海稀土成矿机制和规律。     

Geochemistry of red residua underlying dolomites in karst terrains of Yunnan-Guizhou Plateau: II. The mobility of rare earth elements during weathering

The aim of this study is to characterize the evolution of the rare earth elements (REE) in the Pingba red residua on karst terrain of Yunnan-Guizhou Plateau. The in-situ weathering and the two-stage development of the profile had been inferred from REE criterions. The REE were significantly fractionated, and Ce was less mobilized and separated from the other REEs at the highly enriched top of the profile. This is consistent with the increase of oxidation degree in the regolith. And it is also suggested that the wet/dry climate change during chemical weathering caused Ce alternative change between enrichment and invariance in the upper regolith. Chondrite-normalized REE distribution patterns for samples from dolomites and the lower regolith are characteristic of MREE enrichment and remarkable negative Ce-anomalies patterns (similar to the convex-up REE patterns). The following processes are interpreted for the patterns in this study: (1) the accumulation of MRRE-rich minerals in dolomite dissolution, (2) water–rock interaction in the weathering front, and (3) more leaching MREE from the upper part of the profile. The latter two explanations are considered as the dominant process for the formation of the REE patterns. Samples from the soil horizon exhibit typical REE distribution patterns of the upper crust, i.e., La_N/Yb_N=10 and Eu/Eu*=0.65. All data indicate that the leaching process is very important for pedogenesis in this region. The experiments demonstrating that abnormal enrichment of REE at the upper regolith–bedrock interface is caused by a combination of volume change, accumulation of REE-bearing minerals, leaching of REE from the upper regolith, and water–rock interaction during rock–soil alteration processes. Our results support the conclusion that the weathering profile represents a large, continental elemental storage reservoir, whereas REE enrichment occurs under favorable conditions in terms of stable tectonics, low erosion and rapid weathering over sufficiently long time.     

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.     

长江三峡地区成冰纪-埃迪卡拉纪转换时期微量元素和稀土元素地球化学特征

通过微量元素和稀土元素地球化学分析,对长江三峡地区陡山沱组层型剖面--田家园子剖面成冰系南沱组顶部和埃迪卡拉系陡山沱组下部102个岩石样品进行了地球化学研究。重点分析了氧化还原敏感元素(Zn,Co,U,Mo,Ni,V)的富集特征,并探讨其可能成因机制以及三峡地区成冰纪-埃迪卡拉纪转换时期的水体特征。结果表明:在南沱组顶部仅Zn和Co富集;在盖帽白云岩下部,氧化还原敏感元素均富集,而在盖帽白云岩上部,除Zn和V外,其他氧化还原敏感元素均亏损;在陡山沱组Ⅱ段下部,氧化还原敏感元素由最初的亏损,逐渐变为较稳定的富集。在陡山沱组下部,出现2次明显的富集峰值,分别出现在剖面的0.4m处(盖帽白云岩中间)和6.5m处(陡山沱组Ⅱ段下部)。整个剖面大部分样品具有Eu的轻微正异常(Eu/Eu^*＜1.6), 而在剖面0.4m和6.5m处,Eu具有明显的正异常,结合稀土配分类型、Y/Ho值、La异常、Ce异常等指标,推测这2次异常均可能受到深海热液流的影响,而缺氧海水的上涌造成水体缺氧,导致这些元素出现富集峰值。U/Th、V/(V+Ni)以及稀土元素指标综合指示,三峡地区南沱组顶部冰碛岩应为氧化环境下的沉积物;随着冰川消融,冰融淡水注入古海洋,陡山沱组盖帽碳酸盐的沉积受冰融淡水的影响,深部缺氧海水的上涌使沉积水体经历氧化-缺氧-氧化的转变,海水的分层性较强;而陡山沱组Ⅱ段下部沉积环境以分层性较弱的弱氧化环境为主。     

The behaviour of the rare earth elements during mixing of river and sea waters

Rare earth element concentrations have been measured in organic-rich Luce river water and coastal sea water. Concentrations (e.g. ～350?1850 pmol/kg Nd in the Water of Luce and ～45?350 pmol/ kg Nd in Luce Bay) are related to the presence of particles, with 30–60% of the REE associated with >0.4?0.7 μm particles, and to riverine Fe concentrations. REE fractionation occurs in the river water the submicrometre river water is heavy REE enriched whereas the coarser fraction has a more shale-like REE pattern.Laboratory experiments show that the REE in organic-rich river waters are chiefly associated with Feorganic matter colloids which flocculate during estuarine mixing. Preferential removal of heavy REE (～95%) relative to light REE (～60%) occurs, but no Ce anomaly is developed. In contrast, no REE removal occurs during estuarine mixing with organic-poor river water.     

State of rare earth elements in the rare earth deposits of Northwest Guizhou,China

We studied the states of rare earth elements in ore of the Xianglushan rare earth deposit. Rare earth ore samples were tested and examined by scanning electron microscope, electron probe, and chemical leaching. No independent rare earth minerals were detected by scanning electron microscope. Elements detected by the electronic probe for the in situ micro-zone of the sample included: O, Al, Si, Ca, Mg, Fe, Ti, K, Na, S, Cl, C, Cu, Cr, V, and Pt. Rare earth elements were not detected by electron probe. (NH4)₂SO₄, (NH₄)Cl, NaCl, and H₂SO₄ were used as reagents in chemical leaching experiments that easily leached out rare earth elements under the action of 10% reagent, indicating that the rare earth elements in ore are mainly in the ionic state rather than present as rare earth minerals.     

The behavior of actinides,phosphorus, and rare earth elements during chondrite metamorphism

New data on the U, Pu, and P distributions in less metamorphosed H-chondrites (type 3–5), coupled with literature results, permit a provisional picture to be assembled of the chemistry of these elements and for the rare earth elements in ordinary chondrites and the changes brought about by chondritic metamorphism. Preferential associations of phosphates with metals and/or sulndes in all chondrites strongly indicate an “initially” siderophile or conceivably chalcophile character for P in ordinary chondrite precursor materials with phosphate subsequently formed by oxidation. This oxidation occurred prior to or during chondritic metal-silicate fractionation. Uranium is initially concentrated in chondrule glass at ~ 100 ppb levels with phosphates (primarily merrillite) in H-3 chondrites being essentially U-free (<20 ppb). As chondrule glass devitrified during metamorphism, U migrated into phosphates reaching ~ 50 ppb in Nadiabondi (H-5) merrillite and 200–300 ppb in merrillite from equilibrated chondrites but “froze out” before total concentration in phosphates occurred. Relative ²⁴⁴Pu fission track densities in the outer 5 μm of olivine and pyroxene grains in contact with merrillite and with chondrule mesostasis in Bremervörde (H-3) give Pu(mesostasis)/Pu(merrillite) <0.01, implying total concentration of Pu in phosphates. Similarly, no detectable Pu (<0.1 ppb) was found in chondrule mesostasis in Tieschitz and Sharps; whereas, direct measurements of tracks in phosphates in H-3 chondrites are consistent with high (?10 ppb) Pu concentrations. Thus, a strong Pu-P correlation is indicated for ordinary chondrites. There is variable Pu/U fractionation in all chondritic phosphates reaching an extreme degree in the unequilibrated chondrites; therefore, the Pu/U ratio in phosphates appears relatively useless for relative meteorite chronology. Literature data indicate that the REE are located in chondrules in unequilibrated chondrites, most likely in glass; thus there may also be strong Pu/Nd fractionation within these meteorites. Like U, the REE migrate into phosphates during metamorphism but, unlike U, appear to be quantitatively concentrated in phosphates in equilibrated chondrites. Thus relative ages, based on Pu/Nd, may be possible for equilibrated chondrites, but the same chronological conclusions are probably obtainable from Pu concentrations in phosphates, i.e., on the Pu/P ratio. However, Pu/P chronology is possible only for ordinary chondrites; so there appears to be no universal reference element to cancel the effects of Pu chemical fractionation in all meteorites. Available data are consistent with — but certainly do not prove-that variations in Pu/P represent age differences, but if these age differences do not exist, then it is conceivable that the solar system ${}^{244}\text{Pu}{}^{238}\text{U}$ ratio, important for cosmochronology, is still lower than the presently accepted value of 0.007.     

Extensive degradation and fractionation of organic matter during subsurface weathering

Organic carbon, sulphur, ¹³C_org, iron, manganese and calcium have been measured across a subsurface-weathering front in Pliocene sediments in southern Sicily. The results show an almost quantitative removal of C_org and sulphur and an increase in iron and manganese oxides over the weathering front, accompanied with a significant shift of the ¹³C_org to lower values. These data are among the first to support the rapid, extensive weathering of sedimentary organic matter and sulphur, a basic assumption made in global biogeochemical models on a Phanerozoic timescale.     

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.     

Boron metasomatism and behaviour of rare earth elements during formation of tourmaline rocks in the eastern Arunta Inlier,central Australia

Tourmaline rocks of previously unclear genesis and spatially associated with W- (Cu)-bearing calc-silicate rocks occur in Palaeoproterozoic supracrustal and felsic intrusive rocks in the Bonya Hills in the eastern Arunta Inlier, central Australia. Tourmalinisation of metapelitic host rocks postdates the peak of regional low-pressure metamorphism (M₁/D₁, ~500 °C, ~0.2 GPa), and occurred synkinematically between the two main deformation events D₁ and D₂, coeval with emplacement of Late Strangways (~1.73 Ga) tourmaline-bearing leucogranites and pegmatites. Tourmaline is classified as schorl to dravite in tourmaline–quartz rocks and surrounding tourmaline-rich alteration zones, and as Fe-rich schorl to foitite in the leucogranites. Boron metasomatism resulted in systematic depletion of K, Li, Rb, Cs, Mn and enrichment of B, and in some samples of Na and Ca, in the tourmaline rocks compared to unaltered metasedimentary host rocks. Whole-rock REE concentrations and patterns of unaltered schist, tourmalinised schist and tourmaline–quartz veins—the latter were the zones of influx of the boron-rich hydrothermal fluid—are comparable to those of post-Archaean shales. Thus, the whole-rock REE patterns of these rocks are mostly controlled by the metapelitic precursor. In contrast, REE concentrations of leucogranitic rocks are low (10 times chondritic), and their flat REE patterns with pronounced negative Eu anomalies are typical for fractionated granitic melts coexisting with a fluid phase. REE patterns for tourmalines separated from metapelite-hosted tourmaline–quartz veins and tourmaline-bearing granites are very different from one another but each tourmaline pattern mirrors the REE distribution of its immediate host rock. Tourmalines occurring in tourmaline–quartz veins within tourmalinised metasediments have LREE-enriched (La_N/Yb_N=6.3–55), shale-like patterns with higher REE (54–108 ppm). In contrast, those formed in evolved leucogranites exhibit flat REE patterns (La_N/Yb_N=1.0–5.6) with pronounced negative Eu anomalies and are lower in REE (5.6–30 ppm). We therefore conclude that REE concentrations and patterns of tourmaline from the different tourmaline rocks studied are controlled by the host rock and not by the hydrothermal fluid causing boron metasomatism. From the similarity of the REE pattern of separated tourmaline with the host rock, we further conclude that incorporation of REEs in tourmaline is not intrinsically controlled (i.e. by crystal chemical factors). Tourmaline does not preferentially fractionate specific REEs or groups of REEs during crystallisation from evolved boron- and fluid-rich granitic melts or during alteration of clastic metasediments by boron-rich magmatic-hydrothermal fluids.Editorial responsibility: J. Hoefs     

Geochemistry of rare earth elements in oceanic phillipsites

The behavior of rare earth elements (REE) was examined in oceanic phillipsites collected from four horizons of eupelagic clay in the Southern Basin of the Pacific. The REE concentrations were determined in the >50-μm-fraction phillipsite samples by the ICP-MS method. The composition of separate phillipsite accretions was studied using the electron microprobe and secondary ion mass-spectrometry. Rare earth elements in phillipsite-only samples are related to the admixture of ferrocalcium hydroxophosphates. The analysis of separate phillipsite accretions reveals low (<0.1–18.1 ppm) REE (III) concentrations. The Ce concentration varies between 2.7 and 140 ppm. The correlation analysis shows that REE (III) are present as an admixture of iron oxyhydroxides in separate phillipsite accretions. Based on the REE (III) concentration in iron oxyhydroxides, we can identify two generations of phillipsite accretions. Massive rounded accretions (phillipsite I) are depleted in REE, while pseudorhombic (phillipsite II) accretions are enriched in REE and marked by a positive Ce anomaly. Oceanic phillipsites do not accumulate REE or inherit the REE signature of the volcaniclastic material and oceanic deep water. Hence, the REE distribution in phillipsites does not depend on the sedimentation rate and host sediment composition.     

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ⁵⁶Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ⁵⁶Fe. For all soils the lightest isotopic composition was observed in a 1 M NH₂OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.     

Distribution and fractionation of rare earth elements and Yttrium in suspended and bottom sediments of the Kali estuary,western India

Concentrations of rare earth elements (REE) and yttrium (Y), and major metals (Al, Fe and Mn) were measured in suspended particulate matter (SPM) and bottom sediments of the Kali estuary, western India, for their distribution and fractionation. The contents of SPM and metals in it were more uniform along the longitudinal transect during the monsoon. During the post- and pre-monsoons, low SPM in the upper/middle estuary coincided with high Fe and Mn and total REE (∑REE). But in the lower estuary SPM and its ∑REE content increased seaward, while Fe and Mn decreased. The Y/Ho ratios decreased seaward during the monsoon but increased during the post-monsoon. Sm/Nd ratios were more uniform along the transect during monsoon but decreased marginally seaward in other seasons. The Post-Archean Average Australian Shale (PAAS)-normalized REE patterns exhibited middle REE and heavy REE enrichment with positive Ce (\({\text{Ce}}/{\text{Ce}}^{*}\)), Eu (\({\text{Eu}}/{\text{Eu}}^{*}\)) and Y anomalies. The \({\text{Ce}}/{\text{Ce}}^{*}\) increased but \({\text{Eu}}/{\text{Eu}}^{*}\) decreased marginally seaward. The fine-grained sediments showed higher ∑REE and lower Y/Ho ratios than in coarse-grained sediments. The PAAS-normalized REE patterns of sediment were similar to that of SPM. The results revealed two processes, colloidal flocculation and coagulation of metals in the low-salinity zone and an estuarine turbidity maximum in the high salinity zone. Rare earths and yttrium (REY) in SPM and sediments primarily reflected the source rock composition than that of chemical weathering. Apart from physico-chemical processes, the mineralogy and grain size of sediments controlled the distribution and fractionation of REY in the estuary.     

南岭热带一亚热带风化壳中稀土元素赋存形式的初步研究

通过对南岭及海南岛热带－亚热带地区几十个风化壳剖面中稀土元素分布特征的研究表明，ＲＥＥ有如下五种主要赋存形式：①呈可交换状态赋存于粘土中；②富集于次生铁锰氧化物中；③呈次生稀土矿物或类似的富稀土微质点；④风化残余稀土（或含稀土）副矿物；⑤赋存于残留造岩矿物碎屑中。控制化学风化条件下ＲＥＥ淋滤、沉淀的主要因素是原岩中稀土赋存矿物的稳定性、介质环境的ｐＨ和Ｅｈ条件、ＲＥＥ的电子层结构及其化学键性质以及