Isotope Dilution MC-ICP-MS Rare Earth Element Analysis of Geochemical Reference Materials NIST SRM 610, NIST SRM 612, NIST SRM 614, BHVO-2G, BHVO-2, BCR-2G, JB-2, WS-E, W-2, AGV-1 and AGV-2

We present data for the concentrations of eleven rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu) in eleven international geochemical reference materials obtained by isotope dilution multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We have analysed both rock powders and synthetic silicate glasses, and the latter provide precise data to support the use of these as reference materials for in situ trace element determination techniques. Our data also provide precise measurements of the abundance of mono-isotopic Pr in both glasses and powders, which allows more accurate constraints on the anomalous redox-related behaviour of Ce during geochemical processes. All materials were analysed in replicate providing data that typically reproduce to better than one percent. Sm/Nd ratios in all these materials also reproduce to better than 0.2% and are accurate to < 0.2% and can thus be used as calibrants for Sm-Nd geochronology. Our analyses agree well with existing data on these reference materials. In particular, for NIST SRM 610, USGS BHVO-2, AGV-1 and AGV-2, our measured REE abundances are typically within < 2% (and mostly 1%) of REE concentrations previously determined by isotope dilution analysis and thermal ionisation mass spectrometry, consistent with the higher degree of precision and accuracy obtained from isotope dilution techniques. Close agreement of results between basaltic glass reference materials USGS BHVO-2G and BCR-2G and the BHVO-2 and BCR-2 powders from which they were created suggests that little fractionation, concentration or dilution of REE contents occurred during glass manufacture.     

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.     

Geochemistry of peridotite and granite xenoliths during the early stage of weathering in the Nyos volcanic region (NW Cameroon): Implications for PGE exploration

Peridotite and granite xenoliths, in the early stage of weathering, occur in the Nyos volcanic region (NW Cameroon). Geochemical data shows that peridotites are marked by high concentrations of MgO (42.30 wt.%, with SiO₂/MgO ∼ 1), chromium (2100 ppm), nickel (2100 ppm) and cobalt (104 ppm), as well as by low lanthanide contents (ΣREE: 7.41 ppm). Granites display SiO₂ contents (70–73 wt.%), and are mostly peraluminous (1.40 > A/CNK < 1.6). They are also characterized by low contents in chromium (<24 ppm), nickel (ranging from 6 to 15 ppm) and cobalt (ranging from 3 to 6 ppm). Granites possess high lanthanide contents (ΣREE varying between 248.00 and 463.00 ppm), particularly in light lanthanides (LREE/HREE ratios ranging from 21 to 32). The chondrite-normalized patterns of the studied xenoliths are characterized by: (i) LREE enrichments in both rock types; (ii) negative Eu anomalies ([Eu/Eu*] ranging from 0.45 to 0.64) and weak positive Ce anomalies ([Ce/Ce*] ranging from 1.06 to 1.46) in granites. The weathering process provokes a remobilization of several trace elements notably light lanthanides.The geochemical survey of Platinum-Group Elements (PGE) done in these rocks in the early stage of weathering shows that PGE contents are less than 7 ppb in the peridotites. The highly concentrated elements are ruthenium (6.26 ppb) and platinum (5.53 ppb). The total PGE content is 14.57 ppb. These concentrations normalized with respect to chondrites display a flat spectrum from iridium to platinum. PGE contents in the granites are below detection limit except for two samples (LNY01 and LNY02) whose platinum content is close to 0.23 ppb.     

REE and Sr isotope characteristics of carbonate within the Cu–Co mineralized sedimentary sequence of the Nchanga Mine,Zambian Copperbelt

Carbonate, largely in the form of dolomite, is found throughout the host rocks and ores of the Nchanga mine of the Zambian Copperbelt. Dolomite samples from the hanging wall of the mineralization show low concentrations of rare-earth elements (REE) and roof-shaped, upward convex, shale-normalized REE patterns, with positive Eu*_SN anomalies (1.54 and 1.39) and marginally negative Ce anomalies (Ce*_SN 0.98,0.93). In contrast, dolomite samples associated with copper and cobalt mineralization show a significant rotation of the REE profile, with HREE enrichment, and La/Lu_SN ratios <1 (0.06–0.42). These samples also tend to show variable but predominantly negative Eu*_SN and positive cerium anomalies and an upwardly concave MREE distribution (Gd-Er). Malachite samples from the Lower Orebody show roof-tile-normalized REE patterns with negative europium anomalies (Eu*_SN 0.65–0.80) and negative cerium anomalies (Ce*_SN 0.86–0.9). The carbonate ⁸⁷Sr/⁸⁶Sr signature correlates with the associated REE values. The uppermost dolomite samples show Neoproterozoic seawater-like ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7111 to 0.7116, whereas carbonate from Cu–Co mineralized samples show relatively low concentrations of strontium and more radiogenic ⁸⁷Sr/⁸⁶Sr, ranging between 0.7136–0.7469. The malachite samples show low concentrations of strontium, but give a highly radiogenic ⁸⁷Sr/⁸⁶Sr of 0.7735, the most radiogenic ⁸⁷Sr/⁸⁶Sr ratio. These new data suggest that the origin and timing of carbonate precipitation at Nchanga is reflected in the REE and Sr isotope chemistry. The upper dolomite samples show a modified, but essentially seawater-like signature, whereas the rotation of the REE profile, the MREE enrichment, the development of a negative Eu*_SN anomaly and more radiogenic ⁸⁷Sr/⁸⁶Sr suggests the dolomite in the Cu–Co mineralized samples precipitated from basinal brines which had undergone significant fluid–rock interaction. Petrographic, REE, and ⁸⁷Sr/⁸⁶Sr data for malachite are consistent with the original sulfide Lower Orebody being subject to a later oxidizing event.     

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.     

Genesis of the Jinding Zn-Pb deposit,northwest Yunnan Province,China: Constraints from rare earth elements and noble gas isotopes

The giant sediment-hosted Jinding zinc-lead deposit is located in the Lanping Basin, northwestern Yunnan Province, China. The genesis of the deposit has long been debated and the sources of the ore-forming fluids and metals are controversial. This study presents rare earth element (REE) and noble gas isotope data that constrain the origins of the ore fluids and the heat source driving the hydrothermal circulation. The early-stage sulfides are enriched in light REEs and have high ∑REE values (30.8–94.8 ppm) and weakly negative Eu (δEu 0.85–0.89) and Ce anomalies (δCe 0.84–0.95), suggesting that the fluids were likely derived from dissolution of Upper Triassic marine carbonates with input of REEs from aluminosilicate rocks in the basin. In contrast, the late-stage sulfides have irregular REE patterns, generally low ∑REE values (0.24–10.8 ppm) and positive Eu (δEu 1.22–10.9) and weakly negative Ce anomalies (δCe 0.53–0.90), which suggest that the ore-forming fluids interacted with evaporite minerals. The ³He/⁴He (0.01–0.04 R_a) and ⁴⁰Ar/³⁶Ar values (301–340) of the ore-forming fluids indicate crustal and atmospheric origins for these noble gases. These findings are in agreement with the published fluid inclusion microthermometry data and the results of H, O, C, S, Pb and Sr isotope studies. Our data, in combination with published results, support a two-stage hydrothermal mineralization model, involving early-stage basinal brines and late-stage meteoric water that acquired metals and heat from crustal sources.     

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.     

Rare earth elements in corals from the Isla de Sacrificios Reef,Veracruz, Mexico

Rare earth elements (REE) analysis was carried out in two coral species Diploria strigosa and Copophyllia natans from Isla de Sacrificios Reef (ISR) (19° 10′ 51.6″N; 96° 5′ 45.6″W) Veracruz, Mexico. Both corals were cut at the top, middle and bottom parts to detect possible differences in REE concentrations related to water masses and sediment inputs. An enrichment in heavy rare elements (HREE) compared to light rare elements (LREE) at the top of Diploria strigosa and Copophyllia natans, evidenced by (La/Lu)_SN <0.5, (La/Yb)_SN <0.5 and (Pr/Yb)_SN <0.5 is observed. This HREE enrichment in both corals is probably due to the high pH and CO₃^2? content in the seawater. A negative Ce anomaly is observed throughout Diploria strigosa and Copophyllia natans, probably linked with well oxygenated, highly oxidative modern shallow waters, and high nutrients related to suspended matter. Positive Eu anomalies in both corals are due to development of the ISR in shallow waters. Ce/Ce* vs. (Pr/Yb)_SN diagram suggests the input of terrigenous material, as all samples have Ce/Ce* and Pr/Yb values outside the seawater range signature. However, the Nd/Yb and (Nd/Yb)_SN suggest that the top of Diploria strigosa and Copophyllia natans are associated with coastal waters at about 50 m depth.     

Determination of the Rare-Earth Elements and Yttrium In 37 International Silicate Reference Materials By Inductively Coupled Plasma-Atomic Emission Spectrometry

The rare-earth elements (REE) and yttrium have been determined in 37 international rock and mineral reference materials. Samples were prepared using conventional rock-dissolution techniques, and the REE and yttrium were separated from the other constituents using cation-exchange chromatography. The REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) and yttrium were determined simultaneously by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Results for four well-characterised USGS standard rocks agree favourably with "recommended" values and with REE determinations made previously by workers using ICP-AES, isotope dilution mass spectrometry, instrumental neutron activaton analysis and X-ray fluorescence spectrometry.
Les éléments de terres rares (TR) et yttrium ont été dosés dans 37 échantillons internationaux de réféence. Les échantillons ont été décomposés par dissolution acide et les TR séparés par résine échangeuse de cations. Les TR (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) et yttrium ont été dosés simultanément par la spectrométrie d'émission-plasma inductif. Les résultats obtenus pour quatre échantillons de référence bien charactérisés de I'USGS se comparent favorablement avec ceux obtenus par la spectrométrie d'émission-plasma, la dilution isotopique, I'activation neutronique et par la spectrométrie d'é fluorescence-X.     

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(–Fe) Deposits in Japan

Abstract: Systematic data of rare earth elements (REEs) are presented in order to put some constraints on the origin of hydrothermal fluids responsible for two contrastive skarn deposits in Japan; the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(-Fe) deposits. Carbon and oxygen isotopic studies have demonstrated that the hydrothermal fluids responsible for the Kamioka Zn-Pb deposits are of meteoric water origin whereas those for the Yoshiwara-Sannotake Cu(-Fe) deposits are of magmatic water origin. The REE abundances of epidote skarn derived from aluminous rocks, garnet and clinopyroxene in calcic exoskarn derived from limestone, and interstitial calcite associated with sulfide minerals were determined for these contrastive skarn deposits by inductively-coupled plasma mass spectrometry (ICP-MS). A significant difference in the REE concentrations is not found between epidote skarn and aluminous original rock (plagioclase-clinopyroxene rock, called Inishi rock) from the Kamioka Zn-Pb deposits, indicating that the REEs are generally immobile during the formation of epidote skarn, and that the REE concentrations of the hydrothermal fluid are considerably low relative to the aluminous original rock. In contrast, the epidote skarn exhibits enrichment of Eu with increasing total REE concentrations relative to the aluminous original rock (quartz diorite) in the Yoshiwara-Sannotake Cu(-Fe) deposits, implying a contribution of magmatic fluid derived from granitoids during the skarn formation. Limestone generally has much lower REE concentrations related to surrounding aluminous rocks, and thus the REE concentrations of garnet and clinopyroxene in calcic exoskarn, originated from limestone, are variable due to the interaction with the hydrothermal fluids. The chondrite-normalized REE patterns of garnet, clinopyroxene, and interstitial calcite exactly provide useful information on origins of hydrothermal fluids. The REE patterns of these minerals from the Kamioka Zn-Pb deposits show lower (Pr/Yb)cn ratios, and negative Ce and Eu anomalies inherited from limestone with the decrease of This suggests that the hydrothermal fluids responsible for the Kamioka Zn-Pb deposits were depleted in REEs, and were not magmatic water in origin, but presumably meteoric one. In striking contrast, the REE patterns of exoskarn minerals and calcite from the Yoshiwara-Sannotake Cu(-Fe) deposits exhibit a positive Eu anomaly, and high (Pr/Yb)cn ratios with the considerable increase of σREE and the disappearance of negative Ce anomaly, implying that the fluids were dominantly of magmatic origin. The REE indices are very likely to be an excellent indicator to origins of the skarn deposits.     

Use of rare earth element patterns to trace the provenance of the atmospheric dust near Beijing, China

Atmospheric dust is one of the important indicators of urban air quality. In this study, atmospheric dust and topsoil samples were collected monthly from four sites in Beijing and surrounding areas, and analyzed for rare earth elements (REEs). Total REE concentrations (∑REE) in the dusts ranged from 43.10 to 164.43 mg kg^?1; concentrations in Beijing and Miyun were higher than those in Zhangbei and Fengning. Most of sampling sites showed the same seasonal depletion in dust ∑REE concentrations in summer, probably caused by the “dilution effect” of added organic matter in summertime samples. Most of the dusts have consistent Ce-anomaly (Ce/Ce*) values (0.91–1.00) and Eu anomaly (Eu/Eu*) values (0.93–1.36); some dusts show slight positive Eu anomalies. The REE patterns of both the dusts and topsoils (normalized to post-Archean shales from Australia, PASS) show different signatures at different sites, whereas the temporal patterns are consistent at each site. These results suggest that local topsoils are likely to be the main provenance of the dusts in the study area.     

冀东、五台和吕梁地区条带状铁矿的稀土元素特征及其地质意义

详细报道了冀东、五台和吕梁地区条带状铁矿全岩样品的稀土元素分析结果。结果表明,研究区BIF具有非常相似的特征：稀土总量均较低;经页岩标准化的稀土元素配分模式均呈现轻稀土亏损、重稀土富集的特征;Y/Ho比值较高;具有明显的Eu、Y、La的正异常,且这些特征表明研究区BIF的稀土元素来源于火山热液和海水的混合溶液。虽然BIF均显示Eu正异常,但不同类型、不同沉积年龄BIF的铕异常程度不同：与吕梁地区Superior型铁矿相比,冀东和五台地区的Algoma型铁矿显示了更大的Eu正异常;并且自中太古代-新太古代-古元古代,BIF的铕正异常逐渐减小,这可能反映了随着BIF沉积年龄的减小,进入到该地区海水中的高温热液流体逐渐减少;同时,研究区BIF缺乏明显的Ce负异常,可能暗示在BIF沉积时海水的氧化还原状态为缺氧环境。     

Geochemistry of rare-earth elements in shallow groundwater,northeastern Guangdong Province,China

Shallow groundwater and hot springs were collected from northeastern Guangdong Province, Southeast China, to determine the concentrations and fractionation patterns of rare-earth elements(REE). The results show that the La, Ce and Nd of REEs are abundant in groundwater and rock samples, and the ∑REE contents in groundwater and rock samples range from 126.5 to 2875.3 ng/L, and 79.44 to 385.85 mg/L, respectively. The shallow groundwater has slightly HREE-enriched PAAS-normalized patterns. However, the granitic rocks PAAS-normalized patterns, with remarkable negative Eu anomalies, are different from that of shallow groundwater. The enrichment of HREE is considered to be controlled by REE complexation and readsorption for most groundwater has Ce and Eu positive anomalies. The Ce and Eu anomalies in groundwater are controlled by redox conditions. Moreover, the Fe-contain sediments dissolution and/or the reduction of Fe oxyhydroxides are another factor contributing to Ce anomalies. The Eu anomalies in groundwater are controlled by the preferential mobilization of Eu2+ during water-rock interaction compared to Eu3+.     

老挝西北部琅勃拉邦构造带放射虫硅质岩及其构造意义

琅勃拉邦构造带内放射虫硅质岩含有放射虫Entactinia vulgaris Won, Entactinosphaera palimpola Foreman和Belowea variabilis (Ormiston et Lane),时代为早石炭世,为老挝境内首次报告。硅质岩样品具有很高的SiO2质量分数(95.29%~98.17%),大部分样品表现出相类似的稀土配分模式,部分样品配分模式图表现为上凸状,具有中稀土富集,均具有明显的Ce负异常,Ce/Ce*值为0.64~0.74,其中部分样品具有Eu的负异常,为0.58~0.68。Y/Ho比值为31.05~40.96,类似日本Sasayama中-晚二叠世的远洋硅质岩。地球化学显示其为含酸性火山碎屑非热液成因的远洋硅质岩。这些研究证实了在思茅板块和印支板块之间存在一个开阔的石炭纪时期弧后盆地。     

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.     

鄱阳湖流域赣江北支水体和沉积物中稀土元素的含量和分异特征

稀土的开发和广泛应用使得人们倍加关注其在环境中的分布及其环境地球化学行为。赣江作为鄱阳湖流域五大入湖河之一,发源于稀土资源富集的赣南地区,而其下游水体及周边地下水中稀土元素的含量和分异特征目前尚不完全清楚。以赣江北支水体及沉积物为研究对象,开展了稀土元素地球化学研究。结果表明,赣江北支水体中稀土元素总量在地表水中为230~1 146 ng/L(均值458.85 ng/L),地下水中为284~1 498 ng/L(均值634.94 ng/L),沉积物中稀土元素总量为177.9~270.7 mg/kg(均值226.99 mg/kg)。PHREEQC模拟计算表明,水体中的稀土元素主要以碳酸根络合物(REEC0₃⁺)的形式存在。地表水和地下水总体上均表现为重稀土元素相较于轻、中稀土元素富集,沉积物未表现出明显的富集特性;水体具有Ce、Eu负异常特点,而沉积物表现为Ce正异常和Eu负异常,指示氧化还原环境和水岩相互作用对稀土元素在水-沉积物系统中迁移转化的影响。地下水中稀土元素的含量沿流向具有上升趋势,而水体中重稀土元素的富集程度不断减弱,同时碳酸根络合物(REEC0₃⁺)的占比不断降低,反映水体中稀土元素的含量受到pH、胶体吸附、络合作用以及地下水-地表水相互作用的影响。水体中重稀土元素的富集受到碳酸根络合反应的影响,Ce、Eu负异常与Ce氧化沉淀和母岩特性相关。Gd异常值表明,研究区中下游水体中的Gd元素受到人为输入的影响。     

Petrogenetic significance of rare-earth element behavior in the basement rocks of southern Obudu Plateau, Bamenda Massif, southeastern Nigeria

Rock samples representing various igneous and metamorphic rocks of southern Obudu Plateau were analyzed for rare-earth element ( REE ) behavior by ICP-MS. Results of the analyses indicate a range of REE abundances and distinctive patterns from highly fraetionated patterns with negative Eu anomalies in granitic rocks to relatively low abundances and less REE fractionated flat patterns with little Eu anomaly in some paragneisses, schists, enderbites and dolerites to unfractionated patterns with positive Eu anomalies in some paragneisses and charnockites. Over all, there are low to high ∑ REE contents with negative to positive Eu anomalies. The ratios of different parameters, especially La/Yb and Ce/Yb, show behaviors consistent with crustal to mantle derivation. The heterogeneity of REE abundances and REE patterns reflects mantle to crustal petrogenetic variations of different rock suites on the Plateau. The LREE content is higher than the HREE content in the highly differentiated rocks, as evidenced by their La/Yb,Ce/Yb and La/Sm ratios, which are normally higher in residual products than in primary melts. The dominantly intermediate nature of the source rock of the orthogneisses is suggested by the generally low ∑ REE. The granites enriched in LREE and depleted in HREE and some of the charnockites with negative Eu anomalies were probably formed by partial melting and crystallization.     

Rare-earth abundances in chondritic meteorites

Fifteen chondrites, including eight carbonaceous chondrites, have been analyzed for rare earth element (REE) abundances by isotope dilution. These analyses complement and extend earlier isotope dilution REE determinations in chondrites, performed in other laboratories, so that coverage of major chondrite classes is now complete. An examination of this body of precise and comparable REE data from individual chondrites reveals that only a small proportion of the analyses have flat, unfractionated REE patterns within experimental error. A statistical procedure is used to derive revised chondritic abundances of REE by selection of unfractionated patterns. A number of the remaining analyses show Eu anomalies and fractionated patterns consistent with magmatic fractionation as encountered in the products of planetary differentiation. However, many patterns exhibit features not readily explicable by known magmatic processes; in particular, positive Ce anomalies are often encountered. Abundance anomalies can be quantitatively determined by the use of a least-squares curve fitting procedure. The wide variety of anomalous patterns and the uncertainties in model parameters preclude detailed modeling of the origin of anomalies, but it is probable that at least some arise from fractional condensation in the solar nebula, as has been demonstrated for Allende inclusions. Elemental abundance anomalies are found in all major chondrite classes. If these anomalies are ignored, the range and nature of variation within chondrite classes are consistent with a parent body model, in which solid-liquid or solid-solid equilibria induce variations from an unfractionated bulk composition. Absolute abundances in the H, L and LL parent bodies are almost twice those of the E parent body.The persistence of anomalies in chondritic materials relatively removed from direct condensational processes implies that anomalous components are resistant to equilibration or were introduced at a late stage of chondrite formation. Large scale segregation of gas and condensate is also implied, and raises the possibility of bulk variations in REE abundances between planetary bodies.     

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.     

内蒙古科右前旗大石寨组火山岩锆石LA-ICP-MSU-Pb年龄及其形成背景

对大石寨组火山岩的形成时代和形成背景的认识存在较大的分歧。对采自建组剖面底部英安岩样品中的锆石进行阴极发光照相、微区原位LA-ICP-MS微量元素分析和U-Pb测年。锆石U-Pb同位素分析结果显示,锆石发育典型的岩浆震荡环带, 高Th/U(0.51~1.57),轻稀土元素亏损,重稀土元素富集,具有强烈的正Ce异常和强烈的负Eu异常等特征,表明锆石均属于岩浆成因。22个分析点获得的谐和年龄为(314±1)Ma(MSWD=0.88),代表了大石寨组火山岩的形成时代。结合前人的资料,认为大石寨组火山岩为裂陷早期的产物,而晚古生代的沉积岩石组合为在这一基础上发展起来的具有裂陷盆地性质的沉积组合。