Geochemical Behaviors of REE and Other Trace Elements during the Formation of Strata-bound Skarns and Related Deposits: A Case Study of the Dongguashan Cu (Au) Deposit, Anhui Province, China

REE and other trace elements in the altered marbles, massive skarns and ores, as well as garnet and quartz were determined in order to examine the behaviors of trace elements during hydrothermal alteration. It is demonstrated that the high-field-strength (HFS) elements Zr, Hf, Th and Nb were immobile while other trace elements were mobile during the formation of skarns and related deposits. REE and ore-forming elements such as Cu and Ag in hydrothermally-altered marbles and skarns were provided primarily by hydrothermal fluids. In the direction transverse of the strata, the more deeply the marbles were altered, the higher the total REE abundance and the larger the negative Eu anomalies would be. The chondrite-normalized REE patterns of skarns are similar to those of the marbles, but the former are distinguished by much higher REE contents and more remarkable negative Eu anomalies. Those patterns were apparently not inherited from the marble protolith, but were controlled by garnets, which were determine     

我国台湾浅滩海底沉积物稀土元素地球化学

REE geochemistry of sea-floor sediments from the Taiwan Shallow has been studied.∑ REE of 76 samples from the Taiwan Shallow was determined by chemical extraetion-spectrophotometry, of which 7 samples were analyzed for 15 rare earth elements by XRF. The analytical results show that ,∑ REE of the samples increases gradually with a decrease in grain size. The average REE contents are 60 ppm for coarse-grained sediments,82 ppm for medium-coarse-grained ones, 145 ppm for fine-grained ones, and 211 ppm for silt. The REE content of the samples is controlled mainly by the grain size and mineralogical composition of sediments. The ehondrite-normalized REE distribution patterns in sediments from the Taiwan Shallow are similar to those in granites in Fujian Province, China, which show a negative Eu anomaly and a positive Ce anomaly. The distribution curves are negative in slope. It is considered that based on REE geochemical characteristics, mineralogical composition and related oceanographic information, the Taiwan Shallow sediments seem to be largely residual deposits of ancient littoral facies from various types of continental rocks during Pleistocene glacial period. These sediments have also been reworked by modern sedimentatoion.     

黄土中稀土元素的初步探讨

REE oxides in loess are estimated to amount to about 200 ppm. The REE distribution patterns in loess and its clay fraction are characterized by the enrichment of rare earth elements of Ce family. The REE distribution patterns of loess in the middle Huanghe (Yellow River) Valley are consistent with those of sands from the Tengeli desert, probably indicating the consistency of their material sources. The REE distribution patterns are similar to each other in the elay fractions of Malan loess everywhere in the middle Huanghe Valley, indicating the homogeneity in their composition. Close to the average value of the earth‘s crust, the REE distribution patterns in loees and its clay fraction are similar to that of sedimentary rocks (e.g., North American shales), but different from that of chrondrites. It seems to show that large amounts of loessic material were transported from the provenance by moving water into sedimentarysy stems after it had been separated from its precursor, and then transported by wind to where it is now distributed.     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.     

Geochemistry and Modes of Occurrence of Hazardous Trace Elements in the No. 11 Coal Seam, Antaibao Surface Mine, Shanxi Province

Concentrations of seventeen hazardous trace elements including As, Pb, Hg, Se, Cd, Cr, Co, Mo, Mn, Ni, U, V, Th, Be, Sb, Br and Zn in the No.ll coal seam, Antaibao surface mine, Shanxi Province were determined using Instrumental Neutron Activation Analysis （INAA）, Inductively Coupled Plasma Atomic Emission Spectrometry （ICP-AES）, Cold-Vapor Atomic Absorption Spectrometry （CV-AAS） and Graphite Furnace Atomic Absorption Spectrometry （GF-AAS）. Comparisons with average concentrations of trace elements in Chinese coal show that the concentrations of Hg and Cd in the No. 11 coal seam, Antaibao surface mine are much higher. They may be harmful to the environment in the process of utilization. The variations of the trace elements contents and pyritic suffur in vertical section indicated that： （a） the concentrations of As, Pb, Mn, and pyritic sulfur decrease from roof to floor; （b） the concentrations of Cr, Zn and Mo are higher in roof, floor and lower in coal seam; （c） the concentration of Br, Sb, and Hg are higher in coal seam and lower in roof and floor; （d） the concentrations of Mo, V, Th and AI vary consistently with the ash yield. Cluster analysis of trace elements, pyritic sulfur, ash yield and major elements, such as AI, Fe, P, Ca shows that： （a） pyritic sulfur, Fe, As, Mn, Ni, Be are closely associated and reflect the influence of pyrite; （b） Mo, Se, Pb, Cr, Th, Co, Ca and A! are related to clay mineral, which is the main source of ash; （c） U, Zn, V, Na, P maybe controlled by phosphate or halite; （d） Hg, Br, Sb and Cd may be mainly organic-associated elements which fall outside the three main groups. The concentration distribution characteristics of trace elements in coal seam and the cluster analysis of major and trace elements showed that the contents of trace elements in the No. 11 coal seam, Antaibao surface mine, are mainly controlled by detrital input and migration from roof and floor.     

Modes of Occurrence and Cleaning Potential of Trace Elements in Coals from the Northern Ordos Basin and Shanxi Province, China

Based on the analyses of 43 elements in 16 samples of the raw coal and feed coal collected from the northern Ordos basin and Shanxi Province, the modes of occurrence of these elements were studied using the method of cluster analysis and factor analysis, and the cleaning potential of the hazardous elements relatively enriched in the coals was discussed by analyzing six samples of the cleaned coal from the coal-washing plants and coal cleaning simulation experiments. The results shows that the elements Br and Ba show a strong affinity to the organic matter, Cs, Cd, Pb, Zn and Hg partly to the organic matter, and the other trace elements are mainly associated with the mineral matter. Cs, Mo, P, Pb, Zn and S have positive correlations with the two principal factors, reflecting the complexity of their modes of occurrence. Some elements that were thought to show a faint relationship (Be with S and Sb with carbonates) in other rocks are found to have a strong interrelation in the coals. Clay minerals (mainly k     

Geochemistry of sulfur and hazardous trace elements in coals and its bearing on human health

Hazardous air pollutants, including compounds of sulfur and toxic trace elements, are emitted during coal combustion. Geochemical studies of these constituents in coals provide information about their species, regional distribution and origins. The data are useful in understanding the cause and scope of human health problems related to these hazardous elements and in designing preventive or remedial measures. Sulfur in coal is a problem because sulfur dioxide emitted during coal combustion is a main source of acid rain. The sulfur isotopic evidence shows that sulfur in low-sulfur coal is derived primarily from parent plant materials. Sulfur enrichment in medium- and high-sulfur coals is caused by the sulfate in seawater that flooded the peat swamp during coal formation. The sulfur content of a coal is controlled primarily by the depositional environment of coal seams. Only pyritic sulfur can be removed by physical coal cleaning processes （coal preparation）. Sulfur dioxide emission can be reduced using clean coal technologies, such as flue-gas desulfurization, fluidized-bed combustion, and integrated gasification and combined cycle.     

REE Geochemistry of Surficial Sediments from the Yellow Sea of China

REE geochemical studies of surficial sediment samples from the Yellow Sea of China have shown:(1)The average content of RE2O3 in the Yellow Sea sediments is 175 ppm,close to that in the East China Sea sediments.The REE distribution patterns in the Yellow Sea sediments are also similar to anomalies.These REE characteristics are typical of the continental crust.(2)The contents of REE are controlled mainly by the sediment grain size,i.e.,REE contents increase gradually with decreasing sediment grain size.REE are present mainly in clay minerals.In addition,REE contents are controlled obviously by heavy minerals.REE abundances in heavy minerals are much greater than those in light minerals.(3)Correlation analysis shows that REE have a close relationship with siderophile elements,especially Ti,which has the largest correlation coefficient relative to REE.Terrigenous clastic materials subjected to weathering and transport are suggested to be the main source of REE in the Yellow Sea sediments.     

Geochemical characteristics of the coal gangues from the Du’erping coal mine,Xishan coalfield,North China

Inductively coupled plasma mass spectrometry, inductively coupled plasma optical emission spectroscopy, hydride generation-atomic fluorescence spectrometry, emission spectrometry, X fluorescence spectrometry, and X-ray diffraction were employed to study the geochemistry and mineralogy of coal gangues from Nos. 2, 3, and 8 coal seams of the Du’erping coal mine, Xishan coalfield, Taiyuan, Shanxi Province. The study revealed that compared with the sedimentary cover, upper continent crust, Carboniferous-Permian coal from North China, as well as most coal in China, coal gangues from Nos. 2 and 3 coal seams are rich in Li, Be, Sc, Cr, Cu, Ga, Ba, Th, Nb, Cd, Pb, Ta and rare-earth elements, and coal gangues from No. 8 coal seam are rich in Li, Sc, V, Cr, Ga, U, and rare-earth elements. Compared with the Carboniferous-Permian coal from North China and most coal in China, coal gangues from Nos. 2, 3 and 8 seams are rich in Rb, V, Cs and Sr. Therefore, The Du’erping coal gangues in the Xishan coalfield are rich in most hazardous trace elements and rare-earth elements, wherein the contents of Ga and Li reach the industrial grade and have significance for industrial utilization. On the whole, coal gangues of the Shanxi Formation from the Permian are rich in more trace elements than those of the Carboniferous Taiyuan Formation. The distributions of REE show obviously dipping rightwards with negative Eu anomalies. The contents of rare-earth elements in the three seams are quite different. All of the above indicate that the source of the rare-earth elements is terrigenous debris. Minerals in No. 2 seam identified by X-ray diffraction mainly include quartz, kaolinite, in addition to calcite, pyrite, apatite, epidote, and epsomite. No. 3 seam mainly contains quartz, kaolinite, in addition to a small amount of sodium feldspar, calcium nitrate, iron ore, gypsum, and vivianite. No. 8 seam mainly contains kaolinite, dickite, quartz, illite, and a small amount of hematite and U. The correlations between major elements and trace elements in coal gangues of the Du’erping coal mine analyzed by using SPSS (Statistical Product and Service Solutions) indicate that the trace alkali elements and rare-earth elements occur mainly in such clay minerals as kaolinite.     

Occurrence and migration of hazardous trace elements in coals from Guizhou Province, China

Coals from Guizhou Province, Southwest China, attract many researchers＇ attention for their high concentrations of hazardous trace elements, sulphur and mineral components. Trace elements in coals have diverse modes of occurrence that will greatly influence their migration in the process of coal preparation. Mode of occurrence is also important in determining the partitioning during coal combustion. The coal floatation test by progressive release was used to study the migration of trace elements and mineral components in the process of froth floatation. Inductively coupled plasma mass spectrometry （ICP-MS） was used to determine the absolute concentrations of trace elements including As, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Th, U, V and Zn in the parent coals and the floatation fractions. Precise determination of the mineral matter percentage in coals was obtained by low-temperature ashing. The mineral compositions in coals were quantified using Rietveld-based X-ray diffraction analysis package on low-temperature ash. Scanning electron microscope equipped with energy dispersive X-ray detector was used to provide information on the forms of occurrence of mineral components in coal. Five floatation fractions were obtained from the pulverized coal samples. The contents of trace elements and mineral components decrease from the first tailings to the last cleaned coal. The concentrations of trace elements and mineral components in parent coals and different floatation samples show that trace elements and mineral components are mainly concentrated in the first tailings samples. Nearly 60% of mineral components are enriched in the first tailings, whereas less than 1.3% remains in the cleaned coal. The ratio of sixteen trace elements concentrations in the first tailings to the corresponding concentrations in the cleaned coal ranges from 1.6 to 22.7. Quantitative mineralogical analysis results using the full-profile general structure analysis system （GSAS） showed that the main compositions of LTA include quartz, calcite, kaolinite, pyrite, chlorite, montmorillonite, illite, anatase and pyrite.     

晋北中高硫煤中稀土元素的地球化学特征

应用中子活化分析方法，测定了晋北两层中高硫煤中稀土元素的含量。通过对稀土元素的分布模式，相关分析和聚类分析的研究，得出如下认识；成煤环境对稀土元素的含量具有控制作用。但中高硫煤中稀土元素总量会受到沉积期后酸性溶液下渗淋滤作用的影响；同一煤层中各分层的稀土元素应具有基本相同的分布模式，异常的稀土元素分布模式指示了沉积期后地质作用的影响；煤中稀土元素的主要赋存状态为无机相，主要来源为陆源碎屑矿物；煤中与稀土伴生的有害元素有V，P，Mo,Cr,Cu,Mo,Th和Cd等，在加工洗选过程中有洁净潜势。     

陈家山矿煤中微量元素和稀土元素地球化学特征

通过对陈家山煤矿中下侏罗统延安组4#主采煤层中微量元素和稀土元素的测试分析,发现煤中富集亲花岗岩的钨钼族元素W、Mo、Bi、Sn、Ba、Sr和Li,说明该区煤系形成期间的陆源碎屑主要来自花岗岩和花岗片麻岩等中、酸性岩石。4#煤中ΣREE平均值为98.2×10-6,稀土元素分布模式十分相似,呈左高右低的宽缓“V”型曲线,Eu负异常明显,反映出稀土元素与陆源碎屑岩关系密切,成煤期间稀土元素来源一致,陆源物质的供应相对稳定。      

鄂尔多斯盆地北缘延安组2号煤层稀土元素异常原因及其地质意义

鄂尔多斯盆地北缘延安组2号煤层稀土元素的异常原因一直存在着争议,以2号煤发育较完整的榆林大海则煤矿为例,运用电感耦合等离子质谱（ICP-MS）、扫描电子显微镜（SEM）等方法,分析煤及夹矸中稀土元素（REE）含量及其矿物学特征,并揭示稀土元素异常原因。结果显示:煤中总稀土元素（∑REE）含量为3.71~46.21 μg/g,轻稀土元素（LREE,La-Eu）比重稀土元素（HREE,Gd-Lu）更富集;稀土元素标准化配分模式图显示少数样品为Eu正异常;稀土元素含量较高的样品和拥有Eu正异常的样品主要分布在与夹矸距离较近的煤层中,表明煤中稀土元素分布受到了夹矸的影响;在夹矸中发现很多晶型较好的锆石、磷灰石、透长石及锐钛矿,这些矿物是在聚煤过程中接受火山物质的直接证据。综合认为,鄂尔多斯盆地延安组2号煤沉积期,盆地周缘存在一次火山活动,火山灰降落覆盖在泥炭沼泽之上,影响了聚煤作用,致使煤中稀土元素分布异常。研究结果解释了鄂尔多斯盆地北缘的煤中稀土元素异常原因,为研究区煤的加工利用方式提供参考。      

REE characteristics of the coal in the Erlian Basin,Inner Mongolia,China, and its economic value

The rare earth elements (REE) content of the coal in the Erlian Basin was determined by inductively coupled plasma mass spectrometry (ICP-MS), and it turns out that the REE content from different geological age shows a significant difference: The REE content of the coal in the Jurassic Alatanheli Group is from 152.05×10⁻⁶ to 1416.21×10⁻⁶, with an average value of 397.31×10⁻⁶, and the relative concentration factor shows enriched; the REE content of the coal in Early Cretaceous Baiyanhua Group is from 20.65×10⁻⁶ to 102.53×10⁻⁶, the mean value is 49.06×10⁻⁶, and the relative concentration factor shows normally. The REE distribution patterns samples in Jurassic and Cretaceous shows the difference: The REE pattern in Jurassic coal mainly manifests as H-type distribution, with the Y, Lu positive anomaly, it is speculated that the fluid carried REE ions into the coal-bearing basin, and the heavy REE gather in the coal due to the different chemical properties of each REE. The REE occurrence mode is presumed to be mainly organic. Flat type is the REE main distribution pattern in Cretaceous coal. The REE patterns in clastic rocks of the roof, parting and floor of coal seam are similar to the REE patterns in the coal and the most possible reason is that the REE main source is from the clastic rock. It showed that the coal of the Early Jurassic, especially of Amugulen coalfield has resource value.     

淮北花沟西井田煤中微量元素及其环境意义分析

通过对30件煤样微量元素含量的测定,分煤层、分类型(稀土元素、环境意义微量元素)讨论了煤中微量元素的分布特征。研究发现各样品的稀土元素主要赋存于矿物质中,稀土元素含量均呈正常质量分数水平分布,各煤层的稀土元素分布表现为轻稀土富集、重稀土亏损。受陆源影响的煤,ΣREE含量高,稀土元素主要由陆源物质继承而来。受海水影响的煤,ΣREE含量低,分布模式具有海水性质。形成后受河流冲刷的煤,灰分增加,煤中稀土元素含量增加。该研究成果为煤炭资源的合理开发和利用提供基础资料。     

淮南矿区煤的稀土元素地球化学

采用INAA测试了淮南矿区 13个煤层煤样的稀土元素含量,研究了稀土元素地球化学特征,得出以下认识 :各煤层样品的稀土元素含量、分布模式变化都很大。煤中稀土元素主要来源于陆源碎屑,来源于海水和植物的不多;稀土元素在粘土矿物中含量高,主要以高岭石的形式赋存。稀土元素具有指相意义,随着成煤沼泽中海水影响的减弱,陆源影响的增强,煤中稀土元素的含量增加;煤的稀土元素分布模式也作有规律的变化,从类似于海相生物的分布模式到类似于陆源碎屑岩的分布模式。Eu异常是由源岩继承下来的,Eu负异常的减弱,估计是由于陆源控制减弱、海水影响增强引起的。在成煤沼泽环境中,海水的影响并未造成Ce严重亏损。     

Geochemistry of rare earth elements in a marine influenced coal and its organic solvent extracts from the Antaibao mining district, Shanxi, China

Twenty-six samples including roof, bottom and coal plies of a marine influenced coal bed were collected from the Antaibao mining district, Shanxi, China. The rare earth elements (REEs) were determined in solids and organic solvent extracts. The distribution pattern showed three distinct patterns: shale-like, LREE-rich and HREE-rich. This is attributed to the variable microenvironment of peat-forming swamp, the degree of marine influences and different REE sources. REEs in the coal are mainly controlled by detrital minerals but also affected by seawater. The chondrite-normalized REE patterns of the organic solvent extracts are distinctly different from those of corresponding original coal samples, which show a negative Eu anomaly, a depletion of middle REEs and an enrichment of HREEs. The LREEs in coal extracts are likely adsorbed by hydrogen-containing functional groups, and HREEs are likely bonded to carbon atoms.     

Occurrence modes and cleaning potential of sulfur and some trace elements in a high-sulfur coal from Pu’an coalfield,SW Guizhou,China

In this research, a float-sink test was applied to a Late Permian high-sulfur coal collected from Pu’an coalfield, Southwest in Guizhou, China. To investigate the occurrence modes and the mobility of various trace elements, as well as the cleaning potential of some harmful elements in density separation, coal quality parameters and concentrations of 46 elements of 7 density fractionated samples were determined and statistically analyzed. Results show that larger size and higher density fractions have higher total sulfur content and ash yield than the smaller and lower ones. In fact, most (74.39 %) of the total sulfur occurs in the inorganic matter. Affinity and correlation analysis show that Mo and Ni have apparently strong organic affinity, whereas Rh, Cs, Sr, Co, Nb, Zr, V, Ga, Sc, Be, Ge, Hf, Th, U, Ag, As, In, Cu, Cd, Ta, Li, TI, and Ba are mostly in the heavy fractions. Rare earth element (REE) patterns for the seven density fractions present good uniformity and show that they are of right-inclined pattern type characterized by Light REE (LREE, La ~ Eu) enrichment relative to Heavy REE (HREE, Gd ~ Lu) and pronounced negative δ _Eu anomalies. This suggests that REE was mainly derived from basalt-weathered materials. LRREE/HREE ratio variations reveal that LREE has stronger affinity with the organic matter relative to the HREE, while high LRREE/HREE in heavy fractions may be related to pyrite. Supposing the maximum sulfur content of the cleaned coal is 1.00 %, the theoretical removal ratios of Co, TI, and Ba are as high as 90.94, 93.73, and 92.29 %, respectively, while those of As, Ni and Mo are only 56.33, 48.85, and 45.05 %, respectively. As these figures change with different maximum sulfur contents required for the cleaned coal, not only the decrease of sulfur and ash in coal washing, but also the mobility of some harmful trace elements should be taken into consideration.     

东胜煤田侏罗系延安组煤中稀土元素地球化学特征

采用中子活化分析方法（INAA）测定了鄂尔多斯盆地东北部东胜煤田侏罗系延安组煤中稀土元素（REE）的含量,绘制了稀土元素分布类型曲线并计算了多种化学参数.在对REE的地球化学环境和地球化学特征分析的基础上,得出以下结论：①侏罗纪低灰低硫煤中REE的含量较低,且普遍低于华北盆地石炭二叠纪低灰低硫煤中的REE含量.②侏罗纪煤中的REE主要来自于物源区的陆源碎屑.东胜煤田北部靠近物源区,因此REE含量较南部高,且REE含量与灰分产率和SiO2含量有一定的相关性.③侏罗纪煤中REE的分布类型主要取决于母岩.除两个样品外,其他煤样普遍存在Eu负异常,无正Ce异常存在.④与其他岩石相比,煤中REE的分布类型极其复杂,原因在于开放盆地体系的煤中物质不断的改变和再分配.