Partitionings and kinetic behaviors of major-to-ultratrace elements between industrial waste incineration fly and bottom ashes as studied by ICP-AES and ICP-MS.

The partitionings of major-to-ultratrace elements between industrial waste incineration fly ash (IWIFA) and industrial waste incineration bottom ash (IWIBA) in industrial waste incinerators were investigated by measuring their concentration distributions, where the incineration ash samples were collected from three different types of industrial waste incinerators. The concentrations of the elements in the incineration ash samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from mg g(-1) to sub-microg g(-1) could be determined in both IWIFA and IWIBA samples. The concentration ratios of CF/CB (CF, concentration in fly ash; CB, concentration in bottom ash) for analyte elements were used to evaluate the partitionings of the elements between fly and bottom ashes. Then, the correlations between the CF/CB values of the elements and the dissociation energies of their monoxides were examined to evaluate the kinetic behaviors of the elements during the incineration processes. It was found that lithophile and siderophile elements, which have a large affinity with oxygen, were almost equally distributed between fly and bottom ashes, regardless of the dissociation energies of their monoxides. On the other hand, chalcophile elements with rather large volatility provided different behaviors; the elements with the smaller dissociation energies of monoxides were more partitioned in fly ashes than those with the larger ones.     

Major-to-ultratrace elements in bone-marrow fluid as determined by ICP-AES and ICP-MS.

The major-to-ultratrace elements in human bone-marrow fluid were determined by ICP-AES (inductively coupled plasma atomic emission spectrometry), and ICP-MS (inductively coupled plasma mass spectrometry). The bone-marrow fluid sample was centrifuged prior to acid digestion to exclude the bone piece from bone marrow, and then digested with nitric acid. As a result, 20 elements could be determined over the concentration range from 1610 microg g(-1) for Na to 0.00043 microg g(-1) for W. It was found that Fe, Zn and Sb were enriched by ca. 264-, 7- and 15-fold, respectively, in bone-marrow fluid, compared to those in human blood serum. Alkali metals (K, Rb, Cs), except for Na, were also significantly enriched in bone-marrow fluid. Furthermore, the concentrations of various elements, such as Fe, P, Al, Zn, Cu, Se, Zr, Sn, Ag and W, were significantly higher than those in open seawater.     

Chemical characterization of airborne particulate matter in ambient air of Nagoya, Japan, as studied by the multielement determination with ICP-AES and ICP-MS.

The multielement determination of PM(10) (airborne particulate matter smaller than 10 microm) samples, which was collected by a high volume air sampler at the urban site of Nagoya City, was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The present analytical method was validated by analyzing urban particulate matter standard reference material of NIST SRM 1648. The analytical data for ca. 30 elements in PM(10) samples collected during a period from 8 September to 9 October, 2003, were obtained in the concentration range from sub-microg g(-1) to several-10 mg g(-1), but the data for 18 elements among ca. 30 elements were available for the characterization of PM(10) samples in ambient air, because of problems caused by the filter blanks. Then, the trends concerning the distributions of diverse elements in PM(10) samples were analyzed based on the enrichment factors and size distribution factors. The lithophile and siderophile elements were distributed more than 50% in coarse particle fraction (>2.1 microm), which was derived mainly from natural sources, such as soils and crustal minerals. On the other hand, chalcophile elements were distributed more than 50% in fine particle fraction (<2.1 microm), which was derived mostly from anthropogenic emission sources. The large enrichment of chalcophile elements in PM(10) samples as well as their mining influence factors (MIFs) suggested their wide use in industrial productions.     

Determination of trace rare earth elements in natural water by electrothermal vaporization ICP-MS with pivaloyltrifluoroacetone as chemical modifier

A novel method based on gaseous compounds introduction into the plasma as their pivaloyltrifluoroacetone (PTA) chelates was developed for electrothermal vaporization inductively coupled plasma mass spectrometry determination of trace rare earth elements (REEs) in natural water. The factors affecting formation of the chelates and their vaporization behaviors were studied in detail. Under the optimized conditions, the limits of detection (3σ) of REEs for this method were from 0.20 to 0.91 ng L⁻¹, the relative standard deviations for 0.1 μg L⁻¹ REEs were 2.5–9.1% (n = 9), and the linear ranges of calibration curve for REEs covered at least three orders of magnitude. The proposed method had been applied to the determination of trace REEs in water samples of Yangtze river, Han Shui river and East lake (Wuhan), and the recoveries for the spiked water samples were 93–105%.     

Multielement determination and speciation of major-to-trace elements in black tea leaves by ICP-AES and ICP-MS with the aid of size exclusion chromatography.

A multielement determination of major-to-trace elements in black tea leaves and their tea infusions was carried out by ICP-AES (inductively coupled plasma atomic emission spectrometry) and ICP-MS (inductively coupled plasma mass spectrometry). Tea infusions were prepared as usual tea beverage by brewing black tea leaves in boiling water for 5 min. About 40 elements in tea leaves and tea infusions could be determined over the wide concentration range in 8 orders of magnitude. The extraction efficiency of each element was estimated as the ratio of its concentration in tea infusions to that in tea leaves. From the experimental results for the extraction efficiencies, the elements in black tea leaves were classified into three characteristic groups: (i) highly-extractable elements (>55%): Na, K, Co, Ni, Rb, Cs and Tl, (ii) moderately-extractable elements (20-55%): Mg, Al, P, Mn and Zn, and (iii) poorly-extractable elements (<20%): Ca, Fe, Cu, Sr, Y, Zr, Mo, Sn, Ba and lanthanoid elements. Furthermore, speciation of major-to-trace elements in tea infusions was performed by using a combined system of size exclusion chromatography (SEC) and ICP-MS (or ICP-AES). As a result, many diverse elements were found to be present as complexes associated with large organic molecules in tea infusions.     

Electrothermal atomic absorption determination of ultratraces of suspended and dissolved species of elements in natural water

Direct and adsorption-atomic absorption procedures are proposed for the determination of suspended and dissolved species of elements in natural water. The procedures involve the fractional vaporization of solid samples (suspensions or adsorbent concentrates) in a graphite crucible atomizer with the simultaneous condensation of filtered and unfiltered element vapors on the surfaces of graphite rods placed above and below the crucible. The obtained microsample condensates were analyzed by independently heating the vaporization and atomization zones and localizing the element vapors in the isothermal analytical zone. The proposed approach makes it possible to use and compare various methods for suppressing matrix interference in a single analysis and to improve the performance characteristics of element determination.     

Composition and origin of trace elements in fog water studied by INAA

Characterization of dilute solution of gamma-irradiated polymethyl methacrylate (PMMA) in acetone has been carried out. The polymer sample in form of natural beads was administered a gamma-ray dose of 30 kGy by a cobalt-60 radiationsource. Various types of viscosities, viscosity average molecular weight, shape and size of irradiated PMMA and its two fractions were calculated. The results were compared with those for unirradiated PMMA. Degradation of PMMA as a result of irradiation has been observed.     

Separation and determination of dissolved and particulate humic substances in river water

Distribution of humic and fulvic acids in participate or dissolved form is studied by using simple leaching and sorption techniques. After filtration of water sample (100–200 ml), the filter along with suspended particles is treated with 5 ml of chloroform and 3 ml of 0.1 mol/l sodium hydroxide solution. The filter dissolves completely in the organic phase, while the suspended particles remain in the aqueous phase enabling a leaching of humic substances. The leaching is repeated once more with 2 ml of 0.1 mol/l sodium hydroxide solution. The humic and fulvic acids in the combined solution are fractionated at pH l by filtration, where the membrane filter is preliminarily coated with sodium dodecyl sulfate. On the other hand, dissolved humic substances are concentrated from a 50-ml filtered sample by sorption on a DEAE-cellulose column. They are desorbed with 5 ml of 0.1 mol/l sodium hydroxide solution and fractionated at pH 1. The spectrophotometric analysis of river water reveals that fulvic acid is predominant in suspended particles as well as in filtered samples. The concentration of dissolved humic and fulvic acids is approximately ten times that of suspended particles.     

Speciation of rare earth elements in soil by sequential extraction then HPLC coupled with visible and ICP-MS detection

The distribution of rare earth elements (REE) in a pooled soil sample collected from Zhangzhou, Fujian Province, China, was screened by a five-step sequential extraction procedure coupled with ICP–MS determination after preconcentration of REE and removal of the matrix by extraction with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP). The results showed that the distribution of REE in the different fractions of the pooled soil sample studied followed the order soluble species (46.76%) > species bound to organic matter (22.08%) > species in the residue (16.77%) > species bound to Fe–Mn oxides (2.02%). An effective method for speciation of REE, which utilized weak cation-exchange HPLC separation hyphenated with post-column derivatization and visible or on line ICP–MS detection, was, moreover, developed and successfully applied to the speciation of REE in the soluble extract of the pooled soil sample. The stability of known complexes of lanthanum during the HPLC separation was investigated with fluoride, citrate, and ethylenediamine tetraacetic acid (EDTA) chosen as ligands modeling those in the soil. REE in the soluble extract of the pooled soil sample were subsequently classified into three types of species –≤ + 1 charged complexes (negatively charged, neutral, and +1 charged), + 2 charged complexes, and “free” REE species. This method is expected to be useful for identification of bioavailable (or toxic) species of REE in environmental samples. Received: 14 November 2000 / Revised: 26 January 2001 / Accepted: 30 January 2001     

弱酸阳离子交换纤维柱富集-电感耦合等离子体原子发射光谱法测定水样中的稀土

提出了聚丙烯基弱酸性阳离子交换纤维柱富集痕量稀土元素,1.0 mol/L HCl溶液作为洗脱剂,电感耦合等离子体原子发射光谱法测定水样中稀土元素的方法。在优化的试验条件下,弱酸性阳离子交换纤维对La、Nd、Eu、Gd、Er和Yb的吸附容量分别为86.5,98.2,98.7,99.2,84.9,91.5 mg/g;La、...     

Annual variations of the elemental concentrations of PM10 in ambient air of Nagoya City as determined by ICP-AES and ICP-MS.

PM10 samples were collected at an urban site of Nagoya City during September, 2003, to August, 2004, and annual variations of the concentrations of the elements in PM10 samples were examined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The annual concentration variations of ca. 30 elements in ambient air were in the range from sub-ng m(-3) to several microg m(-3). From an evaluation by the enrichment factors of the elements, elements such as Al, Ca, Fe, Mg, Ti, Mn, Ba, Sr, Ce, La, Nd, Co, Cs, and Pr, in PM10 samples were found to have originated mostly from natural sources, while the elements such as S, Zn, Pb, Cu, Ni, Sb, Sn, Cd, Bi, W, Tl, and In originated from anthropogenic emission sources. Furthermore, in seasonal variations of the elemental concentrations of PM10 samples in ambient air, the elements originated mostly from natural sources provided significantly high concentrations in spring during the "Kosa" period (the dust season from March to May). On the other hand, the elements mainly from anthropogenic emission sources provided relatively higher concentrations in autumn and winter, which may be explained by the fact that the urban atmospheric structure is stabilized by the temperature-inversion layer formed over the city in those seasons. In addition, all of the elements provided significantly low concentrations in the summer, due to the dilution effect of the oceanic winds as well as due to the convection of air mass up to the high levels.     

Determination of toxic elements in coal by ICP-MS after digestion using microwave-induced combustion

A microwave-induced combustion (MIC) procedure was applied for coal digestion for subsequent determination of As, Cd and Pb by inductively coupled plasma mass spectrometry (ICP-MS) and Hg using cold vapor (CV) generation coupled to ICP-MS. Pellets of coal (500 mg) were combusted using 20 bar of oxygen and ammonium nitrate as aid for ignition. The use of nitric acid as absorbing solution (1.7, 3.5, 5.0, 7.0 and 14 mol L⁻¹) was evaluated. For coal samples with higher ash content, better results were found using 7.0 mol L⁻¹ HNO₃ and an additional reflux step of 5 min after combustion step. For coal samples with ash content lower than 8%, 5.0 mol L⁻¹ nitric acid was suitable to the absorption of all analytes. Accuracy was evaluated using certified reference material (CRM) of coal and spikes. Agreement with certified values and recoveries was better than 95 and 97%, respectively, for all the analytes. For comparison of results, a procedure recommended by the American Society of Testing and Materials (ASTM) was used. Additionally, a conventional microwave-assisted digestion (MAD) in pressurized vessels was also performed. Using ASTM procedure, analyte losses were observed and a relatively long time was necessary for digestion (>6 h). By comparison with MAD procedure, higher sample mass can be digested using MIC allowing better limits of detection. Additionally, the use of concentrated acids was not necessary that is an important aspect in order to obtain low blank levels and lower limits of detection, respectively. The residual carbon content in digests obtained by MAD and MIC was about 15% and <1%, respectively, showing the better digestion efficiency of MIC procedure. Using MIC it was possible to digest completely and simultaneously up to eight samples in only 25 min with relatively lower generation of laboratory effluents.     

电感耦合等离子体原子发射光谱法和电感耦合等离子体质谱法测定不同肥料产品中铊含量比对

铊是一种高毒性的微量元素,具有较强的富集能力,已被列为肥料的强制性检验项目。选择了水溶性肥料、复混肥料、有机肥料3种代表性的肥料样品,通过比对微波消解和电热板敞口消解前处理方式;分析电感耦合等离子体原子发射光谱(ICP-AES)法和电感耦合等离子体质谱(ICP-MS)法主要干扰来源;通过建立各自的标准工作曲线、比对方法检出限、精密度、加标回收率,探讨研究肥料产品中铊含量测定方法。研究结果表明：微波消解法和电热板敞口消解法各有优点,可以根据样品实际情况灵活选择。ICP-AES法主要干扰为光谱干扰,需要在前处理过程中除去Mn元素,而ICP-MS法主要干扰为基体效应,可以使用内标物加以校正。ICP-MS法的检出限低于ICP-AES法。由于微波消解-ICP-AES法无法除去消解液中的Mn元素带来的光谱干扰,因此不适合测定铊含量。而微波消解-ICP-MS法、电热板敞口消解-ICP-AES法和电热板敞口消解-ICP-MS法这三种方法测定结果无明显差异,测定标准化肥质控样品均在指定值范围内,加标回收率为86%-110%。实验室可以根据肥料样品的数量、组成、性质合理选择搭配前处理方式和测定方法。     

Sample introduction systems for the analysis of liquid microsamples by ICP-AES and ICP-MS

There are many fields in which the available sample volume is the limiting factor for an elemental analysis. Over the last ten years, sample introduction systems used in plasma spectrometry (i.e., Inductively Coupled Plasma Atomic Emission Spectrometry, ICP-AES, and Mass Spectrometry, ICP-MS) have evolved in order to expand the field of applicability of these techniques to the analysis of micro- and nanosamples. A full understanding of the basic processes occurring throughout the sample introduction system is absolutely necessary to improve analytical performance. The first part of the present review deals with fundamental studies concerning the different phenomena taking place from aerosol production to analyte excitation/ionization when the liquid consumption rate does not exceed 100 μl/min. Existing sample introduction systems are currently far from the ideal and a significant effort has been made to develop new and efficient devices. Different approaches for continuously introducing small sample volumes (i.e., microsamples) have been reviewed and compared in the present work. Finally, applications as well as basic guidelines to select the best sample introduction system according to the sample particularities are given at the end of this review.     

Determination of gold in sludge and soil by sequential ICP-AES after preconcentration and separation with thiol-cotton fibre

Summary A method is presented for the determination of gold in sludge and soil samples by sequential ICP-AES after preconcentration and separation from the common alkali and alkaline-earth metals, as well as other matrix components, e.g. iron, by a thiol-cotton fibre column. The cotton fibre, impregnated with thioacetic acid, quantitatively adsorbs gold, thus eliminating the severe spectral interferences encountered by direct ICP-AES analysis. After preconcentration and separation the results obtained at Au 242.795 nm and Au 267.595 nm agree with each other. A quantitative recovery for added spikes was obtained. The method allows the determination of gold in complex matrices such as soil or sludge samples that have been proven to be impossible by conventional ICP-AES without separation from the matrix.On leave from Shanghai Institute of Metallurgy, Academia Sinica, Shanghai 2000 50, China     

电感耦合等离子体原子发射光谱法和电感耦合等离子体质谱法检测药品中元素杂质的研究进展北大核心CSCD

随着国际人用药品注册技术协调会(ICH)Q3D元素杂质指导原则的实施及中国加入ICH,中国于2020年1月执行ICH Q3D,药物中元素杂质逐渐成为人们的关注热点.电感耦合等离子体原子发射光谱法(ICP-AES)和电感耦合等离子体质谱法(ICP-MS)是两种美国药典(USP)‹233›推荐的元素杂质的检测方法,并成为多元素杂质检测方法的替代方法.概述了ICH Q3D规定元素杂质及其来源,总结了两种方法的主要优点、局限性及样品制备方法,涵盖了近年来文献中报道的主要用于活性药物成分(API)、原料和药物的应用,讨论了在采用ICP-AES和ICP-MS分析药品过程中的干扰.目前采用ICP-AES和ICP-MS检测药物中的元素杂质已经是一种趋势,综述(所引文献75篇)可为元素杂质检测方法的开发提供一定的参考.     

Crucible atomizer for determining dissolved and suspended forms of elements in natural waters

A model of a specialized microcolumn has been proposed and tested, namely, a crucible atomization microcolumn for electrothermal atomic absorption analysis of natural waters in which the zone of isolation of suspended matter and the zone of dynamic preconcentration of dissolved forms of elements are separated. A direct independent analysis of solid suspended matter and DETATA concentrate is possible upon completion of preconcentration. Such an approach is used to determine suspended and dissolved forms of cadmium and lead in river water and soil groundwater.     

电感耦合等离子体发射光谱法测定磷酸中的金属元素

建立了一种用电感耦合等离子体发射光谱仪(ICP-AES)测定磷酸中金属元素的分析方法。实验结果表明：选择合适的样品前处理方式和优化的仪器操作条件,方法的检出限可达到0.0012 ug/g~0.0552ug/g、加标回收率达到95%~105%,满足实际样品分析要求。     

High throughput online sequential extraction of natural rare earth elements and determination by mass spectrometry

At the beginning of rare earth industry,several days are normally required for characterization of rare earth elements(REEs)fractionation in ore samples.Herein,rapid fractionation analysis of 15 REEs and accompanied metal(Fe,Mn,etc.)in ore samples has been achieved within 1 h using ICP-MS with a homemade device for online sequential solvent extraction.As a result,five fractionations for REEs occurrences,i.e.,water soluble,exchangeable,reducible,oxidizable and crystalline,have been identified,offering chemical insights which not only reveal the formation mechanism of REEs ores but also show great implications for guiding the exploitation and separation of REEs.In comparison with conventional methods,the present approach significantly shortened the analysis time(1 h vs.~80 h)and reduced the sample consumption(1.0 mg vs.5.0 g)with high recovery(>95%),providing a useful platform for the rapid quantitative fractionation analysis of REEs in complexed samples such as ore and fossils.