Evaluation of Dissolved Species of Rare Earth Elements in Environmental and Biological Samples by Cation Exchange Chromatography and Electrospray Ionization Mass Spectrum

As the separation and purification methods of rare earth elements(REEs) were well developed,REEs have been widely used at present in many fields of industry and agriculture. The widespread application of REEs as the additives in fertilizers will inherently lead to their residues in environment, accumulation in organism,and entering into a food chain. The bioavailability and toxicity of REEs mainly depend on its dissolved species which can be partly assimilated by plants and animals,thus, the speciation of REEs in environment and organisms becomes more and more important today.     

Studies of the Distribution of Rare Earth Elements in Marine Organisms Using ICP-MS

Rare earth elements (REEs) have been used as fertilizer to promote agriculture production in China for over two decades. REEs are widely spread in environment, and eventually enter the food chain.     

稀土元素在植物中的分异研究进展

有关对稀土农用的理论和实践、天然和农业生态系统中稀土的地球化学行为及稀土的增产生理过程与毒理等方面已开展了大量研究,而对稀土进入植物体内的迁移过程、分布分异现象和机制缺乏必要的了解。稀土元素在植物中的分异研究有助于“示踪”稀土元素在土壤(溶液)-植物系统中的迁移路径,进而查明控制稀土元素迁移和积累的体外和体内敏感因素。本文结合近5年的研究工作,就近年来国内外有关稀土元素在植物中的分异现象、机制及其研究意义进行了综述,并展望了此方面的研究趋势,期望能为稀土以及重金属的生物有效性研究开辟一条新思路。     

Development of a Mixed Organic Acid Extractant for the Evaluation of Plant Availability of Rare Earth Elements in Soils

In recent years, fertilizers containing rare earth elements (REEs) have been used widely in agriculture (1, 2) and it may result in a potential increase in the contents of REEs in soil and cause environmental pollution. Therefore it is very important to obtain more knowledge of environmental effects of REEs in order to predict any possible deleterious effect occasioned by their use.     

The effect of humic acid on the adsorption of REEs on kaolin

For a better understanding of adsorption of the rare earth elements (REEs) onto minerals and its controlling factors, adsorption experiments were performed at pH range of from 3 to 10 with kaolin (1500 mg/L) in a matrix of various concentration of NaNO₃ and about 20 μg/L of the total REEs as well as various amounts of humic acid (HA). The adsorption of HA onto the kaolin occurred over a wide pH range and decreases with increasing pH and with increasing HA concentration. The results show that humic acid has ability to either increase or decrease the adsorption of the REEs onto kaolin, depending on pH, which may be related to their speciation distribution, interaction of HA with the mineral surface. Furthermore, the light REEs are more adsorbed onto kaolin in presence of higher concentration of HA, presumably because the increase in HA concentration in the solution enhance stronger complexing of HA with heavy REEs as compare to light REEs. The ionic strength has strong effect on the adsorption of HA and REEs onto the kaolin but little on the REEs fractionation. The results presented here indicate that mineral/water adsorption may generate the enrichment of the dissolved heavy REEs in the presence of a significant amount of humic acid, which is consistent with the fractionation of REEs in the most of natural waters.     

Spectral Interferences in the Determination of REEs in Samarium and Dysprosium Matrices by High Resolution Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES)

There is an increasing need for sensitive, accurate and convenient analytical techniques for rare earth elements (REEs) analysis and determination with their expanding applications. Rare earth elements (REEs) are widely used in the areas of industry, agriculture and modern technologies, e.g., as growth promotion agent in agriculture,catalyst in oil refining, additives in new ceramic material and special steels, etc. It is also finding important application in nuclear industry.     

稀土发挥生物效应的机制及其作用物种探讨

稀土在工业、医药领域、基础研究以及在我国的广泛农用引起了人们对其生物效应机理以及可能毒性的关注.在稀土生物学效应机理及毒性的研究中,无论是在动物水平还是细胞层次,引起生物学效应的稀土物种都是一个关键问题,一直存在争议.本文对以动物、细胞为模型的生物效应研究中的实验条件进行分析,对生理条件下引起稀土生物学效应的可能物种提出"稀土离子池"(rare earth ion pool)模型,并对其引起生物学效应的活性物种以及与细胞膜相互作用的方式进行了探讨,以期为阐明复杂生物学体系中稀土化合物的作用机制提供思路.     

稀土元素日允许摄入量与农用安全性探讨

稀土农用是我国独立开创的稀土应用领域,30年来,取得了巨大的经济效益。然而,作为元素周期表中第ⅢB主族的重金属,稀土元素不是动植物的必需微量元素,其生理效应的机制还不清楚,稀土农用的安全性问题一直受到密切的关注。本文从稀土元素分析方法与人均总膳食摄入量、稀土元素毒理实验方法与日允许摄入量、稀土农用对土壤中稀土元素含量和化学形态的影响、以及稀土农用对食物中稀土元素含量影响的4个方面,对文献报道作了分析、整理和评定,结论是只要对使用的范围、剂量及施用方式进行限制,稀土农用是一种安全的农业增产方式。     

Celastraceae sesquiterpenoids: biological activity and synthesis

Plant extracts of the Celastraceae have been used for centuries throughout South America and China as insect repellents and insecticides in traditional agriculture, and also for the treatment of a plethora of medical ailments from stomach complaints and fever to rheumatoid arthritis and cancer. Many of the medicinally interesting properties associated with these crude preparations have now been attributed to a large family of highly oxygenated sesquiterpenoids based on a tricyclic dihydroagarofuran skeleton. In this article, the structural diversity and range of biological activities associated with this intriguing class of natural products are examined with a view to stimulating interest in their total synthesis. Existing synthetic endeavours towards their synthesis are also evaluated.     

Anticipation on the Development of Polycarbonate Production Technology by Using Ester-interchange Method in China

Polycarbonate (hereinafter referred to as "PC ") is the sole product having good transparency among the 5 major engineering plastics. In 2000, the worldwide PC production capacity was reached up to 2,800,000 tons of several hundreds of brands of various grades. It is estimated that the global PC production capacity will exceed 3,500,000 tons in 2005. The global demand for PC was 1,900,000 tons in 2000, which will reach to 2,600,000 tons and more than 3,000,000 tons in 2003 and 2005 respectively according to relevant estimations. The total production capacity of PC of the whole country reached to 3000-4000 tons in 2003. PC imported to China in 2003 was up to 534,000 tons and the apparent amount of consumption of that year was 447,000 tons.The scientific and technical personnel of Chenguang Chemical Research Institute engaged in the research and development of PC production technologies have been advancing wave upon wave with a combatant spirit and the spirit of "Storming the gate" for more than 40 years, having made important breakthroughs in a continuous PC manufacturing process by using ester-interchange method and in project amplification techniques. We consider that favorable conditions are now already available in China for building up PC production plants (each has an annual production capacity of 10,000 tons or above) by using ester- interchange method.In the recent 2 years, the growth rate of domestic annual PC consumption was up to more than 30 %, almost all of which relied on imports from foreign countries. Consequently, the development of domestically made PC has become a task, which brooks no delay. At present, conditions for building up domestic large-scale PC production plants are already available. It should be noted that PC production technologies are matured, PC products have a huge market potential and the returns on investment are optimistic. Therefore, building PC production plants, each with an annual production capacity of 10,000 tons ( approx. ) making use of domestic scientific research achievements and engineering technologies are fully in conformity with the industry policies issued by the State, which will have very important practical significance and far-reaching strategic significance for alleviating a sharp contradiction between PC supply and demand existed in China nowadays, breaking down the blockage against PC production technologies in China and the monopolization over the supply of PC products and product prices of foreign companies and developing our national industries having our own autonomous intellectual properties by means of our own intellectual properties.     

中国不同类型土壤中稀土元素的形态分布特征

采用中子活化分析地中国不同地带土壤中的稀土元素含量分布模型及其赋存形态进行了系统的研究。结果表明，黄棕壤，褐土，淋溶黑钙土及白浆土中稀土元素的分布均为轻稀土富集，Ｅｕ亏损型，砖红壤，红壤为轻稀土富集，Ｃｅ亏损型。     

我国稀土生物无机化学研究进展

我国稀土生物无机化学研究的特点是紧密结合稀土在农用及药物中应用所提出急需回答的问题, 经过长期的工作, 已在稀土的跨细胞膜运转, 稀土进入动物体内后的物种分布, 稀土与细胞膜的作用, 稀土对血红蛋白结构与载氧功能的作用, 稀土对骨细胞及骨结构的影响以及稀土在大鼠肝脏中的积累等方面取得了满意的结果. 从而可以为今后开展稀土元素在农用及药用中危险性评价的基础数据, 同时亦将促进稀土细胞化学的发展.     

Trace element speciation by ICP-MS in large biomolecules and its potential for proteomics

Latest studies on the chemical association of trace elements to large biomolecules and their importance on the bioinorganic and clinical fields are examined. The complexity of the speciation of metal-biomolecules associations in various biological fluids is stressed. Analytical strategies to tackle speciation analysis and the-state-of-the-art of the instrumentation employed for this purpose are critically reviewed. Hyphenated techniques based on coupling chromatographic separation techniques with ICP-MS detection are now established as the most realistic and potent analytical tools available for real-life speciation analysis. Therefore, the status and potential of metal and semimetals elemental speciation in large biocompounds using ICP-MS detection is mainly focused here by reviewing reported metallo-complexes separations using size-exclusion (SEC), ion-exchange (IE), reverse phase chromatography (RP) and capillary electrophoresis (CE). Species of interest include coordination complexes of metals with larger proteins (e.g. in serum, breat milk, etc.) and metallothioneins (e.g. in cytosols from animals and plants) as well as selenoproteins (e.g. in nutritional supplements), DNA-cisplatin adducts and metal/semimetal binding to carbohydrates. An effort is made to assess the potential of present trace elements speciation knowledge and techniques for "heteroatom-tagged" (via ICP-MS) proteomics.     

Microwave assisted extraction for mercury speciation analysis

The application of microwave-assisted extraction (MAE) to the work-up of environmental and biological samples in the study of mercury speciation analysis has increased in recent years and is now increasingly accepted as a standard approach. The review provides a brief theoretical background of microwave heating and the basic principles of microwave energy used for extraction. The advantages and disadvantages of (a) MAE techniques, (b) the influence of the main parameters affecting the extraction, (c) statistical optimization approaches, and (d) strategies for method validation also are highlighted. Recent applications of MAE to mercury species analyses in biological samples, soils, sediments, and crude oil samples are surveyed and critically reviewed. In addition, comparisons of its use with other well-established extraction procedures are discussed.

巢湖、龙感湖水体中稀土元素的无机形态研究

运用MINTEQ化学平衡软件对巢湖、龙感湖中溶解态稀土的形态进行模拟。模拟结果表明，在巢湖和龙感湖中Ln（CO3）^2-，LnCO3^＋是溶解态稀土的最主要的存在形式，当8pH〉7．19时，REE主要以LnCO3^＋形式存在，当pH〉8时，REE主要以Ln（CO3）2^-形式存在，并且∑Ln（CO3）n^3-2n（n=1和2）形态的稀土基本上占溶解态稀土总含量的93％以上。Ln^3＋在巢湖和龙感湖水体中平均丰度为5．03％，Ln^3＋的丰度和pH值成反相关关系。LnPO4在湖水中平均丰度为1．61％，但这种形式的稀土在巢湖和龙感湖中非常重要。巢湖和龙感湖中LREE的LnPO4均处于过饱和状态，甚至巢湖西半湖区丰水期HREE的LnPO4的也都处于过饱和状态，PO4^3＋对稀土的存在有很强的限制作用。InSO4，LnF^2＋，LnOH^2＋，LnCl^3＋等形态的各元素平均丰度均小于1％，在富营养化的淡水中通常可以忽略不计。     

Distribution of rare earth elements among chloroplast components of hyperaccumulator<Emphasis Type="Italic"> Dicranopteris dichotoma</Emphasis>

A rare earth element (REE) hyperaccumulator, Dicranopteris dichotoma, that accumulates more than 0.1% REEs dry leaf mass has been discovered in southern China. The different components of chloroplast were isolated and the concentration of REEs in each component was determined by ICP-MS. The experimental data indicated that about 8% of total leaf REEs was present in the chloroplast of Dicranopteris dichotoma. In order to thoroughly study the distribution of REEs among different components of chloroplast, the membrane of chloroplast, the intact thylakoid and the photosystem II (PS II system) of D. dichotoma were isolated from the chloroplast. It was found that half of total chloroplast REEs was stored at the membrane of the chloroplast and another half was in the thylakoid. And 25% of total chloroplast REEs was bound with PS II system of D.dichotoma. The concentration of REEs in chlorophyll a was only at the level of g/g on the bases of chlorophylls. These data are useful for understanding of both the storage of REEs in chloroplast and the effect of REEs on the photosynthesis of plants.     

Peculiarities of rare-earth-element distribution in environmental objects

The effect of the production of phosphorus fertilizers on the pollution of the environment by rare-earth elements is reviewed. The main sources of rare-earth element pollution in the environment are described. The levels of REEs in components of the environment — atmosphere, snow, different types of soil, native and agricultural types of vegetation — that provide evidence for their participation in the biological cycle of plants are considered. The high values of the correlation coefficients lead one to think that the REE distribution in vegetation occurs under specific laws true for this family of elements.     

Analytical methodologies for aluminium speciation in environmental and biological samples--a review

It is recognized that aluminium (Al) is a potential environmental hazard. Acidic deposition has been linked to increased Al concentrations in natural waters. Elevated levels of Al might have serious consequences for biological communities. Of particular interest is the speciation of Al in aquatic environments, because Al toxicity depends on its forms and concentrations. In this paper, advances in analytical methodologies for Al speciation in environmental and biological samples during the past five years are reviewed. Concerns about the specific problems of Al speciation and highlights of some important methods are elucidated in sections devoted to hybrid techniques (HPLC or FPLC coupled with ET-AAS, ICP-AES, or ICP-MS), flow-injection analysis (FIA), nuclear magnetic resonance (27Al NMR), electrochemical analysis, and computer simulation. More than 130 references are cited.     

Analytical methodologies for aluminium speciation in environmental and biological samples – a review

It is recognized that aluminium (Al) is a potential environmental hazard. Acidic deposition has been linked to increased Al concentrations in natural waters. Elevated levels of Al might have serious consequences for biological communities. Of particular interest is the speciation of Al in aquatic environments, because Al toxicity depends on its forms and concentrations. In this paper, advances in analytical methodologies for Al speciation in environmental and biological samples during the past five years are reviewed. Concerns about the specific problems of Al speciation and highlights of some important methods are elucidated in sections devoted to hybrid techniques (HPLC or FPLC coupled with ET–AAS, ICP– AES, or ICP–MS), flow-injection analysis (FIA), nuclear magnetic resonance (²⁷Al NMR), electrochemical analysis, and computer simulation. More than 130 references are cited.     

Efficient recovery of rare earth elements from coal based resources: a bioleaching approach

Rare earth element (REE) resources in coal-related materials are vast. Assuming a coal production rate of 600 million short tons per year with an average REE content of 200 ppm, the potential REE resource is 120,000 tons per year, which is similar to the annual global production of REEs. Most of those resources that are associated with coal-related materials are found in association with the gangue or ash-based content from the coal ore. Under normal coal plant operation, the REEs often end up in refuse piles or tailings impoundments. In many cases, these REEs can be recovered at low cost using appropriate coal preparation, heap leaching, solvent extraction and/or selective precipitation, followed by subsequent separation and purification of individual REEs. In the present research, the processing approach uses a natural pyrite stream, which was removed during coal cleaning and used to enhance leaching. Bio-oxidation has been used commercially to accelerate leaching, and this approach has been applied to coal-based materials. The ferric ions generated from bio-oxidation oxidize sulfide minerals such as pyrite, which generates acid. Both acid and ferric ions are helpful for leaching REEs, as well as for removing residual sulfides, thereby preventing future acid mine drainage and related liabilities. It can be seen that, recovery of REEs from coal waste materials can enable coal producers to use untapped REEs resources to produce revenue and extend resource life while simultaneously reducing future environmental issues and costs.