Biogeochemical characteristics of the Hetai goldfield, Guangdong Province, China

In the Hetai goldfield, Guangdong Province, China, samples including rocks, soils and leaves of four plants (Pinus massoniana, Rhodomyrms tomenlosa, D. linearis var. dichotoma and Embelia laeta) collected from the gold mineralization zone and the background area were analyzed for Au, Ag, Cu, Pb, Zn, Hg, As and physiological parameters. The objective of this investigation is to study the geochemical and biogeochemical characteristics of studied plants, aiming at biogeochemical methods in Au exploration. The goldfield region shows geochemical and biogeochemical anomalies. Abundances of Au in rocks, soils, plants and the leaf pigments in the mineralized area are much higher than those in the surrounding region. The plants display unhealthy physiological and ecological characteristics in the Hetai goldfield area. The cell structures of the goldfield plants were anomalous and aberrant, and there were many nano-metal particles diffused in mitochondria and chloroplasts. Macro- and microscopic evidences of the vegetation in the goldfield areas are distinctly different from the background regions. The strongly anomalies in responses to Au are profound in further geochemical and botanic exploration studies.     

Geochemistry and biogeochemistry of rare earth elements in a surface environment (soil and plant) in South China

Plants and soils derived from different kinds of parent materials in South China were collected for analyses of rare earth elements (REEs) by inductively coupled plasma-mass spectrometry (ICP-MS). The distribution patterns and transportation characteristics of REEs in the soil–plant system were studied. The results show that geochemical characteristics of REEs depend on the types of soils, soils derived from granite being the highest in REE concentration. In a soil profile, REE concentrations are higher in B and C horizons than those in A horizon, with Eu negative anomaly and Ce positive anomaly. Plants of different genera growing in the same sampling site have quite similar REE distribution pattern, but plants of the same genera growing in different soils show considerable variation in characteristics of REEs. The patterns of the different parts of plant resemble each other, but the slope of the patterns becomes different. REEs have fractionated when they were transported and migrated from soil to plant root, stem and leaf, revealing that heavy REEs are relatively less available. REEs distributions in plants are influenced by the soil they grow in and also characterized by their individual biogeochemical characteristics. Biological absorption coefficients indicate difference of REE absorption capacity of plants. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Fractionation characteristics of rare earth elements (REEs) linked with secondary Fe,Mn, and Al minerals in soils

Soil secondary minerals are important scavengers of rare earth elements (REEs) in soils and thus affect geochemical behavior and occurrence of REEs. The fractionation of REEs is a common geochemical phenomenon in soils but has received little attention, especially fractionation induced by secondary minerals. In this study, REEs (La to Lu and Y) associated with soil-abundant secondary minerals Fe-, Al-, and Mn-oxides in 196 soil samples were investigated to explore the fractionation and anomalies of REEs related to the minerals. The results show right-inclined chondrite-normalized REE patterns for La–Lu in soils subjected to total soil digestion and partial soil extraction. Light REEs (LREEs) enrichment features were negatively correlated with a Eu anomaly and positively correlated with a Ce anomaly. The fractionation between LREEs and heavy REEs (HREEs) was attributed to the high adsorption affinity of LREEs to secondary minerals and the preferred activation/leaching of HREEs. The substantial fractions of REEs in soils extracted by oxalate and Dithionite-Citrate-Bicarbonate buffer solutions were labile (10 %–30 %), which were similar to the mass fraction of Fe (10 %–20 %). Furthermore, Eu was found to be more mobile than the other REEs in the soils, whereas Ce was less mobile. These results add to our understanding of the distribution and geochemical behavior of REEs in soils, and also help to deduce the conditions of soil formation from REE fractionation.     

Mobility of rare earth elements in the system soils–plants–groundwaters: a case study of an arid area (Oman)

Groundwater samples from six wells and various species of plants from soils developed on ophiolites were collected from an arid area (AlKhod area, Oman) and analyzed for trace elements including rare earth elements (REEs). The distribution patterns of REEs in plants indicated an enrichment in middle REEs (MREEs?=?Sm to Dy) and heavy REEs (HREEs?=?Ho to Lu), when they are normalized to the REE composition of the Post Archean Australian Shale (PAAS), with a significant negative anomaly in Ce and a positive anomaly in Eu. Compared to Oman ophiolites, the REEs in different species of plants are depleted in Ce and enriched in MREEs and slightly enriched in light REE (LREE?=?from La to Nd). Relative to PAAS, the distribution of REEs in groundwaters revealed similar patterns to the REE distribution in plants. The distribution patterns of REEs in plants relative to those in waters are nearly flat. These patterns suggest that the transfer of REEs from soil solutions to the groundwaters in Oman occurs without any significant fractionation.     

The rare earth element compositions of sediments from the loess tableland in the Liyang Plain,southern China: implications for provenance and weathering intensity

To identify the weathering intensity and to deduce the provenance of sediments (black-brown soil and loess) from the loess tableland in the Liyang Plain is of great importance for understanding the development and origin of civilization of this critical region in China. The geochemical results show similar REE distribution patterns among sediments sampled from the YC profile in the Liyang Plain, reticulated red soils from the Dongting lake area, Xiashu loess in Zhenjiang, and loess from the Loess Plateau in China. These similarities imply a single provenance, from dust storms. REEs, especially the LREE/HREE ratio and Eu anomaly, can trace weathering intensity. Higher LREE/HREE ratios, and remarkably Eu anomalies, are present in the top loess (L₀), Lower LREE/HREE ratios and insignificant Eu anomalies are present in black-brown soil (S₀*) from the Liyang Plain. These demonstrate that the black-brown soils have undergone a lower intensity of weathering than the loess of YC profile. Moreover, CIA values for sediments from the YC profile provide powerful evidence to support the above result. Comparisons of analyses of the REE contents of sediments from the YC profile, of reticulated red soils from the Dongting Lake area, Xiashu loess from the Yangtze River, and loess from the Loess Plateau, clearly show the weathering intensity decreases according to the following sequence: reticulated red soil from the Dongting Lake area > sediments of YC profile from the Liyang Plain, which formed from dust storms ≈ Xiashu loess from lower reach of the Yangtze River > loess from the Loess Plateau.     

广西某地花岗岩风化壳中稀土元素特征与iREE矿床成矿机制

为了解风化壳中离子交换相稀土元素的特征,对广西某地花岗岩风化壳剖面样品进行了X射线衍射及主量、稀土元素地球化学特征的研究.剖面自上而下可划分为腐殖土层(A₁)、亚粘土层(A₂)、网纹状风化层(B₁)和全风化层(B₂);自A₁至B₂,粘土矿物的含量和化学风化蚀变指数快速降低;与母岩相比A₁、A₂、B₁中全相Ce、Nd和HREE相对富集,B₂中全相稀土与母岩特征相似,所有样品的离子交换相HREE亏损,Y相对富集;离子交换相轻、重稀土一起富集在B₂中.据此推测,花岗岩中褐帘石、榍石等易风化的稀土矿物为离子交换相稀土提供了主要的物源,锆石、磷钇矿等难风化的稀土矿物的残留及表生稀土矿物的形成使全相HREE相对富集;离子交换相轻、重稀土元素的分馏程度随风化程度的增加而变化.      

Trace element and Nd isotope analyses of apatite in granitoids and metamorphosed granitoids from the eastern Central Asian Orogenic Belt: Implications for petrogenesis and post-magmatic alteration

We present in situ trace element and Nd isotopic data of apatites from metamorphosed and metasomatized (i.e., altered) and unaltered granitoids in the Songnen and Jiamusi massifs in the eastern Central Asian Orogenic Belt, with the aim of fingerprinting granitoid petrogenesis, including both the magmatic and post-magmatic evolution processes. Apatites from altered granitoids (AG) and unaltered granitoids (UG) are characterized by distinct textures and geochemical compositions. Apatites from AG have irregular rim overgrowths and complex internal textures, along with low contents of rare earth elements (REEs), suggesting the re-precipitation of apatite during epidote crystallization and/or leaching of REEs from apatite by metasomatic fluids. ε_Nd(t) values of the these apatites are decoupled from zircon ε_Hf(t) values for most samples, which can be attributed to the higher mobility of Nd as compared to Sm in certain fluids. Apatites from UG are of igneous origin based on their homogeneous or concentric zoned textures and coupled Nd-Hf isotopic compositions. Trace element variations in igneous apatite are controlled primarily by the geochemical composition of the parental melt, fractional crystallization of other REE-bearing minerals, and changes in partition coefficients. Sr contents and Eu/Eu* values of apatites from UG correlate with whole-rock Sr and SiO₂ contents, highlighting the effects of plagioclase fractionation during magma evolution. Apatites from UG can be subdivided into four groups based on REE contents. Group 1 apatites have REE patterns similar to the host granitoids, but are slightly enriched in middle REEs, reflecting the influence of the parental melt composition and REE partitioning. Group 2 apatites exhibit strong light REE depletions, whereas Group 3 apatites are depleted in middle and heavy REEs, indicative of the crystallization of epidote-group minerals and hornblende before and/or during apatite crystallization, respectively. Group 4 apatites are depleted in heavy REEs, but enriched in Sr, which are features of adakites. Some unusual geochemical features of the apatites, including the REE patterns, Sr contents, Eu anomalies, and Nd isotopic compositions, indicate that inherited apatites are likely to retain the geochemical features of their parental magmas, and thus provide a record of small-scale crustal assimilation during magma evolution that is not evident from the whole-rock geochemistry.     

兴蒙-华北地球化学走廊带稀土元素含量与空间分布

为研究兴蒙造山带-华北克拉通地球化学走廊带区域地球化学组成及其横向空间变化,统计分析不同地理单元和五万图幅单元的REE含量并绘制其空间分布折线图.内蒙古半干旱草原土壤中稀土含量较低,与其草原沙土的粘土矿物较少有关;江苏北部冲积平原区的土壤中稀土含量较高,与降雨量存在良好空间对应关系.内蒙古红格尔到河北张家口,土壤与岩石∑REE的比值绝大多数小于1,REE发生贫化;山东章丘到江苏连云港,比值基本大于1,REE发生富集.华北克拉通内蒙地块土壤稀土特征与兴蒙造山带相似,可能受其草原沙土景观的影响.在不同构造单元之间,LREE与HREE亏损与富集的空间分布存在细微差异.结果表明:地理景观,特别是黏土矿物是影响土壤REE含量的重要因素,降雨量与REE存在良好空间对应关系,REE自身的地球化学性质的差异在土壤形成过程中对轻重稀土元素分异具有重要影响.      

Rare earth element distributions among coexisting granulite facies minerals,Scourian complex,NW Scotland

The major rock-forming mineral phases (pyroxenes, plagioclase, garnet, hornblende) of a suite of granulite-facies gneisses from the Scourian complex, NW Scotland, have been analyzed for their rare earth element (REE) content. Although host rock compositions range from felsic to ultramafic, REE abundances and patterns for each mineral group show only limited variation. The REEs exhibit regular and consistent distribution patterns for each mineral which suggest, together with major element and textural considerations, that the observed distribution coefficients approach equilibrium. Total REE content follows the sequence hornblende>clinopyroxene>garnet>plagioclase >orthopyroxene and mass balance calculations show that even in the felsic gneisses>60% of the REEs reside in the major rock-forming minerals. Comparisons of both relative REE abundances and distribution coefficients with those in other rock types reveal a striking resemblance with patterns observed in mineral-liquid pairs of dacitic rocks. These similarities may have arisen during a partial melting episode in which granite-granodiorite melts were generated and removed from the Scourian complex; leaving a residuum which is severely depleted in the incompatible elements, including the REEs.     

Geochemical characteristics and provenance implication of rare earth elements in surface sediments from bays along Guangdong Coast, Southeast China

A systematic study of the granulometric properties and the occurrence and distribution of rare earth elements (REE) within surface sediments from ten bays situated along the coast of Southeast China has facilitated a more rigorous understanding of constraints on sediment provenance in the area. The results show that REE concentrations are similar within a single bay, but vary considerably (133.58–251.77 mg/kg) among the bays. The chondrite-normalized distribution patterns show the typical enrichment of light REEs (LREEs: La–Eu) relative to heavy REEs (HREEs: Gd–Lu), and an apparent depletion of Eu, which is diagnostic of a terrigenous sediment source. Obvious enrichments of the middle REEs (MREEs: Sm–Ho) in the PAAS-normalized (Post-Archean Australian Shale) distribution patterns of these bay sediments are similar to results reported from large rivers in China. Comparing the REE composition of the bay sediments with those of adjoining fluvial sediments and with the bedrock of the surrounding drainage basins, the latter are indicated as the dominant sediment source. The uniform REE distribution patterns, and MREE enrichments, prove that the sediments are derived from the material transported by the streams and rivers that discharge into the bays.     

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.     

离子吸附型稀土矿床形成的矿物表/界面反应机制

华南离子吸附型稀土矿床提供了全球超过90%的重稀土,是我国优势的战略性关键金属矿产资源。掌握这类矿床的成矿机制和禀赋特征,可为增加稀土资源储量和高效利用稀土资源提供理论支撑。离子吸附型稀土矿床主要发育在富稀土花岗岩、浅变质岩及火山岩的风化壳中。基岩中的(含)稀土矿物是风化壳中离子态稀土的主要来源,其矿物组合很大程度上决定了稀土矿床的禀赋和分异特征。在物理-化学风化和微生物作用下,造岩矿物、含稀土矿物和稀土独立矿物逐渐溶解,使稀土元素活化和再富集。一方面,母岩风化形成的黏土矿物和铁锰氧化物具有较大的比表面积和一定的表面电荷密度,是稀土离子的主要载体;另一方面,稀土离子通过离子交换、表面吸附与络合、共沉淀,以及形成次生稀土矿物等途径富集在次生矿物表面,其富集-分异特征和赋存状态受矿物类型、pH、微生物活动等因素所控制。利用高分辨透射电镜结合选区电子衍射和电子能量损失谱,以及同步辐射X射线吸收精细结构谱,有望在原子级尺度查明稀土的微观赋存状态。未来研究需更多关注基岩中(含)稀土矿物组合及其演化路径的制约因素、微生物风化对离子吸附型稀土矿床成矿作用的约束,以及稀土元素的微观赋存状态等问题。     

Phase relations of REE-bearing minerals during the metamorphism of carbonaceous shales in the Tim-Yastrebovskaya structure,Voronezh Crystalline Massif,Russia

Paleoproterozoic carbonaceous shales in the Tim-Yastrebovskii ancient rift, which underwent zonal metamorphism at 350–550°C, contain REE mineralization of silicates (allanite, thorite, and Ce-P huttonite) fluorcarbonates (bastnaesite and synchysite), phosphates (monazite and xenotime), and REE-bearing apatite. The reason for the wide occurrence of bastnaesite and other REE minerals is relatively high REE concentrations in the sulfide-bearing carbonaceous shales, with these elements accumulated in the organic matter in the course of diagenesis. Reaction textures with REE-bearing chlorite, bastnaesite, and allanite suggest that REE-bearing chlorite and bastnaesite provided REE for the forming of higher temperature allanite and monazite. This is corroborated by the REE patterns of the monazite, allanite, and bastnaesite, which are almost identical and are characterized by the strong predominance of LREE. The replacements of REE minerals during metamorphism at 350–550°C took place via a number successive transitions: (1) Mnz → Aln, Chl _REE → Bst, Chl _REE → Aln, Bst → Aln and (2) Bst → Mnz and Ap _LREE → Mnz. These replacements can be accounted for by prograde metamorphic reactions.     

Geochemistry of soils of King George Island, South Shetland Islands, West Antarctica: Implications for pedogenesis in cold polar regions

Fine fractions of soils on the Barton Peninsula, King George Island, West Antarctica have been forming during the last 6000 yr since the last deglaciation. Texturally, they are mostly composed of mineral and rock fragments with some volcanic ashes, which are also indicated by geochemical compositions representing for the nonclay silicate minerals and low values of chemical index of alteration. No significant changes are observed in major- and trace element abundances. Such geochemical characteristics suggest that chemical weathering of bedrocks on the Barton Peninsula seems insignificant and that the soils are composed of physically weathered mineral and rock fragments which are mixed with eolian additions of volcanic ashes and Patagonian dusts. Chondrite-normalized rare earth element (REE) distribution patterns of the Barton Peninsula soils are slightly different from those of bedrocks, indicating that the REE abundances and characteristics were influenced by eolian additions. Mixing calculations, which mass-balance the REEs, suggest that volcanic ashes blown from Deception Island were the major eolian contributor, followed by atmospheric dusts sourced from Patagonia, South America. Even in the warmer and humid climatic conditions in the maritime Antarctic region, the chemical weathering of bedrocks appears to be insignificant, probably due to the relatively short duration of weathering since the last deglaciation.     

岩石—土壤—铁芒萁系统中稀土元素的分布、迁移和累积

在赣南非稀土矿区和四处不同稀土矿区内取样,用ICP-MS法测定岩石-土壤-铁芒萁系统中15个稀土元素的含量,并对其分布、迁移、累积特征进行了研究。结果表明:稀土元素在岩石、土壤各层含量由高到低的顺序为C(心土层)>A(表土层)>B(底土层)>D(成土母岩);在铁芒萁植物体内的分布规律是:轻稀土元素含量为叶>根>茎>叶柄;重稀土元素含量为根>叶>茎>叶柄;稀土元素演化、迁移的难易是由稀土元素的重轻所决定的;岩-土-芒萁系统各环节间稀土元素的含量模式基本相似,表征元素在岩石→土壤→植物大系统中存在着向量(非均衡性)关系。     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.     

赣南某离子吸附型稀土矿床浅变质岩的矿化特征

近几年在赣南新元古代浅变质岩风化壳中发现了离子吸附型稀土矿床,对矿区及南岭科学深钻中的浅变质岩样品进行了岩石、矿物及地球化学特征研究.矿区内主要出露神山组和库里组（南华系）,前者以千枚岩为主,含少量片岩,后者以厚层变质沉凝灰岩和中厚层变质砂岩为主;南岭科学深钻1 165~1 170.77 m库里组（青白口系）以变质沉凝灰岩为主夹薄层凝灰质板岩.浅变质岩类中新生变质矿物有绢云母、绿泥石、磁铁矿、堇青石、白云母、黑云母等,稀土矿物有新奇钙铈矿、独居石、磷钇矿、水独居石等;稀土含量为162×10-6~723×10-6,富集轻稀土.新奇钙铈矿是矿体中离子相稀土的主要来源;赣南青白口纪-南华纪中厚层变质沉凝灰岩和变质凝灰岩风化壳具有较好的稀土成矿前景.      

Biogeochemical investigation in south eastern Andhra Pradesh: the distribution of rare earths, thorium and uranium in plants and soils

The concentration of rare earth elements (REE), thorium and uranium were determined by inductively coupled plasma mass spectrometry (ICP−MS) in the plant species, Pterocarpus santalinus, P. marsupium and P. dalbergioides, and the soils on which they were growing. Higher concentrations of lanthanum (La), cerium (Ce) were observed in both plants and soils. Large amounts of thorium and uranium were found in the soil. In all tree species, the concentration of REEs were higher in the heartwood than the leaves. The heartwood of P. santalinus accumulated larger quantities of uranium (average concentration of 1.22 ppm) and thorium (mean value of 2.57 ppm) than the other two species. Received: 8 September 1999 · Accepted: 15 December 1999     

Geochemistry of red residua underlying dolomites in karst terrains of Yunnan-Guizhou Plateau: II. The mobility of rare earth elements during weathering

The aim of this study is to characterize the evolution of the rare earth elements (REE) in the Pingba red residua on karst terrain of Yunnan-Guizhou Plateau. The in-situ weathering and the two-stage development of the profile had been inferred from REE criterions. The REE were significantly fractionated, and Ce was less mobilized and separated from the other REEs at the highly enriched top of the profile. This is consistent with the increase of oxidation degree in the regolith. And it is also suggested that the wet/dry climate change during chemical weathering caused Ce alternative change between enrichment and invariance in the upper regolith. Chondrite-normalized REE distribution patterns for samples from dolomites and the lower regolith are characteristic of MREE enrichment and remarkable negative Ce-anomalies patterns (similar to the convex-up REE patterns). The following processes are interpreted for the patterns in this study: (1) the accumulation of MRRE-rich minerals in dolomite dissolution, (2) water–rock interaction in the weathering front, and (3) more leaching MREE from the upper part of the profile. The latter two explanations are considered as the dominant process for the formation of the REE patterns. Samples from the soil horizon exhibit typical REE distribution patterns of the upper crust, i.e., La_N/Yb_N=10 and Eu/Eu*=0.65. All data indicate that the leaching process is very important for pedogenesis in this region. The experiments demonstrating that abnormal enrichment of REE at the upper regolith–bedrock interface is caused by a combination of volume change, accumulation of REE-bearing minerals, leaching of REE from the upper regolith, and water–rock interaction during rock–soil alteration processes. Our results support the conclusion that the weathering profile represents a large, continental elemental storage reservoir, whereas REE enrichment occurs under favorable conditions in terms of stable tectonics, low erosion and rapid weathering over sufficiently long time.