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.     

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。     

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.     

Rare earth element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (⁸⁷Sr/⁸⁶Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]_PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]_PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]_PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] _PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]_PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The ⁸⁷Sr/⁸⁶Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.     

Rare earth element fractionation during the precipitation and crystallisation of hydrous ferric oxides from anoxic lake water

An enrichment of light rare earth elements (LREE) is characteristic for most of the acidic, Fe- and SO₄-rich pit lakes and groundwaters in the lignite mining area of Lower Lusatia (Germany). One of these acidic lakes – the pit lake “RL 1223” – has a strong thermal and chemical stratification. The upper water layer (0–9 m) shows pH values of about 3 during all seasons. The monimolimnion (10–17 m) of the lake is anoxic and has pH values of about 7. The rare earth element (REE) patterns of the upper lake water show enriched LREE (La_N/Yb_N = 1.6) whereas the opposite patterns (depletion of LREE, La_N/Yb_N = 0.4) are found in the anoxic water of the monimolimnion. Experiments were conducted to observe the behaviour of REE during Fe oxidation in water from the monimolimnion (depth 14 m). The sampled monimolimnion water was placed in plastic bottles, and the changing water chemistry was observed for 40 weeks after sampling. Due to the initial anoxic conditions almost all Fe precipitated in the investigated water, and the pH value decreased from about 7 to 3 during the oxidation. The Fe precipitates are identified as ferrihydrite which is transformed into goethite within the oxidation process. Stable pH conditions (pH 3.0) were reached after about 10 weeks of oxidation.The original REE patterns of the investigated water are generally reflected in the Fe precipitates collected at the beginning of the experiment as well as after up to 40 weeks of oxidation. However, in the corresponding water LREE were temporally enriched with a maximum La_N/Yb_N ratio of 1.0 and a maximum La_N/Sm_N ratio of 2.3 after 6 weeks of oxidation time (pH 3.8–4.9). Although complex geochemical changes took place between the start and the end of the experiment REE patterns observed at these points in time are nearly identical. These differences of the REE pattern can be explained by the sampling procedure. The experimental findings can be transmitted to the mining dump aquifers of the study area where geochemical conditions comparable to the experimental oxidation time from 3 to 6 weeks are found and hydrous ferric oxides are precipitating. Groundwater passing through the mining dumps can preferentially desorb LREE from the Fe precipitates and display the typical LREE enrichment and carry it to the epilimnion of the acidic pit lakes in Lower Lusatia.     

Apatite as an indicator mineral for mineral exploration: trace-element compositions and their relationship to host rock type

Over 700 apatite grains from a range of rock types have been analysed by laser-ablation microprobe ICPMS for 28 trace elements, to investigate the potential usefulness of apatite as an indicator mineral in mineral exploration. Apatites derived from different rock types have distinctive absolute and relative abundances of many trace elements (including rare-earth elements (REE), Sr, Y, Mn, Th), and chondrite-normalised trace-element patterns. The slope of chondrite-normalised REE patterns varies systematically from ultramafic through mafic/intermediate to highly fractionated granitoid rock types. (Ce/Yb)_cn is very high in apatites from carbonatites and mantle-derived lherzolites (over 100 and over 200, respectively), while (Ce/Yb)_cn values in apatites from granitic pegmatites are generally less than 1, reflecting both HREE enrichment and LREE depletion. Within a large suite of apatites from granitoid rocks, chemical composition is closely related to both the degree of fractionation and the oxidation state of the magma, two important parameters in determining the mineral potential of the magmatic system. Apatite can accept high levels of transition and chalcophile elements and As, making it feasible to recognise apatite associated with specific types of mineralisation. Multivariate statistical analysis has provided a user-friendly scheme to distinguish apatites from different rock types, based on contents of Sr, Y, Mn and total REE, the degree of LREE enrichment and the size of the Eu anomaly. The scheme can be used for the recognition of apatites from specific rock types or styles of mineralisation, so that the provenance of apatite grains in heavy mineral concentrates can be determined and used in geochemical exploration.     

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.     

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.     

Trace‐element signatures of apatites in granitoids from the Mt Isa Inlier,northwestern Queensland

The concentrations of trace elements in apatite from granitoid rocks of the Mt Isa Inlier have been investigated using the laser‐ablation inductively coupled plasma‐mass spectrometry (ICP‐MS) microprobe. The results indicate that the distribution of trace elements (especially rare‐earth elements (REE), Sr, Y, Mn and Th) in apatite strongly reflects the chemical characteristics of the parental rock. The variations in the trace‐element concentrations of apatite are correlated with parameters such as the SiO₂ content, oxidation state of iron, total alkalis and the aluminium saturation index (ASI). The relative enrichment of Y, HREE and Mn and the relative depletion of Sr in the apatites studied reflect the degree of fractionation of the host granite. Apatites from strongly oxidised plutons tend to have higher concentrations of LREE relative to MREE. Manganese concentrations are higher in apatite from reduced granitoids because Mn²⁺substitutes directly for Ca²⁺. The La/Ce ratio of apatite is well‐correlated with the whole‐rock K²O and Na²O contents, as well as with the oxidation state and ASI. Because apatite trace‐element composition reflects the chemistry of the whole rock, it can be a useful indicator mineral for the recognition of mineralised granite suites, where particular mineralisation styles are associated with granitoids that have specific geochemical fingerprints.     

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.     

Seamount volcanism associated with the Xigaze ophiolite, Southern Tibet

Basaltic lavas at Renbu, Southern Tibet are associated with the Xigaze ophiolite in the Yarlung-Zangbo suture zone. They are alkaline lavas rich in large ion lithophile elements (LILE, Ba, Rb and Sr) and high field strength elements (HFSE, Nb, Ta, Zr and Hf), but poor in Cr, Co and Ni. All of the rocks have chondrite-normalized REE patterns enriched in light rare earth elements (LREE), comparable to modern basalts of the Society Islands, Kerguelen Plateau and Broken Ridge. Abundances of some immobile or moderately immobile elements (Nb, Ta, Zr, Hf, Y, Ti and REE) are also comparable to Kerguelen alkaline basalts. The Renbu basalts are geochemically similar to oceanic island basalts (OIB) and have some elemental ratios, such as Nb/Ta ratios = 15.7–18.1, Th/Nb =  0.06–0.10, La/Nb = 0.59–0.83 and Th/Ta = 1.03–1.52, similar to the primitive mantle. Their ⁸⁷Sr/⁸⁶Sr ratios (0.70453–0.70602) are relatively high, similar to OIB. In the ⁸⁷Sr/⁸⁶Sr vs. εNd(t) diagram, the Renbu basalts plot along a trend from N-MORB to EMII (enriched mantle II), suggesting the involvement of at least two mantle sources in their generation. The Renbu basalts represent seamount volcanism associated with the Xigaze ophiolite. They formed from an OIB-type mantle source within the Neo-Tethyan Ocean that had a composition similar to the modern Indian Ocean mantle.     

Behaviour of rare earth elements at the freshwater–seawater interface of two acid mine rivers: the Tinto and Odiel (Andalucia, Spain)

The concentrations of dissolved and suspended particulate rare-earth elements (REE) are reported in acid-sulphate waters from the Odiel and Tinto rivers. Shale normalized patterns are typically convex and high REE concentrations (e.g., Ce=0.43–65 μg.l⁻¹) are present in the waters. The REE content of the suspended load is greater by a factor of up to 3000. In the Odiel river, REE patterns of the particulates are essentially convex and sub-parallel to those of the waters; speciation calculations indicate that SO₄ complexes play a dominant role in controlling the REE distributions. In the Tinto river, the REE patterns of the suspended load are slightly fractionated and a negative Ce anomaly is apparent in several samples, reflecting the local influence of phosphogypsum deposits.Contrasting with normal estuaries, REE are not intensely removed in the low chlorinity zone. A remobilization in relation to Fe reduction is observed in the Tinto river.     

A new partial substitution mechanism of CO 3 2− /CO3OH3− and SiO 4 4− for the PO 4 3− group in hydroxyapatite from the Kaiserstuhl alkaline complex (SW-Germany)

Based on a detailed mineral-chemical investigation of apatite from a series of carbonatites and associated silicate volcanic rocks of the Kaiserstuhl tertiary alkaline volcanic centre, evidence for a new substitution mechanism was found within the hydroxyapatite group, yielding the following simplified formula: (Ca, Sr, LREE)₁₀(SiO₄)_x(CO₃)_x(PO₄)_6–2x(OH, F)₂ with 03 ^2– and SiO ₄ ^4– for PO ₄ ^3– ; however, excess charge may be subsequently adjusted by CO₃OH^3– partly accompanied by the REE in the Ca site.     

Geochemistry and origin of massif-type anorthosites

Samples of Proterozoic anorthosite complexes from the Adirondack Mountains of New York, Burwash Area of Ontario, and the Nain Complex of Labrador, ranging in composition from anorthosite to anorthositic gabbro, have been analyzed for major elements, Rb, Sr, Ba and nine rare-earth elements (REE), in order to set limits on the compositions and origins of their parent magmas. Similar rock types from the different areas have similar major and trace element compositions. The anorthosites have high Sr/Ba ratios, low REE abundances (Ce about 10, Yb about 0.5–1.5 times chondrites) and large positive Eu anomalies. The associated anorthositic gabbros have lower Sr/Ba ratios, REE abundances nearly an order of magnitude higher than the anorthosites, and small to negligible positive Eu anomalies.Model calculations using the adcumulate rocks with the lowest REE abundances and published distribution coefficients yield parent liquids having REE abundances and patterns similar to those of the associated anorthositic gabbros with the highest REE abundances. Rocks with intermediate REE abundances are the result of incorporation of a liquid component by a plagioclase-rich cumulate similar to the adcumulate samples. The analytical data and model calculations both suggest parent liquids having compositions of 50–54% SiO₂, greater than 20% Al₂O₃, about 1% K₂O, atomic Mg/(Mg+Fe²⁺) ratios (Mg No.'s) of less than 0.4, 15–30 ppm Rb, 400–600 ppm Sr and 400–600 ppm Ba, 40–50 times chondrites for Ce and 8–10 times chondrites for Yb.The low atomic Mg/(Mg+Fe²⁺) values for these rocks combined with geophysical evidence suggesting there are not large quantities of ferromagnesian material at depth, indicate that the anorthositic masses are not products of fractional crystallization of mafic melt derived from melting of the mantle. Rather, it is suggested that they are a result of partial melting of tholeiitic compositions at depths shallower than the basalt-eclogite transformation, leaving a pyroxene-dominated residue.     

Trace element and isotopic variations in a zoned pluton and associated volcanic rocks,Unalaska Island,Alaska: A model for fractionation in the Aleutian calcalkaline suite

Trace elements, including rare earth elements (REE), exhibit systematic variations in plutonic rocks from the Captains Bay pluton which is zoned from a narrow gabbroic rim to a core of quartz monzodiorite and granodiorite. The chemical variations parallel those in the associated Aleutian calcalkaline volcanic suite. Concentrations of Rb, Y, Zr and Ba increase as Sr and Ti decrease with progressive differentiation. Intermediate plutonic rocks are slightly enriched in light REE (La/Yb=3.45–9.22), and show increasing light REE fractionation and negative Eu anomalies (Eu/Eu^*=1.03–0.584). Two border-zone gabbros have similar REE patterns but are relatively depleted in total REE and have positive Eu anomalies; indicative of their cumulate nature. Initial ⁸⁷Sr/⁸⁶Sr ratios in 8 samples (0.70299 to 0.70377) are comparable to those of volcanic rocks throughout the arc and suggest a mantle source for the magmas. Oxygen isotopic ratios indicate that many of the intermediate plutonic rocks have undergone oxygen isotopic exchange with large volumes of meteoric water during the late stages of crystallization; however no trace element or Sr isotopic alteration is evident.Major and trace element variations are consistent with a model of inward fractional crystallization of a parental high-alumina basaltic magma at low pressures (6 kb). Least-squares approximations and trace element fractionation calculations suggest that differentiation in the plutonic suite was initially controlled by the removal of calcic plagioclase, lesser pyroxene, olivine and Fe-Ti oxides but that with increasing differentiation and water fugacity the removal of sub-equal amounts of sodic plagioclase and hornblende with lesser Fe-Ti oxides effectively drove residual liquids toward dacitic compositions. Major and trace element compositions of aplites which intrude the pluton are not adequately explained by fractional crystallization. They may represent partial melts derived from the island arc crust. Similarities in Sr isotopes, chemical compositions and differentiation trends between the plutonic series and some Aleutian volcanic suites indicates that shallow-level fractional crystallization is a viable mechanism for generating the Aleutian calcalkaline rock series.LDGO Contribution no. 2964     

Geochronology and mineralogy of the Weishan carbonatite in Shandong province,eastern China

The Weishan REE deposit is located at the eastern part of North China Craton (NCC), western Shandong Province. The REE-bearing carbonatite occur as veins associated with aegirine syenite. LA-ICP-MS bastnaesite Th-Pb ages (129 Ma) of the Weishan carbonatite show that the carbonatite formed contemporary with the aegirine syenite. Based on the petrographic and geochemical characteristics of calcite, the REE-bearing carbonatite mainly consists of Generation-1 igneous calcite (G-1 calcite) with a small amount of Generation-2 hydrothermal calcite (G-2 calcite). Furthermore, the Weishan apatite is characterized by high Sr, LREE and low Y contents, and the carbonatite is rich in Sr, Ba and LREE contents. The δ¹³C_V-PDB (−6.5‰ to −7.9‰) and δ¹³O_V-SMOW (8.48‰–9.67‰) values are similar to those of primary, mantle-derived carbonatites. The above research supports that the carbonatite of the Weishan REE deposit is igneous carbonatite. Besides, the high Sr/Y, Th/U, Sr and Ba of the apatite indicate that the magma source of the Weishan REE deposit was enriched lithospheric mantle, which have suffered the fluid metasomatism. Taken together with the Mesozoic tectono-magmatic activities, the NW and NWW subduction of Izanagi plate along with lithosphere delamination and thinning of the North China plate support the formation of the Weishan REE deposit. Accordingly, the mineralization model of the Weishan REE deposit was concluded: The spatial-temporal relationships coupled with rare and trace element characteristics for both carbonatite and syenite suggest that the carbonatite melt was separated from the CO₂-rich silicate melt by liquid immiscibility. The G-1 calcites were crystallized from the carbonatite melt, which made the residual melt rich in rare earth elements. Due to the common origin of G-1 and G-2 calcites, the REE-rich magmatic hydrothermal was subsequently separated from the melt. After that, large numbers of rare earth minerals were produced from the magmatic hydrothermal stage.     

皖北新元古界望山组灰岩微量元素地球化学特征*

为研究皖北新元古界望山组灰岩地球化学特征及地质背景,对该地区灰岩进行了系统的岩石学和微量元素地球化学测试。研究结果表明：望山组灰岩中,元素U、Pb、Sr、Sm富集,Nb、Pr、Zr、Hf明显亏损;稀土总量偏低（6.68～42.78 μg/g）,轻稀土略亏损,Nd_SN/Yb_SN值在0.65～0.91之间变化,轻重稀土分异微弱,灰岩样品均具有程度不同的La和Y正异常。U、Th、Ce等元素特征反映了研究区望山组形成于缺氧的水体环境,Sr/Ba、Sr/Cu值反映了望山组灰岩形成于盐度较大的海水环境和干旱的气候条件;La-Th-Sc和Th-Sc-Zr/10图解指示望山组灰岩可能形成于大陆岛弧环境。     

Rare earth and other trace element mobility during mylonitization: a comparison of the Brevard and Hope Valley shear zones in the Appalachian Mountains, USA

In progressing from a granitoid mylonite to an ultramylonite in the Brevard shear zone in North Carolina, Ca and LOI (H₂O) increase, Si, Mg, K, Na, Ba, Sr, Ta, Cs and Th decrease, while changes in Al, Ti, Fe, P, Sc, Rb, REE, Hf, Cr and U are relatively small. A volume loss of 44% is calculated for the Brevard ultramylonite relative to an Al–Ti–Fe isocon. The increase in Ca and LOI is related to a large increase in retrograde epidote and muscovite in the ultramylonite, the decreases in K, Na, Si, Ba and Sr reflect the destruction of feldspars, and the decrease in Mg is related to the destruction of biotite during mylonitization. In an amphibolite facies fault zone separating grey and pink granitic gneisses in the Hope Valley shear zone in New England, compositional similarity suggests the ultramylonite is composed chiefly of the pink gneisses. Utilizing an Al–Ti–Fe isocon for the pink gneisses, Sc, Cr, Hf, Ta, U, Th and M-HREE are relatively unchanged, Si, LOI, K, Mg, Rb, Cs and Ba are enriched, and Ca, Na, P, Sr and LREE are lost during deformation. In contrast to the Brevard mylonite, the Hope Valley mylonite appears to have increased in volume by about 70%, chiefly in response to an introduction of quartz. Chondrite-normalized REE patterns of granitoids from both shear zones are LREE-enriched and have prominent negative Eu anomalies. Although REE increase in abundance in the Brevard ultramylonites (reflecting the volume loss), the shape of the REE pattern remains unchanged. In contrast, REE and especially LREE decrease in abundance with increasing deformation of the Hope Valley gneisses. Mass balance calculations indicate that ≥95% of the REE in the Brevard rocks reside in titanite. In contrast, in the Hope Valley rocks only 15–40% of the REE can be accounted for collectively by titanite, apatite and zircon. Possible sites for the remaining REE are allanite, fluorite or grain boundaries. Loss of LREE from the pink gneisses during deformation may have resulted from decreases in allanite and perhaps apatite or by leaching ofy REE from grain boundaries by fluids moving through the shear zone. Among the element ratios most resistant to change during mylonitization in the Brevard shear zone are La/Yb, Eu/Eu*, Sm/Nd, La/Sc, Th/Sc, Th/Yb, Cr/Th, Th/U and Hf/Ta, whereas the most stable ratios in the Hope Valley shear zone are K/Rb, Rb/Cs, Th/U, Eu/Eu*, Th/Sc, Th/Yb, Sm/Nd, Th/Ta, Hf/Ta and Hf/Yb. However, until more trace element data are available from other shear zones, these ratios should not be used alone to identify protoliths of deformed rocks.     

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.     

Light Rare Earth Elements enrichment in an acidic mine lake (Lusatia,Germany)

The distribution of Rare Earth Elements (REE) was investigated in the acidic waters (lake and groundwater) of a lignite mining district (Germany). The Fe- and SO₄-rich lake water (pH 2.7) displays high REE contents (e.g. La∼70 μg/l, Ce∼160 μg/l) and an enrichment of light REE (LREE) in the NASC normalised pattern. Considering the hydrodynamic model and geochemical data, the lake water composition may be calculated as a mixture of inflowing Quaternary and mining dump groundwaters. The groundwater of the dump aquifer is LREE enriched. Nevertheless, the leachates of dump sediments generally have low REE contents and display flat NASC normalised patterns. However, geochemical differences and REE pattern in undisturbed lignite (LREE enriched pattern and low water soluble REE contents) and the weathered lignite of the dumps (flat REE pattern and high water soluble REE contents) suggest that lignite is probably the main REE source rock for the lake water.