福建东部近海生物中稀土元素的生态化学特征

在福建东部海域16个海湾采集了近海生物鱼、虾、贝壳、藻4大类26小类128个样品,用ICP-MS法测定15种稀土元素的含量,结果表明,轻、重稀土元素存在较大的分镏作用,明显富集轻稀土元素,即轻稀土元素的生物学效应更为明显,鱼类等近海生物稀土元素配分模式总体上与海水和世界页岩稀土元素配分模式接近。稀土元素沿福建东部海域食物链的迁移传递没有表现出明显的生物放大作用。     

Determination of Scandium, Yttrium and Rare Earth Elements in Rocks by High Resolution Inductively Coupled Plasma-Mass Spectrometry

The high sensitivity, minimal oxide formation and single internal standard capability of high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS) is demonstrated in the direct determination of Sc, Y and REE in the international reference materials: basalts (BCR-1, BHVO-1, BIR-1, DNC-1), andesite (AGV-1) andultramafics (UB-N, PCC-1 and DTS-1). Time consuming ion exchange separation or preconcentration were found to be unnecessary. Smooth chondrite normalized plots of the REE in PCC-1 and DTS-1 were obtained in the range 0.8-50 ng g-1 (0.01-0.1x chondrite). Method precision was found to be digestion dependent with an average external repeatability of 2-4% for the basalts, AGV-1 and UB-N, and 10% for PCC-1 and DTS-1. The mass peak due to ⁴⁵Sc was completely resolved from ²⁹Si¹⁶O and ²⁸Si¹⁶O¹H spectral interferences using medium resolution, which casts doubt on the accuracy of Sc determinations using quadrupole ICP-MS. Literature values for Y in rock reference materials were found to be approximately 9% high after HR-ICP-MS and XRF analysis.     

The Mobility of Rare Earth Elements and Redox Sensitive Elements in the Groundwater/Seawater Mixing Zone of a Shallow Coastal Aquifer

The concentrations of Rare Earth Elements (REE) and Redox Sensitive Elements (RSE) were measured in groundwaters along a transect of the forest-marsh interface of a surficial aquifer system in North Inlet, SC. The well transect extended from a forest recharge area across the marsh and tidal creek to a tidal recharge area of beach ridge. The concentrations of the RSE (Fe, Mn, and U) were consistent with reducing conditions through the transect. Fe was present at concentrations ranging from a few micromolar to greater than one hundred micromolar in most wells. U was depleted with respect to salinity predicted concentrations, indicating removal with respect to the seawater endmember. Dissolved Mn concentrations were generally low in all wells, indicating no significant solid source of Mn (as MnOx) in this system. When extrapolated to a global scale, estimates of U removal during seawater exchange with the aquifer solids equaled 10–20% of the total riverine dissolved U input flux. REE concentrations in the forest recharge area were high in shallow wells, and showed a light enriched fractionation pattern, characteristic of soil leaching by Natural Organic Matter (NOM) rich waters. A decrease in REE concentration with depth in the forest wells coupled with a trend towards Heavy REE (HREE) enriched fractionation pattern indicated removal of the REE coincident with NOM and Dissolved Organic Carbon (DOC) removal. The saline waters of the beach ridge wells show a Light REE (LREE) enriched fractionation pattern and have the highest overall concentrations of the REE, indicating a significant REE source to the seawater endmember waters. The concentration gradients along the beach ridge flow path indicate a large source in the deep wells, and net export of dissolved REE to the tidal creek system and the coastal ocean. Ultrafiltration experiments indicate a transition from a colloidal dominated reservoir for the REE in the forest wells to a colloidal and dissolved reservoir in the beach ridge wells. The ultrafiltration data coupled with a correlation with Dissolved Inorganic Carbon (DIC) release suggest that there is diagenetic mobilization of an REE rich organic carbon phase in the saline endmember wells. We suggest here that degradation of this relic terrestrial organic carbon and REE rich phase results in the export of dissolved REE equal to or exceeding river inputs in this region.     

Geochemistry of Rare Earth Elements in the Ocean

This work briefly outlines modern ideas on geochemistry of rare earth elements (REE) in the ocean. Sources of REE and chemical properties of these elements, which govern their migration ability in natural processes, are considered. The REE behavior in the river water–seawater mixing zone is analyzed. The fractionation of dissolved and suspended REE in oceanic water in both aerobic and anaerobic conditions is also considered. It is shown that the variability of REE composition in pelagic sediments reflects the fractionation of these elements in the oceanic water as a consequence of material differentiation in the ocean. The REE distribution in terrigenous, authigenic, hydrothermal, and biogenic constituents of sediments, such as clay, bone debris, barite, phillipsite, Fe–Mn oxyhydroxides (ferromanganese nodules and micronodules), Fe–Ca hydroxo-phosphate, diatoms, and foraminifers, is considered.     

典型稀土矿区周边土壤中稀土元素含量及赋存形态研究

研究不同类型稀土矿区周边土壤中稀土元素(REE)的含量与形态特征,可为矿区周边污染环境治理提供理论支持与科学建议。本文采用欧盟BCR顺序提取法、电感耦合等离子体质谱测定的方法,对内蒙古白云鄂博稀土尾矿区和江西赣南稀土矿区周边6个土壤样品中15种稀土元素进行了含量及形态分析测定。结果表明:矿区周边土壤中稀土元素总量约为264～15955μg/g,明显高于全国土壤背景值(186μg/g),白云鄂博尾矿区周边土壤富集轻稀土元素,稀土元素主要以残渣态富集,占总含量的64.0%～89.4%,生物有效性较低,对环境影响较小;赣南矿区周边土壤富集重稀土元素,稀土元素的主要存在形式是弱酸提取态和可还原态,占总含量的70%以上,易发生迁移转化及对周边环境造成污染。土壤中稀土元素的形态分布与pH值有显著相关性,随着土壤pH值的降低,稀土元素的弱酸提取态含量不断升高,残渣态含量不断降低。     

青藏高原砂质表土样品稀土元素特征的初步探讨

青藏高原上的高山作用(包括冰川研磨作用、山体剥蚀作用、山前冲洪积作用等)形成大量松散砂质物质就近分布于青藏高原及周边地区,这成为亚洲粉尘的源区之一.通过对青藏高原部分典型砂质表土样品的稀土元素特征的初步分析.结果表明:青藏高原砂质表土稀土元素特征主要受原岩性质的控制,同时在不同程度上受到风化作用的影响;其稀土含量变化较大,温暖湿润的藏南地区稀土含量较高,气候寒冷干燥地区则相对偏低;稀土元素的球粒陨石标准化分布模式与现代上地壳和中国黄土的稀土元素分布模式相似,均表现为轻稀土富集,Eu相对亏损的模式.     

Rare Earth Element and Yttrium Variability in South East Queensland Waterways

We present data for the rare earth elements and yttrium (REY) in the National Research Council of Canada natural river water reference material SLRS-4 and 19 natural river waters from small catchments in South-East Queensland, Australia, by a direct ICP-MS method. The 0.22 μm filtered river water samples show a large degree of variability in both the REY concentration, e.g., La varies from 13 to 1157 ppt, and shape of the alluvial-sediment-normalised REY patterns with different samples displaying light, middle or heavy rare earth enrichment. In addition, a spatial study was undertaken along the freshwater section of Beerburrum Creek, which demonstrates that ~75% of the total REYs in this waterway are removed prior to estuarine mixing without evidence of fractionation.     

DBC-偶氮氯膦光度法测定地质样品中 15种稀土元素的研究

建立了DBC-偶氮氮膦-稀土元素显色体系,该体系的灵敏度高,摩尔吸光系数为(1.3×104～1.2×105)L@mol-1@cm-1,体系稳定,重现性好,并将偏最小二秉计算法用于数据处理中,较准确地预测出地质样品中15种稀土元素各自的含量,其标准偏差(S)为3.3×104～9.1 × 103,相对标准偏差为0.81%～5.0%;其相对误差一般都小于15%,结果满足微量稀土元素分析的要求.     

Determination of Rare Earth Elements in Geological Reference Materials: A Comparative Study by INAA and ICP-MS

Data was obtained for the rare earth elements (REE) by instrumental neutron activation analysis (INAA) and inductively coupled plasma-mass spectrometry (ICP-MS) in twenty geological reference materials. In general, the precision obtained by ICP-MS is better for the light REE, decreasing with increasing atomic number. This is partly a result of the occurrence of the heavy REE at low concentrations. The precision of the data obtained by INAA is good (5% RSD). The data obtained also showed that for the elements determined by both methods, the accuracy is similar for the light REE and better for the middle and heavy REEs by INAA. Higher uncertainty is achieved by ICP-MS mainly for elements at very low concentrations, occurring at about ten times the chondritic values.     

X射线荧光光谱法测定稀土精矿中的稀土元素分量

氟碳铈矿、独居石、磷钇矿和风化壳淋积型稀土矿四种稀土精矿样品采用化学法预分离富集,X射线荧光光谱法测定样品中稀土元素和伴生的铀、钍元素含量,选择以硼酸盐为主的混合熔剂高温熔融制样,消除矿物间存在的矿物结构影响,通过加大熔剂稀释比降低元素间的基体效应,人工标准样品绘制标准曲线,用数学校正方法校正元素间的谱线重叠效应。对淋积型稀土矿样品重复测定12次,方法检出限为0.9~42.1 μg/g,待测组分的相对标准偏差(RSD)均小于10%,测定结果与电感耦合等离子体质谱法的测定值基本吻合。此方法应用于国家一级标准物质稀土标准样品定值工作,检出限和精密度能够满足分析要求,报出数据被采用率达到100%。     

南海表层沉积物中细粒组分的稀土元素地球化学特征

对南海表层沉积物中的细粒组分进行电感耦合等离子体质谱法测试, 探讨南海稀土元素分布特征及其影响因素.结果表明, 南海表层沉积物中稀土元素分布主要与陆源物质输入、生物活动和火山物质补给密切相关.南海细粒组分的配分模式与中国黄土的接近, 与周边的珠江、湄公河等河流输入物质也有相似性, 而与南海碱性玄武岩存在显著差异, 表明南海沉积物主要来自于周边大陆.稀土元素趋势分析表明, 珠江口往外至海南岛南部海域中沉积物朝东南方向向陆坡输送; 台西南至珠江口往外海域沉积物大多向南输运; 吕宋岛西部海域包括黄岩岛附近海域的火山物质主要向西北方向输送, 向西可达113°E、向北可至20°N附近; 南海南部沉积物整体上向南沙海槽西北部附近海域输送.      

Rare Earth Elements in Coal-Bearing Deposits: Distribution Features and Geochemical Significance

The examination of Lower Cretaceous coals and clayey fractions of terrigenous host rocks of the Zyryanka Basin has revealed a generally negative type of the relative REE distribution (with a predominance of LREE over HREE) and a similar behavior of Th and U. Analogous characteristics are typical for metamorphic and igneous rocks of intermediate composition dominating in the provenance. In terms of the concentration and distribution of REE, Th, and U coal-bearing terrigenous rocks of the Zyryanka Basin are close to Phanerozoic clays and silty sandstones of the Russian Platform, while coals of the Zyryanka Basin are similar to metal-free coals of various basins (Kizel, Pennsylvanian, and others). Average REE and Th contents in the studied coals are five times lower than those in host terrigenous rocks. The coals differ from these rocks by relatively elevated HREE concentrations largely due to adsorption mechanism of the HREE accumulation. Data obtained on the REE, Th, and U distribution in coals and clayey fractions of host rocks are of fundamental significance for the comparitive analysis of the behavior of these elements in metal-bearing coals of various basins.     

渤海西部表层沉积物的稀土元素分布特征与物源约束

对渤海西部44个表层沉积物样品进行电感耦合等离子体质谱法测试,分析了稀土元素(REE)含量,探讨了渤海西部稀土元素分布特征及其物源约束。结果表明,渤海西部表层沉积物的稀土配分模式与中国黄土的接近,表明研究区沉积物主要来自于周边大陆。渤海西部表层沉积物稀土元素富集与粒度效应研究表明,∑REE与Mg、Ti、Co、Cr、Li和细粒沉积物呈明显正相关,而与砂质沉积物呈显著负相关,与Zr无明显正或负的相关性。渤海西部表层沉积物稀土元素参数特征值离散图和Q-型聚类分析结果,可将研究海域沉积物划分为3个不同的地球化学分区,研究区中部和西北部海域为∑REE高值区,其物质主要来源于海河和黄河;研究区南部、东南部沉积物主要来源于黄河物质输入;研究区东北部滦河口外沉积物主要来源于滦河物质。     

四川稀土精矿的稀土元素和微量元素地球化学特征及开发利用意义

四川省是我国轻稀土的重要产地,开采近二十年来生产了大量稀土精矿,精矿的稀土品位及其他有用元素组成对矿山资源评价及企业生存至关重要。本文对A、B、C三个稀土矿区稀土精矿的稀土元素和微量元素组成特征进行了研究。结果表明:不同矿区、不同选矿方法、不同企业生产的精矿,其稀土元素和微量元素含量存在显著差异;A矿区浮选精矿的稀土含量最低(ΣREEs=41.57%),而C矿区精矿的稀土含量最高(ΣREEs=55.83%);A矿区磁选精矿的稀土含量(ΣREEs=49.96%)高于浮选精矿(ΣREEs=41.57%);B矿区甲公司(ΣREEs=48.35%)精矿产品的稀土含量高于乙公司精矿产品(ΣREEs=42.92%)。精矿的稀土元素配分特征继承了原矿石的同时普遍亏损Tb和Yb,推测是选矿过程导致了元素的亏损。精矿中除了富集稀土元素,Mo、Bi、Pb、Ga、Th、U、W等有用元素也发生了不同程度的富集,综合利用价值高,尤其是Mo(0.56%)和Ga(0.036%)的含量已达到现行边界品位。本文提出,今后在提高精矿稀土品位的同时,需对富集的元素采取恰当的方式加以综合回收。     

四川稀土矿尾砂的稀土元素和微量元素地球化学特征及开发利用意义

四川是我国轻稀土的重要产地,稀土开采至今已有二十多年的历史,积存了大量尾砂。尾砂中仍然有丰富的稀土资源,但这部分资源究竟有多大的量、能不能再次回收,如何回收,则是当务之急。为查明稀土尾砂中各类元素的分布特征,本文对A、B、C、D四个稀土矿山的尾砂开展了稀土元素和微量元素地球化学特征的初步研究。结果表明:尾砂中稀土元素配分特征继承了原矿石,稀土氧化物含量普遍偏高(0.78%~2.12%),均超过了现行工业指标的边界品位(0.5%~1.0%),且老尾砂的稀土含量高于新尾砂;除了富集稀土元素之外,B尾砂中Sr含量超过10%,C矿区尾砂中Sr含量为2.7%,A矿区尾砂中Ba含量可达1.8%。同时,不同矿区的尾砂中Mo、Bi、Pb、Ag等有用元素发生了不同程度地富集(值得综合回收利用),尤其是Mo达到了边界品位(磁选后的尾砂Mo含量达到2.275%)。本文提出,今后不仅要加强保护四川稀土尾砂,而且需对富集的有用元素采取恰当的方式加以综合回收。     

Comparison of Supercontinent Cycles in the Metallogeny of Rare Earth Elements

The distribution of integrated resources of large and superlarge deposits (LSLDs) of rare earth elements (REEs) is compared to the current model of supercontinent cyclicity during Earth’s evolution. It is found that REE LSLDs are related predominantly to igneous complexes (carbonatite, nepheline syenites, syenite-alkaline granites, subalkaline granites), which are often additionally enriched in the hypergenic zone. A certain part of the resources is concentrated in independent hypergenic formations represented by placers and ion-adsorbed clays. Each supercontinent cycle—Kenoran, Columbian, Rodinian, Pangean, and Amasian—is expressed in the REE metallogeny in particular way: we revealed significant intercycle variations in the amount of REE LSLDs, the variety of their types, total accumulated resources, and some other characteristics.     

三稀元素矿床类型及找矿标志

"三稀"元素是当前乃至今后一段时期地质勘查的热门矿种之一。通过对"三稀"元素组合及矿物组合规律的研究,根据成矿地质作用和成矿方式,将"三稀"元素矿床分为七个成矿系列、十四种成因类型,并重点介绍了与岩浆活动有关稀有稀土矿产特征;在此基础上,从控矿条件和矿化指示两方面总结出稀有稀土元素矿床的找矿标志,供广大地质工作者在地质找矿工作中参考。     

碱熔沉淀分离-电感耦合等离子体质谱法测定伴生重晶石稀土矿中的稀土元素

采用电感耦合等离子体质谱法(ICP-MS)测定伴生重晶石轻稀土矿中的稀土元素时,Ba以及轻稀土元素La、Ce、Pr、Nd、Sm等对中重稀土造成严重的质谱重叠干扰,因此在保证矿石完全消解的同时,若能选择合适的前处理方法实现目标元素与基体的有效分离,将有利于减少质谱干扰。本文采用过氧化钠-碳酸钠熔融分解伴生重晶石的稀土矿样品,熔融物用三乙醇胺溶液提取,将沉淀过滤去除硅、铁、锰、铝等大量基体元素,而稀土元素与钡、锶、钙等留存于沉淀中,沉淀经盐酸溶解后再用氨水进行二次沉淀,将稀土元素与伴生的高含量钡、锶、钙等元素分离,分离率超过96%,从而极大地降低了由钡的氧化物和氢氧化物对~(153)Eu等元素质量数的质谱干扰。轻稀土元素对中重稀土元素的干扰则通过测定高浓度的单元素标准溶液在m/z 138～175处的表观浓度来计算干扰校正系数,对干扰量进行扣除校正。该方法通过稀土矿石标准物质GBW07187、GBW07188验证,测定值与认定值的相对误差10%;应用于伴生重晶石稀土矿石实际样品分析,相对标准偏差(RSD,n=12)为0.5%～4.6%,证明了本方法可用于分析高钡矿石中的稀土元素。     

赣南稀土精矿粉配制的稀土溶液反射波谱特征研究

赣南离子吸附型稀土矿是我国重要的稀土资源,本文运用美国ASD FieldSpec-3便携式地物波谱仪,对赣南寻乌稀土矿区稀土精矿粉配置的25个稀土溶液样品进行波谱测试,获取了不同稀土含量的波谱特征,结果表明溶解在水体中的稀土元素在可见光-近红外574 nm、790 nm、736 nm、520 nm、861 nm、443 nm等波段具有多个明显的稀土特征吸收谷及若干次级的稀土特征吸收谷;通过与15种稀土单元素波谱特征对比分析,可见这些吸收特征主要由一种或几种稀土单元素引起;随着稀土浓度的降低,这些吸收特征逐渐减弱甚至消失。这一研究进一步加深了对我国赣南稀土溶液波谱特征的认识,同时为赣南稀土元素的高光谱遥感研究奠定了理论基础。     

Rare and Rare Earth Elements in Lateritized Bauxites of the Chadobets Uplift (Siberian Platform)

Doklady Earth Sciences - The mineral and chemical composition of bauxites from the Chadobets uplift of the Siberian Platform is the total product of laterites on aluminosilicate rocks (source of...