ICP-MS法测定高纯钛中痕量元素

建立了ICP-MS直接测定高纯钛中Be,V,Co,Ni,Ga,Mo,Nb,Cd,Sb,TI,Pb的分析方法,并对ICP-MS工作参数及条件进行了优化和选择.高纯钛用HF与HNO3溶解后加入Sc、Cs、Re内标,用ICP-MS直接检测.方法的检出限为0.03～0.1 ng/mL,测定下限为0.2～0.5 ng/mL,各元...     

Determination of rare earth elements in seawater by on-line column preconcentration inductively coupled plasma mass spectrometry

A home made column of commercially available iminodiacetate resin, Muromac A-1 (50–100 mesh) was used to concentrate rare earth elements (REEs) (15 elements: Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in seawater. An automated low pressure flow analysis method with on-line column preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) is described for the determination of REEs in seawater. Sample solutions (adjusted to pH of 3.0) passed through the column. After washing the column with water, the adsorbed elements were subsequently eluted into the plasma with 0.7 M nitric acid. Calibration curves were accomplished by means of purified artificial seawater with a sample loading time of 120 s. Detection limits (DLs) of the on-line column preconcentration/ICP-MS by eight replicate operations were between 0.040 and 0.251 pg ml⁻¹ for REEs in the artificial seawater. The precision was less than 8.9% for REEs and one sample can be processed in 7 min using a 7 ml of sample. The proposed method was applied to determine REEs in coastal seawater of Hiroshima Bay, Japan.     

ICP-MS determination of heavy metals in submerged cultures of wood-rotting fungi

Accumulation of five heavy metal ions by five species of wood-rotting basidiomycetes during a 9-day cultivation was studied. Contents of Cd, Cu, Pb, and Zn were measured using ICP-MS; the amount of mercury was determined directly in solid samples using the Advanced Mercury Analyser. A standard operation procedure for the sample preparation and determination of metal content was developed and validated. Presence of Cd, Cu, Hg, and Pb decreased the accumulation of zinc by the fungi. The basidiomycete Pycnoporus cinnabarinus exhibited the highest metal binding capacity of all fungi tested.     

Determination of lead in vinegar by ICP-MS and GFAAS: evaluation of different sample preparation procedures

Lead concentrations of 59 different types of vinegars (15-307 μg l⁻¹ in balsamic vinegars and 36-50 μg l⁻¹ in wine vinegars) were determined using both inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption spectrometry (GFAAS). Although the precision of direct analyses, following simple aqueous dilutions, with either instrumental method was poor; that precision, following nitric acid and/or hydrogen peroxide digestions, markedly improved with either instrument and the values obtained with the two instruments were in good agreement. The efficacy of different digestions, including (1) nitric acid using a heating block, with or without addition of hydrogen peroxide and (2) mixtures of nitric acid and hydrogen peroxide using ultraviolet (UV) photolysis, were then assessed. The latter procedure was found to be much faster and more efficient, but it was limited by the relatively high levels of contaminant lead in hydrogen peroxide. Consequently, it is recommended that lead concentrations in vinegar be measured following a nitric acid digestion and UV photolysis to oxidize all organic matter before ICP-MS or GFAAS analysis; and it is further recommend that the thermal settings for the latter analyses be adjusted to account for the apparent presence of relatively volatile organolead compounds in vinegar digests.     

Regional distribution of manganese,iron, copper,and zinc in the rat brain during development

Manganese (Mn), iron (Fe), copper (Cu), and zinc (Zn) concentrations were determined in the brain regions of normal 1-, 3-, 5-, 7-, 14-, 21-, 42-, 77-, and 147-day-old Wistar rats using inductively coupled plasma mass spectrometry (ICP-MS), and their maps were illustrated in color to visually compare the distribution of the elements at various stages of the growth process. Sagittal slices (1-mm thickness) sectioned at the level of the substantia nigra were divided into 18 regions, and the small slice samples were digested in microwave-assisted closed vessels for ICP-MS measurement. Mn, Fe, Cu, and Zn concentrations increased region-specifically with age, and their distributional maps showed some characteristics. These findings are discussed in terms of needs for these trace elements in the normal brain. Among new findings about their brain distribution, it is especially noteworthy that higher concentrations of Mn, Fe, and Zn were observed in the substantia nigra compared with those in neighboring regions. The mapping method in this work is expected to open up possibilities for screening of the in vivo element–element interrelationships among these essential elements.     

Measurement of labile Cu in soil using stable isotope dilution and isotope ratio analysis by ICP-MS

Isotope dilution is a useful technique to measure the labile metal pool, which is the amount of metal in soil in rapid equilibrium (<7 days) with the soil solution. This is normally performed by equilibrating soil with a metal isotope, and sampling the labile metal pool by using an extraction (E value), or by growing plants (L value). For Cu, this procedure is problematic for E values, and impossible for L values, due to the short half-life of the ⁶⁴Cu radioisotope (12.4 h), which makes access and handling very difficult. We therefore developed a technique using enriched ⁶⁵Cu stable isotope and measurement of ⁶³Cu/⁶⁵Cu ratios by quadrupole inductively coupled plasma mass spectrometry (ICP-MS) to measure labile pools of Cu in soils using E value techniques. Mass spectral interferences in detection of ⁶³Cu/⁶⁵Cu ratios in soil extracts were found to be minimal. Isotope ratios determined by quadrupole ICP-MS compared well to those determined by high-resolution (magnetic sector) ICP-MS. E values determined using the stable isotope technique compared well to those determined using the radioisotope for both uncontaminated and Cu-contaminated soils.     

Investigations by various analytical techniques to the correct classification of archaeological finds and delineation of technological features: Late Roman lamps from Egnatia: From imports to local production

Late Roman oil lamps from the archaeological site of Egnatia (Fasano, Brindisi, Italy) were characterized from physical–chemical, mineralogical and morphological points of view. Atomic Spectroscopy, Scanning Electron Microscopy and X-Ray Diffraction analyses were carried out on ceramic body and coatings with the aim of identifying the provenance of lamps, in order to arrive at a correct archaeological classification of finds and to outline their technological features.The analytical results show that the finds differ in raw materials and in production technology. The statistical multivariate treatment of compositional data of ceramic bodies groups the objects into two macro clusters and, according to a study of their different petrographic features and by a comparison with coeval pottery whose provenance is already known, suggests one group to have been imported from North Africa and the other to have been locally produced. Moreover, chemical results and in-depth archaeological analyses allow us to split the imported lamps into two subgroups, hypothesizing the first group to originate from central Tunisia and the second from the north of the same country.The analytical characterisation of finds, by different complementary techniques, has allowed us to identify the raw materials and the technological solutions used by the ancient potters from Egnatia to produce lamps. The potters made lamps which had an external appearance very similar to that of African prototypes, but which were nevertheless different as they employed the locally available materials.     

Speciation of selenomethionine and selenocystine using online micro-column containing Cu(II) loaded nanometer-sized Al2O3 coupled with ICP-MS detection

A flow injection online speciation procedure by using micro-column packed with Cu(II) loaded nanometer-sized Al₂O₃ coupled to inductively coupled plasma mass spectrometry (ICP-MS) for the separation and determination of selenomethionine (SeMet) and selenocystine (SeCys₂) has been developed. The main factors affecting the separation and preconcentration of SeMet and SeCys₂ including pH value, sample flow rate, eluent concentration, eluent volume and flow rate, and interfering ions have been investigated. It was found that SeCys₂ could be selectively retained by micro-column packed with Cu(II) loaded nanometer-sized Al₂O₃ at pH 4.0, and the retained SeCys₂ could be eluted by 1.0 mol L⁻¹ HNO₃, while SeMet was not retained and passed through the micro-column directly at this pH. Both SeMet and SeCys₂ could be quantitatively adsorbed by the micro-column at pH 9.0, and the retained SeMet and SeCys₂ could be easily eluted with 1.0 mol L⁻¹ HNO₃. The content of SeMet was obtained by subtracting the SeCys₂ from the total content of seleno amino acids. With the enrichment factor of 7.8 and 7.7, the limits of detection (LODs) for SeMet and SeCys₂ were found to be 24 pg Se mL⁻¹ and 21 pg Se mL⁻¹, respectively. The relative standard deviations (RSDs) for SeCys₂ and SeMet with seven replicate determinations of 1.0 ng mL⁻¹ SeMet and SeCys₂, were 2.1% and 1.6%, respectively, the sampling frequency of 8 h⁻¹ was obtained. The proposed method was applied to the speciation of SeMet and SeCys₂ in selenized yeast, human urine and serum with satisfactory results.     

Rapid determination of actinides in urine by inductively coupled plasma mass spectrometry and alpha spectrometry: A hybrid approach

A new rapid separation method that allows separation and preconcentration of actinides in urine samples was developed for the measurement of longer lived actinides by inductively coupled plasma mass spectrometry (ICP-MS) and short-lived actinides by alpha spectrometry; a hybrid approach. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration, if required, is performed using a streamlined calcium phosphate precipitation. Similar technology has been applied to separate actinides prior to measurement by alpha spectrometry, but this new method has been developed with elution reagents now compatible with ICP-MS as well. Purified solutions are split between ICP-MS and alpha spectrometry so that long- and short-lived actinide isotopes can be measured successfully. The method allows for simultaneous extraction of 24 samples (including QC samples) in less than 3 h. Simultaneous sample preparation can offer significant time savings over sequential sample preparation. For example, sequential sample preparation of 24 samples taking just 15 min each requires 6 h to complete. The simplicity and speed of this new method makes it attractive for radiological emergency response. If preconcentration is applied, the method is applicable to larger sample aliquots for occupational exposures as well. The chemical recoveries are typically greater than 90%, in contrast to other reported methods using flow injection separation techniques for urine samples where plutonium yields were 70-80%. This method allows measurement of both long-lived and short-lived actinide isotopes. ²³⁹Pu, ²⁴²Pu, ²³⁷Np, ²⁴³Am, ²³⁴U, ²³⁵U and ²³⁸U were measured by ICP-MS, while ²³⁶Pu, ²³⁸Pu, ²³⁹Pu, ²⁴¹Am, ²⁴³Am and ²⁴⁴Cm were measured by alpha spectrometry. The method can also be adapted so that the separation of uranium isotopes for assay is not required, if uranium assay by direct dilution of the urine sample is preferred instead. Multiple vacuum box locations may be set-up to supply several ICP-MS units with purified sample fractions such that a high sample throughput may be achieved, while still allowing for rapid measurement of short-lived actinides by alpha spectrometry.     

Determination of vanadium by reaction cell inductively coupled plasma mass spectrometry

Recent advances in inductively coupled plasma mass spectrometry (ICP-MS) have included the addition of interference reduction technologies, such as collision and reaction cells, to improve its detection capability for certain elements that suffer from polyatomic interferences. The principle behind reaction cell (RC)-ICP-MS is to remove a particular polyatomic interference by dissociation or formation of a different polyatomic species that no longer interferes with the analyte of interest. However, some interferences cannot be removed by commonly reported reaction gases, such as hydrogen, oxygen, or methane, necessitating using more reactive and hazardous gases, such as ammonia. The current study investigates oxygen as a reaction gas in RC-ICP-MS to specifically react with vanadium analyte ions, rather than the interferents, to produce a polyatomic analyte species and thereby provide a way to analyze for vanadium in complex environmental matrices. The technique has been tested on a series of river water, tap water, and synthetic laboratory samples, and shown to be successful in vanadium analyses in high chloride and sulfate matrices. The zinc isobaric interference on the new vanadium oxide analyte at m/z 67 is also investigated, and can be corrected by using a standard mathematical correction equation. The results of this study further increase the utility of RC-ICP-MS analytical techniques for complex environmental matrices.