电感耦合等离子体质谱法同时测定土壤中多种元素含量的研究

采用微波消解土壤样品,建立了利用电感耦合等离子体质谱技术同时测定土壤中铍(Be)、钾(K)、钙(Ca)、镁(Mg)、铁(Fe)、锰(Mn)、铜(Cu)、锌(Zn)、镍(Ni)、钴(Co)、钡(Ba)、钼(Mo)、钒(V)、钍(Th)、铀(U)、铅(Pb)、镉(Cd)、铬(Cr)、砷(As)、锶(Sr)、钪(Sc)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钇(Y)36种元素的分析方法。方法检出限为0.002 9～0.87μg/L,相对标准偏差为0.94%～6.02%,回收率为95.2%～106%。通过土壤标准物质(GBW07427)及回收率试验的验证,该方法具有准确、快速、灵敏度高等特点,适合于土壤中36种元素的同时测定。     

电感耦合等离子体质谱法测定肥料中稀土元素

为将电感耦合等离子体质谱法(ICP-MS)这一先进技术引入肥料稀土元素的测试中,建立了相应的仪器测试条件,并比较了4种酸体系对样品消解的影响.结果表明,利用ICP-MS测定稀土元素时,以铑(Rh)、锗(Ge)、铟(In)作为内标进行校正,可有效降低干扰,弥补基体抑制效应和灵敏度漂移,该法线性范围宽、检出限低、精密度好....     

ICP—AES法测定土壤及肥料中的硼含量

采用岛津ICP－1000Ⅳ型真空单道扫描发射光谱仪测定了土壤及肥料中的硼含量，方法经标准土壤样品验证，并与肥料测定的国家标准方法相比较，结果均十分符合。同时给出方法的精密度、检出限等参数，说明该方法准确度、灵敏度高，操作简便快速。     

电感耦合等离子体光谱法测定土壤中的全硫

硫元素在植物中属于重要的中量元素,是继氮、磷、钾后第4位主要营养成分,是所有植物生长发育不可缺少的元素之一。硫在植物生长发育及代谢过程中具有重要的生理功能。土壤中全硫能够反映出土壤硫的生态和环境效应,因此,对土壤中全硫的测定显得至关重要。以硝酸-双氧水为消解体系,对土壤样品进行消解,将土壤中不同形态的硫转化为可溶性无机硫,利用电感耦合等离子体发射光谱仪测定土壤中全硫含量。称取0.25 g土壤样品,加入10 mL硝酸、5 mL双氧水,在150℃电热板上消解样品,剩余体积为2 mL左右时取下,样品冷却至室温后定容至25 mL,用电感耦合等离子体光谱仪测定硫含量。实验结果表明,分析谱线为182.037 nm时具有灵敏度好、干扰少的优点,以硫含量为横坐标,强度为纵坐标建立线性回归曲线,其线性回归曲线为Y=0.001195C+0.037420,线性相关系数R2为0.9999。在优化的条件下,方法的检出限和定量限分别为7和23 mg/kg。为了验证方法精密度,选择不同含量级别的国家标准物质平行测定6次,结果显示,相对标准偏差为2.2%～6.8%;绝对偏差为2～171 mg/kg,     

ICP-AES法测定土壤及肥料中的硼含量

采用岛津 ICP- 10 0 0 型真空单道扫描发射光谱仪测定了土壤及肥料中的硼含量 ,方法经标准土壤样品验证 ,并与肥料测定的国家标准方法相比较 ,结果均十分符合。同时给出方法的精密度、检出限等参数 ,说明该方法准确度、灵敏度高 ,操作简便快速     

利用电感耦合等离子体质谱仪He碰撞反应模式测定土壤有效钼

土壤有效钼含量测定对评价土壤钼对作物的有效性和土壤钼供应水平具有重要意义。目前常用极谱法和石墨炉原子光谱法测定土壤有效钼,但因操作复杂,多有不足和不便。采用草酸-草酸铵溶液浸提土壤有效钼,不经分离与富集,采用电感耦合等离子体质谱仪He碰撞模式测定浸提液中钼(95Mo),以103Rh为内标元素。结果表明:方法检出限为1.02μg/L;2个国家土壤标准物质(GBW07413a黄潮土和GBW07416a红壤)有效钼的测定值与标准确认值一致;加标回收率在95.1%~152%之间;对5个土壤样品分别重复测定6次,相对标准偏差小于8%。结论认为电感耦合等离子体质谱仪He碰撞模式可以用于测定草酸-草酸铵浸提的土壤有效钼,该方法测定结果准确,重现性好,快速方便。     

当归药材与产地土壤中无机元素的相关分析研究

采用ICP-MS和AAS测定了95批当归药材及其产地土壤中8种重金属元素和7种其他无机元素含量,研究药材与产地土壤中无机元素的相关性。结果表明,当归药材中的特征性无机元素是Fe、Mn、Mg、As、Cr及Ni,土壤中的特征性无机元素是Zn、Mn、Pb、Cr及Ni;当归药材中,无机元素Mn与Zn、Cr、Fe、Cu,Ni与Fe、Cd、Sb、Zn,As与Sb、Pb、Cr、Mn,Cu与Mg、Pb、Zn,Cr与Fe、Pb,Mg与Sb、Zn,以及Ca与Na呈显著正相关,而K与Na、Pb、Cd呈显著负相关;当归对土壤中的Na有富集作用;无机元素Sb、Ca和Na在当归药材与土壤中呈显著正相关。研究发现,中药当归含有丰富的有益无机元素,有害重金属元素含量极低,符合相关标准,在国际贸易及GAP种植方面具有明显的优势和广阔的发展前景。     

电感耦合等离子体质谱法测定土壤中的总碘

采用碱液热浸提法处理土壤样品,通过电感耦合等离子体质谱法(ICP-MS)测定土壤中碘元素的总量。对前处理的3大参数——碱度、温度和时间进行试验摸索,得出适用于土壤的最佳浸提条件。测定结果显示,该方法的线性范围为0~500μg/L,线性相关系数0.999 8,方法检出限0.12μg/g,加标回收率为91.0%~104%,RSD均小于5%。综上,该法是一种能够快速、灵敏、准确地测定土壤样品中碘元素的先进方法。     

DRC-ICP-MS法测定土壤硒前处理方法研究

研究采用电感耦合等离子体质谱(ICP-MS)法测定土壤硒的最佳前处理方法及动态反应池条件下,建立硒干扰校正方程。试验结论:盐酸、硝酸、高氯酸、氢氟酸四酸和王水高温消解前处理方法不适宜ICP-MS法测试土壤硒,质谱干扰严重,DRC反应模式难以减轻或消除干扰,测试结果不准确;硝酸、高氯酸混酸和王水水浴前处理方法适宜ICP-MS法测试土壤硒,CH4作为反应气,建立了干扰校正方程:I ~(80)Se_((实))=I~(80)Se_((测))-I 1×~(82)Kr_((测)),此条件下,选取的不同类型土壤及沉积物测定值基本在标准值范围内,实际样品加标回收率分别为95.0%～107.6%和91.8%～92.9%。本试验方法为ICP-MS法测定土壤硒提供了可行的前处理方法,为行业标准方法扩充提供了方法借鉴。     

广东红壤中稀土元素的含量及分布特征

对广东8种不同母质来源的土壤样品中的稀土元素含量及分布特征进行了研究，结果表明，除了砂岩外，其余母质上发育的红壤稀土元素总量都低于中国土壤平均含量，其中又以Q2粉砂岩、Q1砂岩、老红沙3种母质的红壤表现最为突出。除了铥、镥和铈外，11种稀土元素的平均含量都低于中国土壤平均含量。广东红壤轻组镧系元素（LREE）和重组镧系元素（HREE）的比值较大，其平均值为15．6。各母质土壤中的Eu表现出明显的负异常，δEu值与中国土壤平均值相接近；而Ce表现出明显的正异常，δCe平均值为1．48，明显高于中国土壤平均值。偶数稀土元素含量均明显高出奇数稀上元素。广东红壤中稀土元素的含量分布受母质、成土过程和外部环境等因素的影响。     

Contents and bioavailability of rare earth elements in agricultural soils in Hesse (Germany)

With increasing agricultural and industrial use of rare earth elements (REEs), input of REEs into the pedosphere has risen in parallel. Since total REE budgets for soils in Germany are mainly unknown, this pilot study investigates the concentrations of REEs in three loess soil profiles under agricultural land use in the Wetterau region, Germany. There were no significant REE applications in the past, so the presented data can be considered as background concentrations of REEs in soils. In addition to the total REE contents (aqua regia digestion), potentially plant‐available (EDTA) and at actual conditions available, mobile (NH₄NO₃) REEs have been determined for each horizon. Interactions between REE availability and properties of soils are explained after assessing several chemical and physical properties. The results reveal a wide range of total REE contents, ranging from 222 to 423 mg kg^–1. With 10.1% of total REE amounts, the potentially plant‐available proportions of REEs are generally low. In contrast, yttrium, which showed high available proportion of 24.8%, was found to be comparable with Cd. Cerium is the most abundant REE in aqua regia digests, whereas only small amounts in the potentially plant‐available fraction were found. Thus negative cerium anomalies could be concluded concerning its potential availability. Generally, bioavailability of REE had significant correlations between clay contents and Fe and Mn oxides for the majority of REEs. Due to moderately high pH (CaCl₂) in soils (average 6.6) the mobile fraction for most of the elements was not detectible.     

Rare earth elements and other trace elements in wastewater treatment sludges

In order to evaluate the possibility of contamination of soil with trace elements by the application of sludges to soil, the contents of rare earth elements (REEs; La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) and other trace elements (Be, As, Ag, Cd, Sb, Cs, Bi, and U) in wastewater treatment sludges were determined. In sludges of night soil treatment plants (night soil sludges) and sludges of wastewater treatment plants in the food industry (food industry sludges), the distribution patterns of REEs normalized versus average REEs in the continental crust were almost flat. It was considered that the REE patterns of uncontaminated sludges reflected the pattern of the continental crust. The crust-normalized REE patterns of sludges of wastewater treatment plants in the chemical industry (chemical industry sludges) and municipal sewage sludges did not always show flat plots. The sludges that did not show a flat REE pattern were considered to be contaminated with some of the REEs.

The coefficient of variation of each element determined among the 10 samples of night soil sludges and the 14 samples of sewage sludges ranged from 34 to 77% and from 26 to 84%, respectively. Among the 10 samples of food industry sludges and the 10 samples of chemical industry sludges, the coefficient ranged from 60 to 143% and from 67 to 172%, respectively. The variations of the content of each element among the food industry sludges or the chemical industry sludges were larger than those among the night soil sludges or the sewage sludges.

The contents of Be, As, Cs, REEs, and U in all the sludges were lower than or the same as those in a field soil. Some of the food and chemical industry sludges contained larger amounts of Ag, Cd, and Sb than the soil. All the night soil sludges and sewage sludges contained much larger amounts of Ag and Bi than the soil.     

稀土元素(REE)示踪土壤侵蚀动态过程的降雨模拟试验研究

该文应用稀土元素(REE)示踪法研究土壤侵蚀发生和发展动态过程的方法,分析了土壤侵蚀沿坡面变化的规律。采用Dy、La、Sm、Yb、Ce、Eu、Nd、Tb等8个REE进行了一系列的人工降雨模拟试验,并采用3个雨强(50,100和150 mm/h)和5个坡度(8.74%,17.63%,36.4%和46.63%),分Ⅰ、Ⅱ2个降雨阶段进行,定量分析了土壤表面雨水动力特征与土壤侵蚀之间的动态平衡过程,揭示了土壤侵蚀发生和发展的过程及土壤侵蚀沿坡面分布的规律,结果表明雨强和坡度越大的条件下,侵蚀率越大的区段越靠近坡的顶端,这与细沟发生的部位完全吻合。     

江西省土壤可溶态稀土元素含量和分布规律的研究

对江西 1 1种母质发育的有代表性的水稻土、旱作地、自然土壤 ,61个剖面 ,4 1 2个土样的可溶态稀土元素分析测定 ,统计结果表明 :江西土壤稀土元素的强度因素处于较高水平 ,平均值为 1 9 0mg/kg ,有 4 2 80 %的样点处于丰富级 ;有由南向北 ,由东向西逐渐降低的趋势 .其含量最高的地区是赣南由花岗岩、泥质岩、第四纪红粘土、酸性紫色土、碳质岩类风化物等母质发育的土壤 ,较低的为赣西北由石英岩 ,第三纪红砂岩、石灰岩、下蜀系黄土等母质发育的土壤 ;在土壤剖面分布中 ,旱作地表层低于底层 ,水稻土表层有生物富集作用高于底层 ;影响土壤中可溶态稀土元素含量的主要因子有 :成土母质 ,气候条件 (温度 ,降水量 ) ,土壤 pH ,土壤质地和耕作类型     

稀土元素对生物体CaM水平调节的剂量效应的研究

从Ca^2 、CaM、Ca^2 -ATP酶3个层次综述了稀土元素对生物体CaM水平调节的剂量效应及其作用机理。     

Potential use of rare earth oxides as tracers of organic matter in grassland

Tracing organic matter (OM) in soil is challenging, because runoff and leaching processes are interrelated and have multiple sources. Therefore, multiple tracers with low background concentrations such as rare earth element oxides (REOs) are necessary to delineate the origin of sources of the organic materials in groundwater, rivers or in catchments. The main objective of this study was to examine the potential use of REOs as a tracer in various forms of OM (1) whole slurry, (2) solid, and (3) liquid phase of cattle slurry after mechanical separation. A laboratory experiment was carried out using five REOs (La, Gd, Sm, Pr, and Nd oxides) mixed directly into soil or mixed with various fractions of cattle slurry and then applied to the soil surface. In the additional grassland experiment, Gd oxide was spiked with soil and cattle slurry and then applied to the soil surface. The mineral N in the liquid phase (urine) of the slurry in the grassland experiment was labelled with ¹⁵N urea (16 atom%). In the laboratory experiment, results showed that the five REOs concentration of soil in 0–1 cm soil section after the rainfall simulation was still up to 20 times more than the background values. In 1–2 cm soil section, the concentration of only Gd (two fold higher) and La oxides (50% higher) were significantly higher than the soil background values. Therefore, we hypothesized that Gd and La oxides were associated also with relatively finer organic particles in slurry, thus 1–2 cm soil section were enriched with these oxides. The five REOs concentration below 2 cm soil depth were similar to the background values in all treatments. In line with the laboratory experiment, Gd concentrations in the deeper soil layers (2–4 and 4–8 cm) in the grassland experiment were not significantly affected by any treatment. Both in grassland and laboratory experiment, solid phase of the slurry (dung) was collected from the soil surface after rainfall simulation. Here, about 56% of REOs were measured on the solid phase of the slurry which indicates the strong binding potential of REOs on slurry OM. The present novel study, where REO tagged slurry was uniquely tested to study geochemical cycle of organic fertilizers, clearly highlighted the potential for their use as multiple‐tracers of (animal derived‐) OM in agricultural soils.     

Conditions related to solubility of rare and minor elements in forest soils

Soil solutions expelled by high‐speed centrifugation (13900 g) of intact soil sample cores at field moisture from 30 forest topsoils (A horizons of mainly Dystric and Eutric Cambisols, according to the FAO‐Unesco system) low in clay were subjected to analysis of 60 elements, using ICP‐MS and ICP‐AES. Concentrations measured were related to soil and soil solution properties assumed to be important for the solubility of elements, using stepwise regression analysis. On an average two thirds of the variability in soil solution concentration of elements were accounted for by, in particular, organic C concentrations, pH and/or nitrate concentrations of the solutions, varying among elements from 19 to 90 %. Concentrations of elements strongly positively related to soil solution acidity were Al, Be, Ge, Li, Ni, Pb, and Zn, strongly negatively related to acidity were Ca, Mo, and W. Most positively related to nitrate concentrations in soil solutions were B, Ba, Cd, Mg, Mn, and Sr; negatively were Nb, Ta, and Ti. Concentrations of organic C in the soil solutions correlated positively, often quite closely, with most of the other elements studied, including La, all the lanthanides, and with Ag, Br, Cr, Fe, Ga, Hf, Hg, In, P, Th, U, Y, and Zr. Soluble organic compounds were apparently ’︁carriers’ of these elements in the soil solution. The concentrations of elements in HNO₃ digests of the soils usually accounted for just little or no statistical variability of their soil solution concentrations.     

Applicability of rare earth element oxides as a sediment tracer for coarse-textured soils

A leaching experiment using a mixture of five REE oxides and gravelly, sandy loam soils was conducted to examine the applicability of the REE oxides as a sediment tracer for coarse-textured soils. The experiment showed little leaching of the oxides and an enrichment of various size classes of soil particles with the oxides, which reflected the strong binding capability of the REE oxides with the gravelly, sandy loam soils. It also showed that the REE oxides preferentially bound with small size classes of soil particles. The preferential binding of the REE oxides with fine materials will cause the overestimation of the soil loss from a given area (i.e., tagged with a given REE) if aggregates are broken down during sediment transport and clay materials are preferentially delivered, and if the soil loss is computed by analyzing the REE concentrations in the whole sediment. To address the non-uniform binding issue, the method based on measuring the REE concentrations for four particle size groups was tested. The potential error of the method was evaluated by comparing the soil loss that would be computed in the case that the particle size distribution was shifted to the smallest particle size class within a particle size group and in the case that no sediment sorting occurred. The result showed that the method would produce a potential error of approximately 4% in the estimation of the total soil loss when sediment sorting occurred. The non-uniform binding of the oxides does not preclude the use of the REE oxides on the coarse-textured soils in the presence of non-uniform binding of the oxides, but adjustments in the technique are required for an accurate estimation of soil loss using the REE technique.     

外源稀土对水稻伤流组分的影响

应用微区试验和伤流测定法研究了外源稀土对水稻根系合成氨基酸和激素的效应,以及对伤流中无机营养离子的影响。结果表明,在本试验条件下,土施低浓度稀土能促进根系合成,显著增加氨基酸总量和激素在伤流中的含量,提高营养离子的吸收;但高浓度稀土却有着明显的抑制效应。应用数学模拟的方法计算出稀土抑制氨基酸合成的半效应值(或50值)约为350～500mg/kg。稀土提高了伤流液中钙的含量,而对磷、钾的含量起抑制效应。