太湖水体中稀土元素地球化学特征

以中国第三大淡水湖泊太湖为研究对象,通过液-液萃取、连续提取法以及ICP-MS测试技术对太湖水体中溶解态和悬浮物中的稀土进行分析.结果表明:太湖水体中溶解态稀土含量较低.由于湖水的混合作用整个西太湖水体中稀土元素含量比较相近,东太湖水体由于自净化作用含量低于西太湖.由于颗粒物表层胶体的吸附作用,溶解态稀土呈现出重稀土富集现象.悬浮物AEC态可能由于富含铁的有机胶体、磷酸根络合和富含铁锰次生矿物相等的作用,呈现出中稀土富集.水体中溶解态稀土几乎全部是以有机络合物的形式存在;悬浮物是稀土元素的主要载体,且残渣态＞AEC态＞溶解态.     

临涣采煤沉陷区地表水稀土元素地球化学特征

以淮北临涣采煤沉陷区地表水为研究对象,共采集6个地表沉陷区积水样品、 13个河水样品,采用ICP-MS测定样品中稀土元素含量,分析了水中稀土元素分配模式,利用化学平衡软件MINTEQ(3.1版)计算了水体中稀土元素络合方式。结果表明:研究区地表水中∑REE含量较低,平均含量为0.2121μg·L~(-1),其中沉陷区积水、河水中∑REE平均值分别为0.1967和0.2532μg·L~(-1);水体呈现富轻稀土元素特征,轻稀土/重稀土比值达到1.55,并呈现出显著的Ce负异常及Eu正异常,河水中(La/Yb)_N与pH, HCO~-_3有较为显著的相关性,但沉陷区水中(La/Yb)_N与pH, HCO~-_3相关性不明显;模拟计算结果显示,河水及沉陷区水的Ln(CO_3)~-_2碳酸盐无机络合形式平均占比在90%以上,其次是LnCO~+_3络合形式; pH值, Na~+, Ca~(2+), Mg~(2+)等常量阳离子浓度会影响REE的迁移,偏碱性的水化学性质会影响REE的分异。     

贵州阿哈湖溶解态稀土的垂向分布及形态特征

以中国西南季节性缺氧湖泊阿哈湖为主要研究对象,采用液-液萃取及ICP-MS测试技术,对湖泊不同深度水体中稀土元素进行分析。研究结果表明:随着阿哈湖水体深度增加,从表层至湖上层下部溶解态稀土浓度急剧升高,从湖上层底部至温跃层顶部稀土浓度快速降低,从温跃层上部至湖下层上部溶解态稀土浓度逐渐降低。湖泊颗粒物表面有机碳的矿化作用是造成溶解态稀土在湖上层浓度急剧升高的主要原因,胶体的絮凝作用使溶解态稀土在湖上层底部至温跃层顶部浓度急剧下降,在温跃层上部至湖下层上部水体中,由于新生成的MnO_2吸附作用使溶解态稀土浓度持续下降。形态模拟结果显示,溶解态稀土主要是以稀土有机结合态和稀土碳酸盐结合态两种形式存在。稀土有机络合物占总溶解态的比例遵循以下规律:湖上层温跃层湖下层;LREE-DOCMREE-DOCHREE-DOC。     

北海半岛水体混合过程的稀土元素分布特征

选择北海半岛南流江河口、半岛近岸海域及涠洲岛附近海域为对象,研究河海水混合过程中稀土元素的某些地球化学特征。结果表明,水体中稀土元素主要以悬浮颗粒态存在,溶解态稀土含量及轻、重稀土含量之比从河流到海洋逐渐降低。溶解态稀土含量在南流江河口低盐度区因胶体絮凝而下降,在中高盐度区,颗粒物解吸或部分溶解引起含量上升;pH值对其亦有影响。溶解态稀土分布模式以重稀土相对富集为特征,在此基础上存在中稀土富集,是源区铁锰氧化物和水体中有机胶体共同作用的结果,Ce正异常与水体中有机物有关,Eu负异常是对源区岩石分布模式特征的继承。而原水中稀土含量变化相对复杂,与水动力状况有关,分布模式较为一致,表明河流颗粒物存在均一化趋势。     

天津沿海排污河中稀土元素的地球化学特征

选择天津沿海的南、北排污河为对象，研究了城市排污河中稀土元素的某些地球化学特征。结果表明，在排污河水体中溶解态稀土含量仍很低，但与其他天然大河相比，Eu和重稀土溶解态含量明显偏高。原水中稀土元素含量较高，以悬浮态为主。轻稀土的溶解态与悬浮态分布模式随原子序递增有相反的变化趋势。沉积物与悬浮物中的稀土含量明显低于其他天然河流，而悬浮物中的稀土含量又明显低于沉积物。沉积物与悬浮物中的稀土分布模式相似，均为轻稀土富集、重稀土亏损、Eu正异常型。这种分布模式与其他天然河流不同，而与本地区含有机质丰富的土壤相似，表明其外源为附近土壤。排污河稀土元素地球化学特性与天然河流的差异可能主要由于其水体中含有大量有机污染物造成的。     

赣南小流域水体中溶解态稀土元素地球化学特征

以亚热带富稀土背景区的赣南水系为研究对象,通过ICP-MS测定,探讨了赣南小流域水体中溶解态稀土元素的含量及分布模式,结果表明：赣南小流域溶解态稀土（DREE）含量均值为1.2845μg·L^-1,其浓度高于长江、珠江等内陆天然河流,这反映了其富稀土背景的特点。该区溶解态稀土元素分布模式表现出Ce明显的负异常和Eu正异常,这与同一背景下表土层中的Ce正异常和Eu负异常是相对应的。溶解态稀土元素的页岩标准化分布模式表现为中重稀土（MREE/HREE）富集型,这是由于该区富含重稀土矿物的易风化的氟碳钙钇矿的存在引起的。     

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。     

天津沿海潮间带沉积物中稀土元素的地球化学特征

研究了天津沿海潮间带沉积物中稀土元素(REE)的地球化学特性以及污染条件下稀土元素的环境行为特征,通过稀土分布模式特征探讨了潮间带沉积物的物质来源.结果表明(1)潮间带沉积物中14种稀土含量总和的均值为164.5mg@kg-1,但各岸段又有不同.大致以海河口为界,北部明显高于南部,均值分别为182和150mg@kg-1,均明显高于海洋沉积物稀土含量;(2)海岸带沉积物稀土形态分布特征是自北向南残渣态比例逐渐下降,铁锰氧化物态和有机结合态比例逐渐增高,与黄河、长江等大河相比,残渣态和碳酸盐态比例都显著偏低;(3)稀土元素分布模式均为轻稀土富集、铕中度亏损型,与沿海排污河及内陆大河沉积物稀土分布模式相似,而与海洋大陆架沉积物稀土分布模式有显著差别.     

黄山景观流域溶解态稀土元素地球化学特征

对黄山景观流域径流中溶解态稀土元素进行了研究,以探讨其地球化学特征与物质来源。结果表明,其主要来源为岩石化学风化,其次为大气输入。稀土元素含量枯水期高于丰水期,与蒸发富集效应有关。流域源头稀土元素含量高、重稀土相对富集,中下游稀土含量低、轻稀土相对富集,反映了源头花岗岩到中下游沉积岩对其相应控制。流域水体中Ce为负异常,表现出对流经原岩如花岗岩的继承;Eu为正异常,归因于花岗岩中斜长石/钾长石等矿物的优先风化释放。Y/Ho比值在空间上存在分异,主要为流经岩性不同所致,季节性分异则受到了水/粒相互作用的影响。研究表明,黄山景观流域溶解态稀土元素来源与迁移受流经岩性尤其花岗岩的影响显著。     

酸雨胁迫及稀土农用条件下菠菜及其土壤中稀土元素的赋存

利用盆栽实验研究了酸雨胁迫、稀土农用条件下 ,菠菜及其土壤中稀土元素的含量及分布特征。结果表明 :菠菜地上部分的REE含量为 0 .5 2 7～ 0 .696μg·g- 1 之间 ,地下部 2 .668～ 3 .0 0 3 μg·g- 1 。土壤 2 2 9.0 9～ 2 5 0 .3 μg·g- 1 。酸雨明显地影响作物对REE的吸收和利用 ,酸度越大 ,影响越明显。随着酸雨酸度的增大、植株体内、土壤中的REE受淋洗的作用加强而表现出REE的总量随着pH的减小而逐渐减少。施用稀土后 ,植株的地上或地下部分及其土壤中的REE含量均与对照的土壤中的REE分配模式基本相同 ,遵循稀土元素分布丰度的奇偶 (Oddo Harkins)规则、轻稀土富集 ,Eu弱负异常 ,富铈配分型 ,表明稀土元素仍然主要来自土壤并受其影响。     

Competitive sorption of carbonate and arsenic to hematite: combined ATR-FTIR and batch experiments

The competitive sorption of carbonate and arsenic to hematite was investigated in closed-system batch experiments. The experimental conditions covered a pH range of 3-7, arsenate concentrations of 3-300 μM, and arsenite concentrations of 3-200 μM. Dissolved carbonate concentrations were varied by fixing the CO(2) partial pressure at 0.39 (atmospheric), 10, or 100 hPa. Sorption data were modeled with a one-site three plane model considering carbonate and arsenate surface complexes derived from ATR-FTIR spectroscopy analyses. Macroscopic sorption data revealed that in the pH range 3-7, carbonate was a weak competitor for both arsenite and arsenate. The competitive effect of carbonate increased with increasing CO(2) partial pressure and decreasing arsenic concentrations. For arsenate, sorption was reduced by carbonate only at slightly acidic to neutral pH values, whereas arsenite sorption was decreased across the entire pH range. ATR-FTIR spectra indicated the predominant formation of bidentate binuclear inner-sphere surface complexes for both sorbed arsenate and sorbed carbonate. Surface complexation modeling based on the dominant arsenate and carbonate surface complexes indicated by ATR-FTIR and assuming inner-sphere complexation of arsenite successfully described the macroscopic sorption data. Our results imply that in natural arsenic-contaminated systems where iron oxide minerals are important sorbents, dissolved carbonate may increase aqueous arsenite concentrations, but will affect dissolved arsenate concentrations only at neutral to alkaline pH and at very high CO(2) partial pressures.     

开滦煤洗选过程中稀土元素的迁移和分配特征

以河北开滦矿区晚古生代煤及其洗选产品为研究对象，运用电感耦合等离子体质谱（ICP-MS）和逐级化学提取的方法，对稀土元素的质量分数及其在洗选过程中的迁移和分配特征进行了研究。结果表明，开滦矿区煤中稀土元素没有明显富集；稀土元素在入洗原煤及其洗选产品中，以煤泥中质量分数最高，尾煤次之，在尾煤和煤泥中均相对富集；稀土元素在精煤中的质量分数最低；同原煤相比，中煤的稀土元素质量分数没有明显变化。原煤及其洗选的4种产品中的稀土元素分配模式基本相同，主要差别是质量分数的不同。稀土元素在洗选过程中的分配行为和赋存状态主要受控于黏土矿物，其次是有机质。     

Determination of valuable elements in natural phosphates

Natural phosphates are used on large scale in the fertilizer industry. The usual process of the chemical attack is sulfuric (predominant) and nitric acids. The liquid phosphoric acid phase resulted contains dissolved valuable elements like: uranium and rare earths elements (REEs). Uranium and REEs are recovered in some technologies as valuable products. It is therefore important to know, uranium and REEs content in natural phosphates in view to decide on their recovery. In this paper determinations were carried out to find the uranium and REEs contents. The concentrations involved are low, therefore, it is difficult to find a classical reliable method without incurring important losses, i. e., errors. In this work uranium and REEs were determined by physical methods like: neutron activation analysis (NAA), emission spectroscopy, mass spark spectrometry and X-ray fluorescence. The results obtained were acceptable and intercomparison between various methods was carried out. It was found that most reliable results were given by mass spark spectrometry and activation analysis. The data resulted are in good agreement with uranium and REEs in the green cake (uranium tetrafluoride) and in the REEs concentrate obtained by solvent, extraction from phosphoric acid.     

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.     

Direct determination of rare earth impurities in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry

A novel method was developed for the direct determination of trace quantities of rare earth elements (REEs) in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry (ICP-MS) in this work. The mass spectra overlap interferences arose from Er matrix on the neighbouring and monoisotopic analytes of ¹⁶⁵Ho(100) and ¹⁶⁹Tm(100) were eliminated by adjusting instrumental peak resolution value from 0.7 to 0.3 amu. The matrix suppression effect of Er on the ion peak signals of REEs impurities was effectively compensated with spiking In as internal standard element. The limit of quantitation (LOQ) of REEs impurities was from 0.0090 to 0.025 μg g⁻¹, the recoveries of spiked sample for REEs were found to be in the range of 90.3-107% through using the proposed method and relative standard deviation (R.S.D.) varied between 2.5% and 6.7%. The novel methodology had been found to be suitable for the direct determination of trace REEs impurities in 99.999-99.9999% high purity Er₂O₃ and the results obtained from this method keep in good agreement with that acquired from high resolution ICP-MS.     

Determination of rare earth elements in Indian kimberlite using inductively coupled plasma mass spectrometer (ICP-MS)

A method has been developed for the analysis of rare earth elements (REEs) in kimberlite samples using inductively coupled plasma mass spectrometer (ICP-MS). The samples were dissolved using sodium peroxide fusion and after appropriate dilutions the solutions were analyzed using ICP-MS. The paper presents the concentration of rare-earth elements as determined by ICP-MS in eight kimberlite samples from Central India. The method was validated using certified reference materials STSD-1 and STSD-2 from Canadian Certified Reference Material Project. The method detection limit of various REEs varies from 0.12 to 1.54?mg?kg^?1. The total REE concentrations range from 418 to 726?mg?kg^?1 and fall within the interval of those reported in the literature for kimberlites. Despite the marked difference in the REE contents, all the analyzed samples show similar REE patterns that resemble those for kimberlites. In order to compare ICP-MS results, the samples were analyzed using instrumental neutron activation analysis which is a reference method for determination of REEs in geological samples.     

Determination of rare-earth elements in a limestone geological standard reference material by ICP-MS following solvent extraction.

Rare-earth elements in a limestone geological standard (JLs-1) were determined by inductively coupled plasma mass spectroscopy (ICP-MS) using phosphoric acid 2-ethylhexyl ester solvent extraction, which had been established for seawater analysis. First, the limestone sample was divided into two fractions: acetic acid soluble (carbonate fraction) and insoluble (residue). A modification of the method was undertaken to achieve quantitative recovery. With this method most of the REEs in the carbonate fraction were quantitatively recovered, except for the heaviest three REEs (Tm, Tb and Lu). The reason for the poor recoveries of the three elements was investigated, but still remained unclear. The mass-spectroscopic interference of BaO with Eu made an accurate determination of both lighter REEs and Eu at the same time impossible. The precision of this method was better than 20%. The data adopted after analytical consideration were consistent with those previously reported.