Heavy metals accumulation in plants growing in ex tin mining catchment

The degree of contamination by heavy metals (arsenic, copper, lead, tin and zinc) in soil and transfer to plants has been studied. Specimens of plant species from five locations in an area of 10 × 10 m were sampled with their corresponding soils. Thirty six plant species including two shallow water aquatic plants were identified. Soil and plant specimens were analyzed by using inductively coupled plasma optical emission spectrometry. It was found that metal concentration in soil was highly variable while concentration of metals in plants directly depends on the concentration of metals it was rooted. Roots showed highest metal concentration followed by leaves, shoots and flowers. Bioconcentraion factor and translocation factor were calculated, representing Cyperus rotundus L. as a potential tin-hyperaccumulator plant, previously not reported in literature. Plant Species Imperata cylindrica, Lycopodium cernuum, Melastoma malabathricum, Mimosa pudica Linn, Nelumbo nucifera, Phragmites australis L., Pteris vittata L. and Salvinia molesta, were metal accumulator while Acacia podalyriaefolia G. Don, Bulb Vanisium, Dillenia reticulate King, Eugenia reinwardtiana, Evodia roxburghiania Hk. f. clarke, Gleichenia linearis, Grewia erythrocarpa Ridl., Manihot esculenta Crantz, Paspalum conjugatum Berguis, Passiflora suberosa, Saccharum officinarum, Stenochlaena palustris (Burm.) Bedd. and Vitis trifolia Linn. were tolerated plant species. All other studied plants were excluders. Identified plant species could be useful for revegetation and erosion control in metals contaminated ex-mining sites. Morphological changes such as reduction in size, change in color and deshaping have also been observed in plant species with high metal values.     

Effects of coal fly ash amended soils on trace element uptake in plants

Variations in As, Ba, Bi, Cd, Co, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, Th, Tl, U, W, and Zn uptake were evaluated in young, middle-aged, and mature basil, tomato, zucchini, and sunflower plants grown in soils amended with 5, 10, and 20% by weight fly ash. Elements susceptible to uptake with increasing fly ash were As and Tl, with As exceeding potentially toxic levels in basil and zucchini. Temporal variations in element uptake included (1) increasing Ba and Cd concentrations in tomato and As, Ba, Cd, and Tl in zucchini, (2) decreasing Co concentrations in tomato, zucchini, and sunflower, Ni in zucchini, and Tl in basil, and (3) increasing As and Ni concentrations in basil and Pb in zucchini and sunflower during early growth followed by decreasing concentrations at maturity. Although most of the trace elements were below reported toxic levels, the elevated concentrations of As in plant tissue suggests that fly ash treatment programs can lead to potentially toxic accumulations of As, and thus, should be carefully monitored.     

Patterns of trace element partitioning

When a phenocryst and its lava matrix have been analysed for both major and trace elements, plots of partition coefficient (mineral/matrix) against ionic radius give a family of sub-parallel curves, one univalent, one divalent, etc. Onuma et al. (1968) demonstrated this with two analyses and concluded, from the shape of these curves, that trace element partition between phenocryst and groundmass is determined primarily by crystal structure of the phenocryst. In this study, over 50 such analyses, taken from the literature, have been plotted on modified Onuma diagrams, in order to analyse the constant and variable factors in the curves. It is demonstrated that these curves can provide important additional information in trace element studies by revealing, for example, the site or sites in a mineral which a given element is occupying, the valency state of the element and even, in some cases, the proportion of different valency states present.     

Aluminum-dependent trace element partitioning in clinopyroxene

As technical advances have dramatically increased our ability to analyze trace elements, the need for more reliable data on the compositional dependence of trace element partitioning between minerals and melt has become increasingly important. The late-Cretaceous Carmacks Group of south central Yukon comprises a succession of primitive high-Mg ankaramitic lavas characterized by shoshonitic chemical affinities and containing large complexly zoned clinopyroxene phenocrysts. The compositional zonation of the clinopyroxene phenocrysts is characterized by relatively Fe-rich (Mg^# = Mg/(Mg + Fe) = 0.85), but mottled, cores surrounded by mantles of cyclically-zoned clinopyroxene whose Mg^# varies repeatedly between 0.9 and 0.80. These cyclically zoned clinopyroxene mantles appear to record the repeated influx and mixing of batches of primitive with more evolved magma in a deep sub-crustal (∼1.2 GPa) magma chamber(s). Laser ablation ICP-MS was used to analyze the trace element variation in these zoned clinopyroxenes. The results indicate more than a threefold variation in the absolute concentrations of Th, Zr, rare earth elements (REE), and Y within individual clinopyroxene phenocrysts, with no apparent change in the degree of REE or high field strength element (HFSE) fractionation. The variation in absolute abundances of trace elements correlates closely with the major element composition of the clinopyroxene, with the most enriched clinopyroxene having the lowest Mg^# and highest Al contents. The problem is that the amount of crystal fractionation required to explain the major element variation (∼20%) in these clinopyroxene phenocrysts cannot explain the increase in the abundance of the incompatible trace elements, which would require more than 70% crystal fractionation, if constant partition coefficients are assumed. The anomalous increase in incompatible trace elements appears to reflect an increase in their partition coefficients with increasing Al^IV in the clinopyroxene; with an increase in Al₂O₃ from 1.5 to 4.0 wt.% during ∼20% crystal fractionation over a temperature decrease of ∼100°C being associated with more that a threefold increase in the partition coefficients of Th, Zr, REE, and Y. The magnitude of these increases may indicate that the substitution of these trace elements into clinopyroxene is better modeled in some natural systems by a local charge balance model, rather than the distributed charge model that better replicates the results of annealed experiments. These findings indicate that the effect of Al on the partition coefficients of incompatible trace elements in clinopyroxene may be under appreciated in natural magmatic systems and that the application of experimentally determined clinopyroxene partition coefficients to natural systems must be done with caution.     

Testing models of trace element geochemistry at Poços de Caldas

In order to test the geochemical models used in repository performance assessment, modelling groups were provided with selected major element analyses of Poços de Caldas groundwaters and asked to predict “blind” the solubility, speciation and limiting solid for a number of trace elements. This paper documents these predictions and compares them to field analyses. These tests illustrate particular stengths and weaknesses in current models/databases and allow recommendations for amendments/improvements to be made.     

Systematic use of trace element in igneous process

This paper describes an extended application of the Rayleigh distillation law to trace element behavior in a fractional crystallization sequence. Using a trace element with a very low bulk partition coefficient as a reference (as suggested by Anderson and Greenland, 1969, and extended by Treuil and Varet, 1973), we can derive bulk partition coefficients for other elements and, in turn, the mineralogical composition of the cumulates. Trace elements with large D, such as Ni and Cr, further constrain the system, and we can deduce the initial composition of the magma. An example of this technique is shown for Terceira Island in the Azores.Contribution IPGNS no 229Now at Dept. of Geological Sciences, California Institute of Technology, Pasadena, California, USA     

金红石微量元素电子探针分析

金红石电子探针微量元素分析一般以人工合成的氧化物来作为监测标样,尚较缺乏对金红石标样进行系统地测试分析。本文运用CAMECA SXFive电子探针对金红石标样R10进行微量元素分析,根据金红石中主要微量元素在地质学中的应用,本次共分析了Al、Si、Ti、Fe、Cr、Zr、V、Nb、Ta等9个元素,Ti、Si元素作为本次分析的监测元素。本文通过调整加速电压和电流、背景和峰值测试时长以及干扰谱峰处理等来提高微量元素分析精度和准确度。分析结果显示,其中,Zr(780±29×10~(-6))(1SD,n=25)、Nb(2799±66×10~(-6))、V(1276±33×10~(-6))、Fe(4309±34×10~(-6))、Cr(718±31×10~(-6))的分析结果与二次离子质谱(SIMS)和激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)的推荐值在误差范围内一致。大部分元素数据波动范围在10%以内,V、Fe元素的数据波动范围仅在5%以内。V、Nb和Fe测试精度比前人电子探针分析结果有较大提高。金红石Zr测试误差传递给金红石Zr温度计给出的温度误差一般22℃。本文还对金红石Zr温度计应用、提高Ta元素分析精度和准确度、金红石Fe~(3+)分析等问题进行了探讨。     

The trace element geochemistry of Corsican ophiolites

Ultramafic rocks, gabbros, plagiogranites, dolerites and basaltic dikes and pillows lavas of the ophiolite slices of eastern Corsica have been metamorphosed in both oceanic and orogenic environments. The trace element content of the metabasaltic rocks which exhibit a tholeiitic differentiation trend towards a ferrobasaltic composition, is similar to that of oceanic basalts. The cumulate sequence is interpreted to have been formed by fractional crystallization from an olivine-tholeiite magma. The troctolites representing cumulates derived from melts representing liquid fractions in the range F=1-0.85, gabbros from melts with F=0.85-0.45, and ferrogabbros and plagiogranites from melts with F<0.45. An oceanic environment with moderate spreading rates and magmatic processes similar to present-day normal oceanic ridge segments is considered the more probable original setting of the Corsican ophiolites.Financial support by C.N.R. (Italy) and A.T.P. Géodynamique de la Méditerranée Occidentale C.N.R.S. (France)     

Spatio-temporal variation of trace element contents in Rwanda necrosols

In this study, the spatio-temporal variation of selected trace elements in cemetery soils (necrosols) was investigated. Preliminary results revealed that onsite mean concentration for As, Ba, Cr, Cs, Ga, Ni, Rb, Sc, Th, V, Y, and Zr was generally higher than background offsite values. The trace metal contents of the cemetery soils also showed higher accumulation ratio for As, Cr, Ni, and Sc relative to world averages for soils (Clarke values). Similarly, it was observed that the cemetery soils showed significant enrichment with As and Cr in comparison with world averages for agricultural soils. The exchangeable sodium percentage showed that most of the onsite soil samples are sodic, which may have adverse effect on the growth and yield of crops grown in the study area. The study concludes that decomposition of human remains and grave contents play a significant role in elevating the total trace element contents in soils associated with cemeteries. For this reason, there is need for proactive measures to be taken with respect to the choice of raw materials used for the construction of coffins and funeral materials. There is need for local funeral industries particularly in developing countries and the government to begin to consider and adopt such green or environmental friendly burial options to prevent the potential environmental degradation of cemetery areas.     

煤中微量元素富集的主要因素分析

在对兖州矿区煤中微量元素成因分析及总结前人结论的基础上,将煤中微量元素富集因素划分为原生、次生和后生三个阶段,分别对每一个阶段影响微量元素富集的主要因素进行研究和分析。结果表明,煤在形成的过程中影响微量元素迁移、富集的因素很多,植物生长的种类、生长中水化学条件、泥炭沼泽形成中大气、海水的入侵、煤在煤化过程中岩浆热液的作用、煤与顶、底板岩石的物质交换作用等都影响着煤中微量元素富集。因此,煤中微量元素的形成、聚集是煤在形成的各个时期、各种地质因素综合影响的结果。      

Apatite solubility in carbonatitic liquids and trace element partitioning between apatite and carbonatite at high pressure

We have measured apatite solubility in calcic carbonatitic liquids and determined apatite/melt partition coefficients for a series of trace elements, including the rare earth elements (REE), high field strength elements (HFSE), Rb, Sr, U-Th-Pb. Experiments were performed between 4 and 6 GPa, from 1200 to 1380 °C, using the multianvil apparatus. Trace element concentrations were determined by laser ablation ICP-MS and electron microprobe. In addition, a specific protocol was designed to measure carbon concentration in the apatites, using the electron microprobe. Two starting apatite samples were used in order to test for the effect of apatite chemistry on partitioning behavior.Apatite solubility is lower in calcitic melts by a factor 3-5 compared to dolomitic melts (3-5.5 vs. 10-18 wt.% P₂O₅ in melt). We interpret this difference in terms of solubility product in the liquid and propose an empirical model for apatite saturation that takes into account melt calcium content. We conclude that calcitic melts that may form by melting of carbonated eclogites could be saturated with residual apatite, contrary to dolomitic melts formed in carbonated peridotites.Compatibility behavior of the REE depends on apatite silica content: REE are compatible in apatites containing 3.5-5 wt.% SiO₂, with values between 1.5 and 4, whereas REE are incompatible in apatites containing 0.2 wt.% SiO₂. HFSE, U, Th, and Y are compatible in silica-rich apatite, with while . Strontium is always retained in the melt, with of the order of 0.5. Lead appears to be incompatible in apatite, although this finding is weakened by almost complete Pb loss to sample container. High silica concentration favors REE incorporation in apatite by allowing for charged balanced coupled substitution. Sulfur and carbonate may also favor REE incorporation in apatite. Our results allow to reconcile previously published experimental determinations of REE partitioning. We use our experimentally determined partition coefficients to investigate the impact of residual apatite during partial melting of recycled carbonated material (eclogite + sediments) and discuss how the chemical characteristics of the produced liquids can be affected by residual apatite.     

Microstructural evolution and trace element mobility in Witwatersrand pyrite

Microstructural analysis of pyrite from a single sample of Witwatersrand conglomerate indicates a complex deformation history involving components of both plastic and brittle deformation. Internal deformation associated with dislocation creep is heterogeneously developed within grains, shows no systematic relationship to bulk rock strain or the location of grain boundaries and is interpreted to represent an episode of pyrite deformation that predates the incorporation of detrital pyrite grains into the Central Rand conglomerates. In contrast, brittle deformation, manifest by grain fragmentation that transects dislocation-related microstructures, is spatially related to grain contacts and is interpreted to represent post-depositional deformation of the Central Rand conglomerates. Analysis of the low-angle boundaries associated with the early dislocation creep phase of deformation indicates the operation of <010>{100} slip systems. However, some orientation boundaries have geometrical characteristics that are not consistent with simple <010>{100} deformation. These boundaries may represent the combination of multiple slip systems or the operation of the previously unrecognized <001>{120} slip system. These boundaries are associated with order of magnitude enrichments in As, Ni and Co that indicate a deformation control on the remobilization of trace elements within pyrite and a potential slip system control on the effectiveness of fast-diffusion pathways. The results confirm the importance of grain-scale elemental remobilization within pyrite prior to their incorporation into the Witwatersrand gold-bearing conglomerates. Since the relationship between gold and pyrite is intimately related to the trace element geochemistry of pyrite, the results have implications for the application of minor element geochemistry to ore deposit formation, suggest a reason for heterogeneous conductivity and localized gold precipitation in natural pyrite and provide a framework for improving mineral processing.     

Major and trace element associations in limestones and dolomites

Selective chemical separations of mineralogical constituents of limestones (Carboniferous limestones from the Isle of Man, and Lincolnshire limestone, Middle Jurassic, Lincolnshire) and dolomites (from Carboniferous limestone, Isle of Man) using dilute acetic acid and hydrogen peroxide have been used and the fractions obtained analysed to evaluate mineralogical associations of trace and major elements. Ca, Mg, Mn and Sr are mainly restricted to the carbonate fraction. Fe is found in carbonates, particularly dolomite, and also in sulphides with Zn, Cu, Ni and Pb, and with V and Cr and other traces in “residual” silicate minerals.It is concluded that mineralogical associations of trace elements are complex, and cannot be easily determined by statistical analysis. Selective chemical-separation methods of analysis offer direct indication of element associations with no loss of data. Calculated average concentrations in various fractions of analysed rocks (58 limestones and 19 dolomites) are tabulated.     

锆石微量元素的理论基础及其应用研究进展

锆石是地质学研究中最重要的副矿物,其分布广泛、物理、化学性质稳定,记录了结晶时的年龄、温度、氧逸度以及O-Hf-Si-Zr-Li等多元同位素和微量元素信息,被广泛运用于地球科学的研究中。近年来,随着分析技术的发展,研究者在获取锆石年龄的同时也获取了大量锆石微量元素数据,这些数据的积累推动着研究者对锆石微量元素理论研究的不断深入,并取得了一系列重要进展,如发现锆石微量元素组成受锆石本身的晶格特点主导,符合晶格应变模型和类质同象替代机制;发现锆石微量元素组成受到熔体成分演化影响,锆石结晶时的熔体微量元素组成往往不等同于全岩;发现锆石内部的微量元素不均一特征(矿物包裹体、热点、蜕晶化作用等)可能会严重影响锆石的微量元素组成,继而建立了"干净锆石"的判别指标和筛选机制。此外,锆石微量元素的应用研究也取得了长足进展,研究者们不断尝试通过各类锆石微量元素指标、图解、分配系数,识别母岩浆物理化学性质、反演母岩浆组成,大大推动了锆石微量元素在示踪岩浆源区和岩浆过程中的应用。然而,由于锆石微量元素组成受控于多种因素,使得锆石微量元素在实际应用当中常常面临着多解性问题、重叠问题和分配系数的选择问题,在一定程度上影响了锆石微量元素应用研究的可靠性。未来的锆石微量元素研究将不满足于使用传统的低维指标和图解以及分配系数,而将在充分吸收传统方法精华的基础上,从海量数据与更高的维度中寻找元素之间相关性,基于热力学定律揭示新原理,基于更高空间分辨率揭示动力学因素的影响,从数据驱动和理论驱动的全新视角下深入揭示隐藏在锆石微量元素中的信息。     

Li—F花岗岩液态分离的微量元素地球化学标志

华南和世界其他国家典型Ｌｉ－Ｆ花岗岩１９５个微量元素分析结果的研究表明,随Ｌｉ－Ｆ花岗岩自下而上不同岩相变化：Ｚｒ／Ｈｆ－Ｆ、Ｎｂ／Ｔａ－Ｆ等有负相关变化;同样,随Ｆ增加,Ｔａ（Ｎｂ）、Ｓｎ、Ｗ、Ａｌ升高和Ｎｂ／Ｔａ（Ｚｒ／Ｈｆ）降低;在Ｋ／Ｒｂ－Ｒｂ图中黄英岩成分点位于相关斜线左下方;在Ｋ－Ｌｉ图中有低Ｌｉ、Ｋ的异常变化;在Ｒｂ／Ｓｒ－Ｐ２Ｏ５图中相关的二￣三个数量级异常变化等,均是Ｌｉ－Ｆ花岗     

Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

Role of trace element partition coefficients in models of andesite genesis

Orogenic andesite magmas probably evolve at 1100 to 900°C, have between 1 and 5 wt. % H₂O and f_O2 above the NiNiO buffer during phenocryst precipitation and may be saturated with a second fluid phase prior to eruption. Consequently, many solid/liquid trace element partition coefficients appropriate to andesites are higher than for basalts, perhaps due to the presence of fewer octahedrally coordinated sites in andesite liquids as well as to lower temperatures.Simple quantitative interpretation of trace element concentration data for orogenic andesites in general or for most specific suites is not possible using available partition coefficients. Fractional crystallization models involving magnetite or amphibole or both seem less at odds with available data than do models invoking equilibration with subducted oceanic crust or overlying peridotite. Critical choices between simple models, or identification of supplementary or more complex processes, require a more rigorous data base than presently available.