湘江下游河床沉积物稀土元素分布与污染特征

稀土元素是一种新型环境污染物，其环境危害近年来备受关注。本研究利用电感耦合等离子质谱仪(ICP-MS)测定了湘江下游河床沉积物稀土元素含量，分析沉积物稀土分布特征，评价沉积物稀土污染程度，并对沉积物稀土污染进行生态危害预测分析。结果表明，湘江下游河床沉积物的稀土元素含量较高，其总稀土(ΣREE)含量为106～775 mg/kg(均值为319 mg/kg)。但自株洲河段向下游湘阴段，稀土元素含量明显降低。株洲等各河段沉积物的稀土配分模式都为轻稀土富集的上地壳稀土配分模式。根据沉积物的Eu/Eu^*值，将湘江下游河床沉积物分为页岩型(S-型)和花岗岩型(V-型)两类稀土配分模式。其中V-型稀土模式沉积物的ΣREE为118～775 mg/kg,(均值为370 mg/kg),明显高于S-型稀土模式沉积物的ΣREE(106～396 mg/kg,均值为292 mg/kg),显示V-型的人为源带入特征。地累积指数评价显示，湘江下游河床沉积物的稀土元素污染达轻度到中度污染水平，主要发生在株洲、湘潭河段的沉积物中。潜在生态风险指数评价显示沉积物稀土污染达中度生态风险危害水平，应高度注...     

吉林省桦甸油页岩中稀土元素和微量元素的研究

对桦甸油页岩及其灰渣的矿物成分、主量元素、稀土元素和微量元素含量进行测定。结果表明：油页岩中稀土元素含量低于北美页岩(NASC)中的平均含量,REE球粒陨石标准化的分布模式曲线表现为负斜率,(La/Yb)_N的平均值大于1,属于轻稀土富集型;REE北美页岩标准化的分布模式曲线较平缓,（La/Yb）_S的平均值接近于1,轻重稀土分馏不明显。与球粒陨石和北美页岩相比,Eu有较严重的正异常。油页岩中的微量元素与北美页岩和地壳的平均值相比较,Sb、Nb、Cs、Zn、Bi、W等元素具有较高的富集度。油页岩灰渣中稀土元素和微量元素富集度均高于油页岩。     

曼达岬海盆渐新世-中新世沉积物的稀土元素组成及其物源指示意义

为了探究东南印度洋曼达岬海盆(Mentelle Basin)内沉积物的源-汇过程,利用国际大洋发现计划(IODP)369航次在该海盆内获取的渐新世-中新世岩心沉积物,进行了稀土元素(REE)组成特征及其控制因素和物源指示意义的研究.结果显示,与球粒陨石、上地壳(UCC)和澳大利亚后太古代页岩(PAAS)这三种标准物质相比,所研究沉积物的稀土元素含量(ΣREE)与轻/重稀土含量比值(ΣLREE/ΣHREE)等总体特征与UCC最为相近,其UCC标准化后的稀土元素配分模式则呈现出轻稀土稍富集的整体平缓特征.样品的ΣREE与稀土分馏指标(La/Yb)_UCC和(Gd/Yb)_UCC明显受控于粒度效应与风化作用,而ΣLREE/ΣHREE、δEu、(La/Sm)_UCC和(Sm/Nd)_UCC则基本不受上述两种作用的影响.UCC标准化后的稀土元素配分模式、基于稀土元素组成的物源判别函数以及Zr-Th-Sc物源判别三角图均表明伊尔冈克拉通是所研究沉积物最可能的物源区,并且该物源区的主要源岩在13 Ma时由中基性岩向酸性岩...     

贵州织金新华含稀土磷矿床稀土元素地球化学研究

对贵州织金新华含稀土磷矿床进行的稀土元素及微量元素分析结果表明,磷块岩中普遍富集稀土元素,含稀土总量∑REE较高,并富集Y、La、Nd等重稀土及轻稀土元素.LREE/HREE比值较高,但低于上部围岩之值.含稀土磷块岩普遍具Ce的负异常,显示其对源区的继承性,也指示成磷环境处于氧化程度相对较高状态.稀土元素球粒陨石标准化模式曲线、北美页岩标准化模式曲线、Ce元素异常、LREE/HREE比值、微量元素特征及岩石矿物特征表明,织金新华含稀土磷矿床具以正常海相生物-化学沉积等为主伴有海相热水沉积混合成因的特征.文中讨论了含稀土磷块岩氧化矿石中稀土元素的迁移富集规律及特征.     

湘江悬浮物REE地球化学特征

在湘江长、株、湘潭河段采集悬浮样,利用ICP-MS进行REE分析.结果表明,湘江长株潭断及各河段的河心与两岸水体悬浮物中稀土分布不均匀;稀土分布模式基本相同,均为LREE相对HREE富集,曲线呈明显的右倾状,且与长江、黄河的稀土分布模式相似;Eu、Ce亏损在各河段基本相同,表明湘江悬浮物中的REE主要来源于沉积岩的风化产物,外源性稀土的污染不是很显著.     

中国稀土元素地球化学背景与远景区优选

稀土元素是现代科技、新能源、特种制造的关键性材料, 以其不可替代性和稀缺性, 而备受关注, 很多国家将其列为关键资源或战略资源。地球化学是研究稀土分布和发现稀土矿床的有效方法。本文利用“化学地球”大科学计划获得的全国15个稀土元素地球化学基准数据以及“一带一路”的中蒙边境、中缅老越边境地区地球化学填图数据为基础, 阐述中国稀土地球化学背景和圈定远景区。获得全国岩石和汇水域沉积物15个稀土元素、轻稀土(ΣLREE)、重稀土(ΣHREE)和总稀土(ΣREE)背景值。全国岩石背景值分别为: ΣLREE 121 μg/g, ΣHREE 35.0 μg/g, ΣREE 157 μg/g, 轻重稀土比值为3.5。全国汇水域沉积物背景值分别为: ΣLREE 134.0 μg/g, ΣHREE 38.5 μg/g, 和ΣREE 173 μg/g, 轻重稀土比值为3.5。总体上汇水域沉积物与岩石一致, 但含量略高于岩石。全国共圈定稀土地球化学异常区35处, 其中有26处异常与已知稀土矿或稀土成矿带相吻合, 新发现稀土超富集中心的稀土异常9处, 分别位于内蒙白云鄂博以西的乌拉特中旗—乌拉特后旗、华南异常富集中心、松潘—甘孜—攀西地区、云南红河州—中越边境、三江南段—中缅边境、雅鲁藏布江东段、西藏札达地区、中塔边境、黔东正安—荔波地区。这些异常显示, 是具有寻找白云鄂博型、碱性岩型、离子吸附型、花岗伟晶岩型、磷块岩型和泥岩型稀土矿的有利地区。     

羌塘盆地那底岗日地区布曲组碳酸盐岩烃源岩稀土元素分布特征及意义

对采自羌塘盆地那底岗日地区布曲组碳酸盐岩烃源岩进行了稀土元素地球化学研究,分析结果表明:海相碳酸盐岩烃源岩稀土总量(∑REE)最大值75.21μg/g,最小值20.58μg/g,平均值为36.67μg/g.稀土元素北美页岩标准化后具有相对富集轻稀土,亏损重稀土的特点.布曲组碳酸盐岩烃源岩Ce/Ce*值为0.83～0.9...     

龙感湖稀土元素的地球化学特征

采用液-液萃取法,连续提取法和ICP-MS测试技术,对龙感湖不同季节水和颗粒物中稀土元素进行研究.结果表明,龙感湖的溶解态稀土含量极低,稀土总含量(ΣREE)在3.14～129.81ng/kg之间,且季节性变化明显.龙感湖溶解态稀土元素表现出平坦型的页岩配分模式,这是由于在草型湖泊中溶解态稀土主要以吸附在微细胶体上的形式存在,水粒相互作用在这个过程中起主要控制作用.悬浮物中的稀土含量顺序为:残渣态>>Fe-Mn结合态>>有机态和AEC态,颗粒物中稀土元素主要以残渣态形式存在.Fe-Mn结合态、有机态和AEC态的页岩配分模式为中稀土富集,残渣态的页岩配分模式为平坦型.这说明中稀土与轻重稀土相比具有更强的潜在地球化学活性,但在龙感湖的环境中的迁移能力相对轻重稀土来说较弱.     

贵州织金新华含稀土磷矿床稀土元素地球化学及生物成矿基本特征

对贵州织金新华含稀土磷矿床进行的稀土元素及微量元素分析结果表明，磷块岩中普遍富集稀土元素，稀土总量∑REE较高，并富集Y元素及La，Nd等轻稀土元素。LREE／HREE比值较高。含稀土磷块岩普遍具Ce负异常，显示其对源区的继承性。指示成磷环境处于氧化程度相对较高状态。稀土元素球粒陨石标准化模式曲线、北美页岩标准化模式曲线、Ce元素异常、LREE／HREE比值、微量元素特征及岩石矿物特征表明，织金新华含稀土磷矿床具以正常海相生物-化学沉积等为主伴有海相热水沉积混合成因的特征。在磷矿成矿过程中沉积物沉积时，活体生物及死亡残骸不同程度地摄取和富集了La，Nd，Ce等稀土元素、Y元素及其他微量元素，沉积在含磷层位，构成大量的含稀土、含生物碎屑白云质磷块岩。     

黔中小流域水体悬浮物与沉积物微量元素地球化学特征及物源指示

系统探讨了黔中小流域水体悬浮物和沉积物中微量及稀土元素地球化学特征。结果表明,元素含量在河流与湖泊、悬浮物与沉积物之间均存在明显差异。稀土元素北美页岩标准化分布模式大致为轻稀土相对富集的平坦模式,δEu为0.82～1.25,δCe为0.79～1.25,整体变化不大,均表现为弱异常。麦翁河稀土总量与分布模式均发生异常,主要受上游盘龙煤矿影响。悬浮物的∑REE与pH呈反相关关系,而沉积物的∑REE却与pH表现出正相关关系,表明悬浮物与沉积物中稀土元素行为的控制因素不同。元素相关分析、因子分析及微量元素图解均表明悬浮物与沉积物中的元素具有同源性,主要来源于流域岩石化学风化和土壤物理侵蚀的产物,而某些金属元素Zn、Co、Cu、Cr、Ni则来源于周边工矿企业、农业生产等人为排放。本研究丰富和发展了喀斯特地区水体元素地球化学,揭示了小流域化学风化与物理侵蚀过程中的元素特征和物质输送状况,并为该流域的生态环境现状、治理及管理提供了科学依据和基础资料。     

Geochemistry of rare earth elements in the mainstream of the Yangtze River,China

Water, suspended matter, and sediment samples were taken from 8 locations along the Yangtze River in 1992. The concentration and speciation (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual forms) of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) were determined by instrumental neutron activation analysis (INAA).The contents of the soluble fraction of REEs in the river are low, and REEs mainly reside in particulate form. In the particles, the chondrite-normalized distribution patterns show significant LREE enrichment and Eu-depletion. While normalized to shales, both sediments and suspended matter samples show relative LREE enrichment and HREE depletion. REEs are relatively enriched in fine-grained fractions of the sediments.The speciation characteristics of REEs in the sediments and suspended matter are very similar. The amount of the five forms follows the order: residual>>bound to organic matter∼bound to Fe–Mn oxides>bound to carbonates>>exchangeable. About 65 to 85% of REEs in the particles exist in the residual form, and the exchangeable form is very low. High proportions of residual REEs reveal that REEs in sediments and suspended matter are controlled by their abundances in the earth's crust. Carbonate, Fe–Mn oxide and organic fractions of REEs in sediments account for 2.4–6.9%, 5.2–11.1%, and 7.3–14.0% of the total contents respectively. They are similar to those in the suspended matter. This shows that carbonates, Fe–Mn oxides and organic matter play important roles during the particle-water interaction processes. By normalization to shales, the 3 forms of REEs follow convex shapes according to atomic number with middle REE (Sm, Eu, and Tb) enrichment, while light REE and heavy REE are depleted.     

Rare Earth Element Geochemistry of Late Palaeozoic Coals in North China

Instrumental Neutron Activation Analysis (INAA) was done to determine the abundances of rare earth elements (REE) of 58 samples of Late Palaeozoic Carboniferous-Permian coals and related rocks in North China. Detailed study of REE geochemistry shows that the ∑REE of most coals studied in this paper is in a normal range between 30×10-6 and 80×10-6 with a mean of 56×10-6. The REE in the Taiyuan Formation in the northern part of North China are much richer than those in the southern part. This is due to the shorter distance to the source area in the north. Moreover, the IREE is in positive correlation to coal ash, especially closely related to the content of clay minerals <2μm in size. This reveals that most REE were carried by terrigenous clastic materials, especially fine clay minerals. In the coals the light REE (LREE) are much richer than the heavy REE (HREE), and the LREE/HREE ratio in coals generally varies from 2 to 8. The LREE/HREE ratio of high-ash, low-sulphur coals is higher than that of lo     

Behavior of rare earth elements during mixing of different types of water (Kunashir,the Kurile Islands)

The fractionation of rare earth elements (REE) was evaluated under the conditions of natural acidic water mixing with fresh and sea waters using the example of unique objects on Kunashir Island (the Kislaya and Lesnaya rivers). It was shown that the concentrations and fractionation of REE in the water types considered are diverse and controlled by a number of factors. The concentrations of dissolved REE normalized to the North American Shale Composite show an increase from the light to the heavy REE, which reflects both the character of the REE input with the thermal waters and the more active sorption of the light REE and their preferential removal to suspended solids. This is supported by the similar REE patterns in the suspended matter of the Kislaya River. The mixing of the waters of the Kislaya and Lesnaya rivers, which are assigned to different chemical types, is accompanied by active REE coprecipitation with Fe, Al, and Mn oxides and the more extensive removal of the light REE compared with the heavy REE. During acidic water mixing with seawater, more than 80% of the REE were precipitated at a salinity of 8‰.     

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.     

The REE Characteristics of Oil Shales in the Lower Eocene Celtek Formation (Yozgat,Turkey) and their Relation to Tectonic Provenance

The Lower Eocene Celtek Formation is located in the Sorgun district of thecity of Yozgat in Turkey.In the study area,Paleozoic,Campanian-Maastrichtian,Eocene,Miocene and Quaternary units are exposed.The Celtek Formation is noteworthy with its coal and oil shale deposits.Samples were collected from one exposure(YCOSK)and two boreholes(SJ and C boreholes)at the facility operated by the Yeni Celtek Coal Management.Concentrations of REE in oil shales from these localities were determined using the ICP-MS technique.REE and total organic carbon(TOC)values of a total of 32 samples were compared with normalized REE contents of various environments.TOC contents of the samples ranged from 1.37wt%to 11.8wt%(mean 4.96wt%).The averages of all samples for the all normalized values show similar patterns.Normalized REE patterns are represented by the enrichment in the order of LREE>MREE>HREE and display negative Ce and positive Eu anomalies.ΣREE vs.TOC were compared.ΣREE vs.TOC showed a weak positive correlation,whereasΣLREE vs.(M+HREE)andΣLREE vs.ΣREE were positively correlated.Regarding tectonic provenance characteristics,the Celtek Formation oil shales were formed in microenvironments with physicochemical conditions changing in character from oxic to euxinic,representing a transitional terrestrial–marine environment.     

长江与黄河沉积物稀土元素随粒度变化对比研究

依据Stoke定律将长江小于63 μm的沉积物分成4个粒级.将黄河小于63 μm的沉积物分成6个粒级.采用ICP-MS法分别测试了分粒级沉积物的REE含量,结果显示：相同粒级中长江沉积物的∑REE均高于黄河沉积物.长江沉积物REE的丰度遵循元素的“粒度控制律”,即随粒度变细∑REE含量依次增高;黄河沉积物∑REE呈“高-低-高”的不对称马鞍型分布;北美页岩标准化分布曲线均呈右倾状,轻重稀土分馏明显,相对富集LREE,具弱Ce亏损,明显的Eu正异常.长江与黄河沉积物REE组成特征差异与两条河流流域的风化作用及沉积物的矿物组成密切相关,黄河∑REE的马鞍型分布是细粒级中黏土矿物吸附及粗粒级中相对高含量的重矿物富集作用的结果,而长江沉积物随粒级增大∑REE的衰减趋势主要是随粒级增大逐步增加的石英和长石含量的稀释作用所造成.     

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.     

长江与黄河沉积物REE地球化学及示踪作用

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

中、下扬子地区下寒武统黑色页岩微量元素富集特征

中国南方扬子地区下寒武统黑色页岩分布广泛,主要由黑色页岩、黑色白云质页岩,黑色粉砂质页岩和黑色硅质页岩等组成;并伴生有较厚的磷块岩矿床、钒矿床和镍、钼多元素硫化物矿床。对黑色页岩岩石学特征、元素地球化学特征进行系统研究,并详细分析微量元素的富集成因,结果表明：黑色页岩主要形成于静水还原的浅海-半深海缓坡环境,层状元素富集带为沉积成因,海底热流体提供了丰富物质来源。总体上,Co、Be、Mn、Ga等元素含量较低;Cu、V、Ni、Mo等元素的含量较高,多数超过北美页岩平均值;以Ni、Mo为主的多元素富集层通常位于磷块岩之上,以黑色页岩、黑色白云质页岩中的硫化物和硫酸盐矿物为主要载体,其中有机碳（TOC）含量可达12.2%以上,远高于其他元素富集层,随着页岩内硅质成分增加,Ni、Mo、Fe、Co等元素含量明显降低;以V为主的多元素主要赋存于黑色硅质页岩中的水云母,与页岩内硅质成分具有较好的正相关关系;黑色页岩中稀土元素含量为(76.22~290.67)×10-6,轻重稀土比值LREE/HREE介于1.21~4.22,说明轻稀土更为富集,Sr/Ba值为0.04~0.34,δEu正异常,且北美页岩标准化配分曲线呈现平缓左倾,为沉积过程中存在海底热水流体提供了进一步证据。