Determination of nitrite with a nano-gold modified glassy carbon electrode by cyclic voltammetry

Abstract

Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) was employed to determine the concentration of rare earth elements (REEs) in plants and soils. Sample preparation and analytical conditions were investigated to set up a simple routine procedure for measuring rare earth elements. For prompt sample decomposition, a microwave digestion technique was successfully used with an acid mixture of HCl+HNO₃+HF. Detection limits, reproducibility, accuracy and possible interference were also studied. ICP-MS provided extremely low detection limits for REEs (0.6–6ng/l). Precision was typically better than 6% RSD (relative standard deviation) for soil and 10% for plant. The potential of the method was evaluated by analysis of standard reference materials of soils and plants. A good agreement between the experimental results and certified values was observed. The spectroscopic interference of Ba with Eu and light REEs(LREEs, La-Eu) with heavy REEs(HREEs, Gd-Lu) were eliminated by the algebra correction.

The results suggested that REEs in soil samples existed mainly as light REEs, and the same concentration distribution patterns of Oddo-Hakins law were observed, showing negative gradient from La to Lu concentrations. The REE contents in plants were very low, less than 20μg/g and varied with plant species. Apart from rape leaf(Brassica juncea), the REE distribution patterns in other plant leaves were consistent with soils, indicating that these plants generally absorbed REEs from soil without selectivity. Rape leaf showed selective absorption for LREEs, especially for La. The REE concentration distribution in parts of hot pepper(Capsicum annuum) was characteriaed by root>leaf>stem>fruit. The REEs absorbed by hot pepper concentrated mainly in roots and leaves, very little migrated into fruit. Transfer factors(TFs) of REEs in plants were very low. Although the contents of LREEs were relatively more than those of HREEs, no distinct difference of TFs between LREEs and HREEs was observed, meaning that LREEs and HREEs have the same abilities of transportation. However, for rape leaf, the TFs of LREEs were one or two orders of magnitude higher than those of HREEs.     

Determination of rare earth and other elements in algae by ICP-MS and neutron activation analysis

Several rare earth elements (REEs) and other elements in algae were investigated by ICP-MS and INAA. Algae materials were supplied from an IAEA Intercomparison Study:Chlorella vulg. grown under reduced levels of toxic elements (IAEA-391) and IAEA-393 algae was grown in a medium to which certain toxic elements were added. 34–691 mg of algae samples were dissolved in conc, nitric acid using a microwave sampleppreparation system. REEs could be detected in the order of magnitude of 10⁻³ ng/g by ICP-MS. Activation analysis failed to detect any REEs because of a strong interference due mainly to²⁴Na and³²P. The distriubtion patterns of these REEs in algae slightly differed from those ofCarya sp. and tobacco leaves, and differed significantly from that of fern leaves. The distribution pattern was rather similar to that found in the North American shale composite (NASC).     

Uncertainty propagation through correction methodology for the determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry

Determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry (ICP-QMS) shows several spectroscopic overlaps from M⁺, MO⁺ and MOH⁺ ions. Especially, the spectroscopic interferences are observed from the atomic and molecular species of lighter rare earth elements including Ba during the determination of Eu, Gd and Tb. Mathematical correction methods, knowing the at.% abundances of different interfering isotopes, and the extent of formation of molecular species determined experimentally, have been used to account for various spectroscopic interferences. However, the uncertainty propagated through the mathematical correction limits its applicability. The uncertainty propagation increases with the increase in contribution from interfering species. However, for the same extent of total contribution, the overall error decreases when the interfering species are more than one. In this work, chondrite as well as a few geological reference materials containing different proportions of various rare earth elements have been used to study the contributions of different interfering species and the corresponding uncertainty in determining the concentrations of rare earth elements. A number of high abundant isotopes are proposed for determining the concentrations of various rare earth elements. The proposed isotopes are tested experimentally for determining the concentrations of different rare earth elements in two USGS reference materials AGV-1 and G-2. The interferences over those isotopes are corrected mathematically and the uncertainties propagated due to correction methodology are determined for those isotopes. The uncertainties in the determined concentrations of rare earth elements due to interference correction using the proposed isotopes are found to be comparable with those obtained by the commonly used isotopes for various rare earth elements.     

Element content in a number of plant leaves and accumulation of some elements in typical plant species: A case of Okayama Prefecture

Content of 40 elements in plant leaves, soils and rocks collected from several sampling sites in Okayama Prefecture was analyzed by instrumental neutron activation analysis using the Research Reactor of Kyoto University. Of these, 16 elements were taken up, and the relationship among their amounts in plants, rocks and soils was discussed, focusing mainly on the essential elements of higher plants and related elements in the periodic table. Although most element contents in plant were different among species, the mediam values of the most non-essential elements in the leaf were lower than the contents in the soil and rock samples. However, essential elements showed significantly higher median values than those in the soil and rock samples. Most element contents in leaves showed a logarithmic normal distribution. The normal distribution was observed in most essential elements except for zinc, while non-essential elements did not show a normal distribution. The results obtained by analysis of variance, showed that the plant species studied could be divided into four major groups, namelyDicotyledoneae, Monocotyledoneae, Gymnospermae andPteridophyta. In general,Dycotyledoneae andPteridophyta had higher element contents thanMonocotyledonaeae andGymnospermae.     

Concentration levels of rare-earth elements and thorium in plants from the Morro do Ferro environment as an indicator for the biological availability of transuranium elements

Plants and soils from a natural thorium and rare-earth element occurrence (Morro do Ferro, Brazil) were analyzed by alpha spectrometry (Th) and ICP-AES (REE), after pre-concentration of the elements by solvent extraction, co-precipitation and ion exchange procedures. Leaching experiments with humic acid solutions and different soils were performed to estimate the fraction of elements biologically available. High concentrations of the light rare-earth elements (LREE) and of Th, reaching some hundreds of g/g-ash, were measured in plant leaves from the areas of the highest concentration of these elements in soil and in near-surface waters. Chondrite normalized REE plots of plant leaves and corresponding soils are very similar, suggesting that there is no significant fractionation between the REE during uptake from the soil solution and incorporation into the leaves. However, Ce-depletion was observed for some plant species, increasing forSolanum ciliatum in the sequence: leaves<fruits<seeds. Soil to plant concentration ratios (CR's) for Th and the REE, based on the total concentration of these elements in soils, are in the range of 10^–3 to 10^–2. Leaching experiments confirmed the importance of humic acid complexation for the bio-uptake of Th and REE and further showed that only a very small fraction of these elements in soil is leachable. The implications of these results on the calculated CR's will be discussed.     

Determination of individual rare earth elements in Vietnamese monazite by radiochemical neutron activation analysis

Radiochemical neutron activation analysis (RNAA) has been applied for determination of rare earth elements (REE) in Vietnamese monazite. The chemical separation procedure used is based on the chromatographic elution of rare earth groups, after the separation of²³³Pa(Th) in irradiated monazite samples by coprecipitation with MnO₂, the rare earth elements were retained by Biorad AG1×8 resin column in 10% 15.4M HNO₃-90% methanol solution. The elution of heavy rare earth (HREE) and middle rare earth (MREE) groups was carried out with 10% 1M HNO₃-90% methanol and 10% 0.05M HNO₃-90% methanol solution, respectively; while the light rare earths (LREE) were eluted from the column by 0.1M HNO₃ solution. The accuracy of the method was checked by the analysis of granodiorite GSP-I and the rare earth values were in good agreement.     

Determination of rare earth elements in chloroplasts of Brassia napus by INAA and biochemical separation techniques

Intact chloroplasts were isolated from mesophyll protoplasts of Brassia napus. Concentrations of 8 rare earth elements (REEs) in the chloroplasts were determined by instrumental neutron activation analysis (INAA). The results showed that there were trace amounts of REEs in the chloroplasts, which corresponded to 1 atom of REEs per 2000 chlorophyll molecules. About 30% of the total REEs in the leaves are localized in the chloroplasts and the light REEs were enriched with respect to the heavy elements of the series.     

Distribution of chemical elements inVaccinium myrtillus (blueberry) — basic problems for representative sampling of plants for multi-element analysis in ecosystems

Summary To get more information about establishing a representative sampling program for multi-element analysis in ecosystems, leaves and fruits ofVaccinium myrtillus were investigated for special criteria of seasonal and interherd fluctuations in elemental distribution within a forest ecosystem. Eleven chemical elements were quantitatively determined by AES/ICP. The interherd variances in elemental compositions of different stands ofVaccinium myrtillus (leaves) are between 12% and 45%, the seasonal fluctuations within two months in leaves ofVaccinium myrtillus are between –33% (Rb)and +159% (Ba). Compared with fruits, leaves represent higher concentrations of Mg, Ca, Sr, Ba, Al, Fe, Zn, similar concentrations of K and Cu and lower concentrations of Rb and P. Comparable results from different institutes in multi-element analysis can only be obtained by sampling same plant species in a defined period of the year.

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Verteilung von chemischen Elementen inVaccinium myrtillus (Blaubeere) — grundsätzliche Probleme der repräsentativen Probenahme von Pflanzen für die Multielement-Analyse in Ökosystemen

     

REE bound DNA in natural plant

The binding of rare earth elements (REEs) with nucleic acids in the leaves of fern Dicranopteris dichotoma (DD) has been studied by molecular activation analysis (MAA). The REEs bound DNA (REE-DNA) was obtained from the leaves of DD. The CTAB-based procedure was modified for extraction of total DNA. The purity of DNA was examined by UV spectroscopy. The DNA obtained was separated and determined by agarose gel electrophoresis further. Meanwhile, the contents of eight rare earth elements (La, Ce, Nd, Sm, Eu,Tb, Yb and Lu) in REE-DNA were detected by instrumental neutron activation analysis (INAA). The results showed that REE-DNA with higher purity could be extracted from plant using this method. It was also found that REEs were bound firmly with DNA in the leaves of DD. The molecular weight (MW) of REE-DNA band was about 22 kb in agarose gel electrophoresis.     

Determination of trace amounts of gold in the presence of rare earth elements in rock samples from Makhtesh Ramon (Southern Israel), by instrumental epithermal neutron activation analysis

Epithermal neutron activation analysis (ENAA), followed by high resolution gamma-ray spectrometry, was applied to determine trace amounts of Au in the presence of rare earth elements (REE) from vein samples in the basaltic rocks of Makhtesh Ramon, located in southern Israel. The contribution of¹⁵²Eu (411.1 KeV) to the 411.8 keV peak of¹⁹⁸Au was determined using multiple gamma-peak, ratios derived from Eu standards and mixtures of Au and Eu. The concentration of Au was found to be in the range of 10–80 ppb. A group of rare earth elements: La, Eu, Ce, Tb, Sm, Lu, Yb was identified; the concentration of Eu was found to be 0.5 ppm.     

La、Ce、Yb掺杂对LiNi0.5Mn1.5O4高电压正极材料性能的影响

采用低温燃烧法制备出不同稀土元素掺杂的高电压镍锰酸锂(LiNi_(0.5)Mn_(1.5)O_4)正极材料,探究了不同掺杂比例(物质的量分数0.5%、1%、2%)和不同掺杂稀土元素(La、Ce、Yb)对样品性能的影响,并通过X射线衍射、拉曼光谱、电子顺磁共振和恒电流间歇滴定等技术探究了其影响机理。从X射线衍射图可以看出,稀土掺杂可以抑制Li_xNi_(1-x)O杂质相的产生;电感耦合等离子谱结果表明,掺杂进入的稀土元素与设计比例基本相符;从拉曼光谱图可以看出,稀土元素可以使样品的有序相增多,其中Ce掺杂样品的有序相最多;结合电子顺磁共振波谱氧空位测试,发现Ce掺杂诱导了样品中有序相比例增加,从而使样品的稳定性提高;经恒电流间歇滴定技术测试发现,Ce掺杂镍锰酸锂样品的扩散系数比未掺杂样品高了约15倍;在不同掺杂比例上,1%掺杂量时样品性能最佳。在3种最佳掺杂量的稀土元素样品中,Ce掺杂的样品性能最优,首次放电比容量可以达到133.3mAh·g~(-1),比未掺杂样品放电比容量高且首次效率提高了 18%,在1C下循环200次后,容量保持率为102%,比未掺杂样品提高了 8%。     

Determination of rare earth elements and thorium in britholite ore by energy dispersive X-ray fluorescence spectrometry

A radioisotope-excited X-ray fluorescence technique is applied for the determination of thorium and rare earth elements in britholite ore from Canada. An annular source of⁵⁷Co is employed for excitation of characteristic K X-rays of thorium and rare earth elements. The peak ratios of lanthanides were used to remove the difficulties because of overlapping lines at the 33–50 keV energy region. Matrix effects are examined also in detail and compensated for infinitely thick powdered ore sample. Results obtained in the analysis agree well with recommended values of Canada.     

Determination of rare earth elements in soils and sediments by inductively coupled plasma atomic emission spectrometry after cation-exchange separation

The influence of matrix elements such as Ba, Ca, Fe, K, Na and Ti, on the inductively coupled plasma atomic emission spectrometry determination of the rare earth elements in soils and sediments is investigated and analytical lines with minimal interferences are chosen. The analysis of certified reference materials by two calibration methods (pure rare earth solutions and IAEA-Soil 5) and after cation-exchange proved that calibrations with IAEA-Soil 5 increase the number of accurately determined rare earth elements (REE), permitting the instrumental determination of Ce, Eu, La, Nd, Tb, Yb and Y in soils and some sediments. The cation-exchange procedure permits the determination of 12 REE with very good accuracy (below 10%) and detection limits varying between 0.05 (Eu, Tb, Yb) and 0.5 (Er) mg kg(-1).     

Mutual Separation of Rare Earths in Monazite with Cation Exchange Elution Chromatography

Mutual separation of the individual rare earth elements (exception of cerium) in monazite from different districts was investigated by cation exchange elution method. Strong acid type cation exchange resin, Bio-Rad AG 50 Wx8 and eluting solution of a α-hydroxyisobutyric acid (α-HIBA) were used. Radioactivity tagged Eu-152, 154 or Tb-160 were used as radio active indicator for determination of the distribution coefficients by batch method or for the study of column elution conditions. By gradiently increase of the pH values from 3 to 5 in 0.3 M α-HIBA eluting solution, complete mutual separation of individual rare earth elements, exception of Dy and Y, were obtained. Dy and Y could not be separated by this scheme of separation and their elution zones were overlapped. Rare earth mixture samples of monazite from different districts were separated with this scheme and these results were compared. From this comparison followings were noticed; 1. Compositions of rare earth elements in monazite from different districts are evidently not alike. 2. Samples from Brazil and Southwestern Coast of Taiwan are much more alike in their compositions but not for those from Australia and Outskirt Island. 3. Sample from Outskirt Island has higher in contents of heavier rare earths and also Nd was higher than La.     

土壤-植物体系稀土元素的分异现象

用仪器中子活化分析测定了从同一地点采集的9种不同植物根和叶中8个稀土元素（La,Ce,Nd,Sm,Eu,Tb,Yb和Lu)的含量，研究了稀土元素在植物根、叶及相应母土中的分布特征。结果表明，同一植物的根、叶和母土中稀土分布模式均有较大差异。生长在同一地点不同植物根中稀土分布模式非常相似，而叶中分布规模差别较明显。说明根对单一稀土元素的吸收主要取决于这个元素在土壤中有效态的含量，而在稀土从根到叶的运输和积累过程中出现的分异则由植物自身的结构特征决定。     

Determination of the Contents and Distribution Characteristics of Rare Earth Elements in Solanum lycocarpum from Tropical Ecosystems in Brazil by INAA

We have determined the concentrations of eight REE elements by instrumental neutron activation analysis (INAA) (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) in plant leaves of the species Solanum lycocarpum, a typical Brazilian "cerrado" plant widely distributed around the country, and in the soils in which they grow. Three different ecosystems were studied. Very similar chondrite normalized patterns were observed in the soil and in the plant, presenting an enrichment of the light REE, indicating a typical absorption of these elements by this species.     

Adsorption of fission products onto soils using a fission multitracer

The adsorption behavior of fission products to various soils was studied using a multitracer. The multitracer was prepared by neutron irradiation of ²³⁵U. Distribution coefficients of fission products were obtained for seventeen kinds of Japanese soils. It was found that zirconium, niobium, and rare earth elements show high distribution coefficients for all soil samples, however, elements like alkali metals show varied values.     

稀土在烤烟植株中的分布及其对烟叶化学成份影响的研究

作为一种生理活性物质,稀土施用在烟草上平均增产11％,上中等烟比例提高7．53％左右,稀土应用于烤烟大部分限于田间试验,缺深入的机理研究^[2-4]。本试验用低浓度混合硝酸稀土喷施烤烟叶面,研究了稀土在烤烟植株中的含量,分布及土壤中可溶态稀土的变化情况及稀土对烟叶化学成份的影响,旨在为烤烟施用稀土提供科学依据。     

Variation of the rare earth element concentrations in the soil, soil extract and in individual plants from the same site

Samples of various types (spruce needles, blackberry leaves, soils, and soil extracts) have each been taken at 6 places from the same site. In addition, 4 whirls each from 2 spruce trees were sampled. Rare earth elements (REEs) were determined in these samples by neutron activation analysis with a chemical group separation. Variations between places were found to be small with soils and soil extracts, but large with plants. Variations between whirls were small. Plants neither reflected the soil nor the soil extract. Both plant species were dissimilar, but the logarithm of their ratio was a linear function of the atomic number of the REE. A negative Ce anomaly (with respect to soil) was found in both plant species.     

Carbon Nanofibers as Solid‐Phase Extraction Adsorbent for the Preconcentration of Trace Rare Earth Elements and Their Determination by Inductively Coupled Plasma Mass Spectrometry

Abstract

Systematic investigations were carried out into the sorption of rare earth elements (REEs) on carbon nonofibers (CNFs) by inductively coupled plasma mass spectrometry (ICP‐MS). The experimental parameters for preconcentration of REEs, such as pH, sample flow rate and volume, eluent concentration, and interfering ions on preconcentration of REEs have been examined in detail. The studied metal ions can be adsorbed quantitatively on CNFs in a pH range from 2.0 to 5.0, and then eluted completely with 0.5 mol l^?1 HNO₃. Based on the above facts, a novel method using a microcolumn packed with carbon nanofibers as an adsorption material was developed for the separation and preconcentration of REEs prior to their determination by ICP‐MS. The proposed method has been successfully applied to the determination of light (La), medium (Eu and Gd) and heavy (Yb) rare earth elements in real sample with the recovery more than 90%. In order to validate this method, two certified reference materials of tea leaves (GBW 07605) and mussel (GBW 08571) were analyzed, and the determined values are in good agreement with the certified values.