Most view articles
2022, 43(1):53-59.
DOI: 10.46770/AS.2022.014
Abstract:
Nanophase iron (np-Fe0) is a major product of space weathering and its presence significantly alters the reflectance spectral characteristics of lunar soil. Previous studies have established that the np-Fe0 particles originate from the reduction of ferrous ions in the plasma, in-situ decomposition of olivine and pyroxene, and disproportionation of ferrous ions in solid ferrosilicates. In this study, sample charging effects were eliminated and in situ nanoscale valence state analysis of iron-bearing phases in Chang’E-5 lunar soil was conducted by combining focused ion beam (FIB) microscopy, Auger electron spectroscopy (AES), and transmission electron microscopy-electron energy loss spectroscopy (TEM-EELS) techniques. The results indicate that the contents and valence states of iron in the np-Fe0 particles, amorphous matrix, and ferrosilicates differ. The np-Fe0 particles were found to be composed of pure metallic iron, whereas ferrous and ferric iron ions were present in olivine crystals and the amorphous matrix, respectively. The discovery of both metallic and ferric iron in the amorphous matrix of Chang’E-5 lunar soil offers new insights regarding the disproportionation reaction of Fe2+ on the lunar surface. This study demonstrates that the combination of FIB, AES, and TEM-EELS is an effective and precise approach for analyzing the valence states of iron-bearing phases in lunar soil, which can be extended to other extraterrestrial samples and other multivalent elements.
Nanophase iron (np-Fe0) is a major product of space weathering and its presence significantly alters the reflectance spectral characteristics of lunar soil. Previous studies have established that the np-Fe0 particles originate from the reduction of ferrous ions in the plasma, in-situ decomposition of olivine and pyroxene, and disproportionation of ferrous ions in solid ferrosilicates. In this study, sample charging effects were eliminated and in situ nanoscale valence state analysis of iron-bearing phases in Chang’E-5 lunar soil was conducted by combining focused ion beam (FIB) microscopy, Auger electron spectroscopy (AES), and transmission electron microscopy-electron energy loss spectroscopy (TEM-EELS) techniques. The results indicate that the contents and valence states of iron in the np-Fe0 particles, amorphous matrix, and ferrosilicates differ. The np-Fe0 particles were found to be composed of pure metallic iron, whereas ferrous and ferric iron ions were present in olivine crystals and the amorphous matrix, respectively. The discovery of both metallic and ferric iron in the amorphous matrix of Chang’E-5 lunar soil offers new insights regarding the disproportionation reaction of Fe2+ on the lunar surface. This study demonstrates that the combination of FIB, AES, and TEM-EELS is an effective and precise approach for analyzing the valence states of iron-bearing phases in lunar soil, which can be extended to other extraterrestrial samples and other multivalent elements.
Xiong Wan
,
Chenhong Li
,
Hongpeng Wang
,
Weiming Xu
,
Jianjun Jia
,
Yingjian Xin
,
Huanzhen Ma
,
Peipei Fang
,
Zongcheng Ling
2021, 42(6):294-298.
DOI: 10.46770/AS.2021.608
Abstract:
MarSCoDe (Mars Surface Composition Detector) is China's first instrument for Mars material analysis, which accompanies the Zhurong Mars rover landing on Utopia Planitia and will detect interested Martian rock and soil targets based on laser-induced breakdown spectroscopy (LIBS) technique. MarSCoDe consists of a bioxial pointing mirror (BPM), an optical head, a calibration targets assembly (CTA), a spectrometer module (SM) and a payload controller. The MarSCoDe is scheduled to analyze twelve major elements. To achieve accurate quantitative analysis and classification of Mars targets, a PSO (particle swarm optimization)-based calibration scheme is adopted to correct the spectral shift due to the temperature change on Mars, and then a convolutional neural network (CNN) was proposed to implement the analysis of elements. Finally, the mineral types of Martian objects will be identified according to the alkali silica ratio. The detection results of the MarSCoDe will provide further information about the evolution of Mars.
MarSCoDe (Mars Surface Composition Detector) is China's first instrument for Mars material analysis, which accompanies the Zhurong Mars rover landing on Utopia Planitia and will detect interested Martian rock and soil targets based on laser-induced breakdown spectroscopy (LIBS) technique. MarSCoDe consists of a bioxial pointing mirror (BPM), an optical head, a calibration targets assembly (CTA), a spectrometer module (SM) and a payload controller. The MarSCoDe is scheduled to analyze twelve major elements. To achieve accurate quantitative analysis and classification of Mars targets, a PSO (particle swarm optimization)-based calibration scheme is adopted to correct the spectral shift due to the temperature change on Mars, and then a convolutional neural network (CNN) was proposed to implement the analysis of elements. Finally, the mineral types of Martian objects will be identified according to the alkali silica ratio. The detection results of the MarSCoDe will provide further information about the evolution of Mars.
2002, 23(1):1-6.
DOI: 10.46770/AS.2002.01.001
Abstract:
A powerful multielement analytical technique using laser ablation Inductively coupled plasma source mass spectrometry (LA-ICP-MS) for the sensitive determination of trace impurities in thin glass filaments, used as reinforcing material in the construction industry, was developed. The trace analysis was carried out directly on very thin solid strands (without any sample preparation steps) by LA-ICP-MS whereby a bundle of thin glass fibers (with a filament diameter of about 10 - 20 mum) was fixed on a thin, special tape of a target holder. The fibers were ablated in the ablation chamber with the aid of a commercial laser ablation system using a Nd-YAG laser at a wavelength of 266 nm). In order to verify the trace analytical data, the ablated T-glass fibers were analyzed using a quadrupole (LA-ICP-QMS) and double-focusing sector field mass spectrometer (LA-ICP-SFMS). The detection limits of the trace elements in glass fibers using the LA-ICP-MS with a quadrupole analyzer were in the sub mug g(-1) range, whereas using a sector,field mass spectrometer (LA-ICP-SFMS) the detection limits could be Improved by 3-4 orders of magnitude down to the low and sub ng g(-1) range. The multielement trace analytical method, developed for high-purity glass fibers, was applied to the determination of chemical composition on thin alkati-resistant glass and basalt fibers with finishing additives used in fine concrete for the building industry. The analytical results were quantified using standard reference materials (SRMs) of glass matrix, such as the NIST 612 glass SRM and the basalt geological reference glasses, KL-2G and ML3B-G, for the trace analysis of basalt glass fibers. The experimentally determined relative sensitivity coefficients (RSC) in LA-ICP-MS for both SRMs varied between 0.2 and 3 for most of the elements. An increase of the relative sensitivity coefficients was observed with increasing mass. The relative standard deviation (RSD) of most elements (N = 3) was T between 2 and 10%. The results of the trace element concentrations by LA-ICP-MS using different instrumentation are in good agreement.
A powerful multielement analytical technique using laser ablation Inductively coupled plasma source mass spectrometry (LA-ICP-MS) for the sensitive determination of trace impurities in thin glass filaments, used as reinforcing material in the construction industry, was developed. The trace analysis was carried out directly on very thin solid strands (without any sample preparation steps) by LA-ICP-MS whereby a bundle of thin glass fibers (with a filament diameter of about 10 - 20 mum) was fixed on a thin, special tape of a target holder. The fibers were ablated in the ablation chamber with the aid of a commercial laser ablation system using a Nd-YAG laser at a wavelength of 266 nm). In order to verify the trace analytical data, the ablated T-glass fibers were analyzed using a quadrupole (LA-ICP-QMS) and double-focusing sector field mass spectrometer (LA-ICP-SFMS). The detection limits of the trace elements in glass fibers using the LA-ICP-MS with a quadrupole analyzer were in the sub mug g(-1) range, whereas using a sector,field mass spectrometer (LA-ICP-SFMS) the detection limits could be Improved by 3-4 orders of magnitude down to the low and sub ng g(-1) range. The multielement trace analytical method, developed for high-purity glass fibers, was applied to the determination of chemical composition on thin alkati-resistant glass and basalt fibers with finishing additives used in fine concrete for the building industry. The analytical results were quantified using standard reference materials (SRMs) of glass matrix, such as the NIST 612 glass SRM and the basalt geological reference glasses, KL-2G and ML3B-G, for the trace analysis of basalt glass fibers. The experimentally determined relative sensitivity coefficients (RSC) in LA-ICP-MS for both SRMs varied between 0.2 and 3 for most of the elements. An increase of the relative sensitivity coefficients was observed with increasing mass. The relative standard deviation (RSD) of most elements (N = 3) was T between 2 and 10%. The results of the trace element concentrations by LA-ICP-MS using different instrumentation are in good agreement.
2020, 41(3):127-131.
DOI: 10.46770/AS.2020.03.005
Abstract:
The handheld X-ray fluorescence spectrometer (XRF) has the advantages of being easy to carry, simple in operation, non-destructive, and offers fast and relatively accurate detection, while synchrotron radiation X-ray absorption spectroscopy (XAS) has been used for the selenium (Se) speciation of Se-enriched yeast and Se hyperaccumulators. In this study, we propose the application of a handheld XRF in combination with XAS for the fast quantification and speciation of Se in commercially available dietary supplements. The results of total Se determined by handheld XRF were in good agreement with ICP-MS data, which was also consistent with the labeled value of Se dietary supplements. The XAS analysis of the tested samples showed that Se was mainly present in the form of organic Se. The proposed method is practical and simple for high throughput label verification and quality control of Se dietary supplements. It can, therefore, be a useful method not only for researchers but also for regulators and producers in the analysis of Se dietary supplements.
The handheld X-ray fluorescence spectrometer (XRF) has the advantages of being easy to carry, simple in operation, non-destructive, and offers fast and relatively accurate detection, while synchrotron radiation X-ray absorption spectroscopy (XAS) has been used for the selenium (Se) speciation of Se-enriched yeast and Se hyperaccumulators. In this study, we propose the application of a handheld XRF in combination with XAS for the fast quantification and speciation of Se in commercially available dietary supplements. The results of total Se determined by handheld XRF were in good agreement with ICP-MS data, which was also consistent with the labeled value of Se dietary supplements. The XAS analysis of the tested samples showed that Se was mainly present in the form of organic Se. The proposed method is practical and simple for high throughput label verification and quality control of Se dietary supplements. It can, therefore, be a useful method not only for researchers but also for regulators and producers in the analysis of Se dietary supplements.
Jinhui Liu
,
Lingna Zheng
,
Junwen Shi
,
Xing Wei
,
Xue Li
,
Mingli Chen
,
Meng Wang
,
Jianhua Wang
,
Weiyue Feng
2021, 42(3):114-119.
DOI: 10.46770/AS.2021.102
Abstract:
Single-cell inductively coupled plasma mass spectrometry (SC-ICP-MS) has been introduced for the analysis of intracellular essential elements and nanoparticles (NPs) at the single cell level. However, it is still quite challenging for accurate and reliable determination. In this work, a high-efficiency sample introduction system was used for single cell analysis with ICP-MS. The system includes a microconcentric nebulizer, a low-volume single pass spray chamber, and a syringe pump. The transport efficiency of single cells was greatly improved to ~12%. In addition, 197Au signals in individual HepG2 cells, after incubation with gold nanoparticles (AuNPs) at the concentrations of 0.1, 0.5, and 1 μM for 12 h, were analyzed by time-resolved ICP-MS with dwell times of 100 μs and 5 ms, respectively. The 197Au signal-to-background ratio (S/B) at 100 μs dwell time was much higher than at 5 ms. For quantitative analysis, AuNP standard reference materials were used for calibration. The SC-ICP-MS data using NP calibration were in good agreement with those using solution ICP-MS analysis, validating the developed SC-ICP-MS method.
Single-cell inductively coupled plasma mass spectrometry (SC-ICP-MS) has been introduced for the analysis of intracellular essential elements and nanoparticles (NPs) at the single cell level. However, it is still quite challenging for accurate and reliable determination. In this work, a high-efficiency sample introduction system was used for single cell analysis with ICP-MS. The system includes a microconcentric nebulizer, a low-volume single pass spray chamber, and a syringe pump. The transport efficiency of single cells was greatly improved to ~12%. In addition, 197Au signals in individual HepG2 cells, after incubation with gold nanoparticles (AuNPs) at the concentrations of 0.1, 0.5, and 1 μM for 12 h, were analyzed by time-resolved ICP-MS with dwell times of 100 μs and 5 ms, respectively. The 197Au signal-to-background ratio (S/B) at 100 μs dwell time was much higher than at 5 ms. For quantitative analysis, AuNP standard reference materials were used for calibration. The SC-ICP-MS data using NP calibration were in good agreement with those using solution ICP-MS analysis, validating the developed SC-ICP-MS method.
2021, 42(6):310-327.
DOI: 10.46770/AS.2021.707
Abstract:
Electrothermal or graphite furnace atomic absorption spectrometry (ETAAS or GFAAS) is one of the most widely used techniques for determining elements in different matrices (e.g., foodstuffs, pharmaceuticals, biological specimens, nanomaterials, polymers, fuels and environmental media). Numerous elements can be simply and quickly determined with high precision and accuracy, low detection limits, and at moderate cost. The technique is also suitable for direct solid and slurry sample analysis. A crucial feature of this technique is that it can perform simultaneous or sequential multi-element analysis. Over the years, many instruments have come on the market for multi-elemental analysis using mostly line source (LS) GFAAS and high-resolution continuum source (HR-CS) GFAAS. This review covers publications from 2000 to 2020 related to the simultaneous or sequential multi-elemental analysis by LS-GFAAS and HR-CS-GFAAS. Mainly the applications, the limits of detection, the use of internal standardization and other aspects regarding the matrix, pyrolysis and atomization temperatures and modifiers are discussed. Finally, a critical comparison is made between the LS-GFAAS and HR-CS-GFAAS techniques.
Electrothermal or graphite furnace atomic absorption spectrometry (ETAAS or GFAAS) is one of the most widely used techniques for determining elements in different matrices (e.g., foodstuffs, pharmaceuticals, biological specimens, nanomaterials, polymers, fuels and environmental media). Numerous elements can be simply and quickly determined with high precision and accuracy, low detection limits, and at moderate cost. The technique is also suitable for direct solid and slurry sample analysis. A crucial feature of this technique is that it can perform simultaneous or sequential multi-element analysis. Over the years, many instruments have come on the market for multi-elemental analysis using mostly line source (LS) GFAAS and high-resolution continuum source (HR-CS) GFAAS. This review covers publications from 2000 to 2020 related to the simultaneous or sequential multi-elemental analysis by LS-GFAAS and HR-CS-GFAAS. Mainly the applications, the limits of detection, the use of internal standardization and other aspects regarding the matrix, pyrolysis and atomization temperatures and modifiers are discussed. Finally, a critical comparison is made between the LS-GFAAS and HR-CS-GFAAS techniques.
1999, 20(3):86-91.
DOI: 10.46770/AS.1999.03.002
Abstract:
The metal content in several TCM drugs was determined by ICP-MS. The efficiencies of different sample digestion methods were compared. Since one of the products studied is known to contain arsenic sulfides as a main ingredient, a solvent fractionation scheme was developed and applied to speciate As in the product. The metal content in the same TCM drug produced by different manufacturers was compared. The concentration of some metals such as Pb and Cd differs widely with different manufacturers, suggesting that their origin is primarily from external contamination. The high sensitivity and precision of the ICP-MS technique offers considerable advantages over conventional ICP-OES techniques for the analysis of complex samples such as TCM materials. Standardized analytic protocols based on ICP-MS are being developed fur the determination and characterization of metals and trace elements in TCM materials for product quality assessment.
The metal content in several TCM drugs was determined by ICP-MS. The efficiencies of different sample digestion methods were compared. Since one of the products studied is known to contain arsenic sulfides as a main ingredient, a solvent fractionation scheme was developed and applied to speciate As in the product. The metal content in the same TCM drug produced by different manufacturers was compared. The concentration of some metals such as Pb and Cd differs widely with different manufacturers, suggesting that their origin is primarily from external contamination. The high sensitivity and precision of the ICP-MS technique offers considerable advantages over conventional ICP-OES techniques for the analysis of complex samples such as TCM materials. Standardized analytic protocols based on ICP-MS are being developed fur the determination and characterization of metals and trace elements in TCM materials for product quality assessment.
2008, 29(3):93-98.
DOI: 10.46770/AS.2008.03.004
Abstract:
On-line chemical vapor generation atomic fluorescence spectrometry (CVG-AFS) was, for the first time, used to determine trace copper in biological samples by merging acidified sample solution with potassium tetrahydroborate aqueous solution in the presence of micro-amounts of 1,10-phenanthroline. Nitric acid, for both sample digestion and chemical vapor generation, was used as the acid medium. CVG conditions and instrumental parameters were optimized for the best CVG efficiency, good gas/liquid separation, and efficient atomization/excitation. Under the optimized conditions, a limit of detection of 4 ng mL(-1) was obtained for copper, with a linear dynamic range of over three orders of magnitude. The proposed method was successfully applied to the determination of copper in biological certified reference materials.
On-line chemical vapor generation atomic fluorescence spectrometry (CVG-AFS) was, for the first time, used to determine trace copper in biological samples by merging acidified sample solution with potassium tetrahydroborate aqueous solution in the presence of micro-amounts of 1,10-phenanthroline. Nitric acid, for both sample digestion and chemical vapor generation, was used as the acid medium. CVG conditions and instrumental parameters were optimized for the best CVG efficiency, good gas/liquid separation, and efficient atomization/excitation. Under the optimized conditions, a limit of detection of 4 ng mL(-1) was obtained for copper, with a linear dynamic range of over three orders of magnitude. The proposed method was successfully applied to the determination of copper in biological certified reference materials.
Lihui Jia
,
Yi Chen
,
Qian Mao
,
Di Zhang
,
Jiangyan Yuan
,
Xiaoguang Li
,
Shitou Wu
,
Danping Zhang
2022, 43(1):42-52.
DOI: 10.46770/AS.2022.002
Abstract:
Spinel, an important mineral in basalts and ultramafic rocks on Earth, Mars, and the Moon, is sensitive to petrologic and geochemical processes, and redox evolution. Due to the small grain size of extraterrestrial samples, investigations on the composition of spinel samples including presence of trace elements and ferric iron have been hindered by the lack of appropriate in-situ analytical techniques with high spatial resolution and the shortage of reference materials. This paper presents a combined method of simultaneously measuring the major and trace elements, and Fe3+/∑Fe ratio in spinel samples using electron probe microanalysis (EPMA). Our new EPMA method is performed under double beam condition at a beam current of 200 nA for trace elements (Ti, V, Mn, Co, Ni, and Zn) and 60 nA for major elements (Mg, Fe, Al, and Cr) with an acceleration voltage of 25 kV. In addition, large analyzing crystals and peak overlap corrections were applied to reduce the detection limits and improve the analytical precision. The detection limits of 16–55 μg/g (3σ) for trace elements were achieved, and the estimated accuracies for the major elements and trace elements were within ± 2 and ± 6% (1σ), respectively. We selected seven spinel samples from the Luobusha and Stillwater intrusions to evaluate the validity of our method. They were sufficiently homogeneous with a relative standard deviation (RSD) of ± 2.0% (1σ) for the major elements (except MgO in 16SW3-9) and ± 7.0% (1σ) for the trace elements. The EPMA results obtained for the major and trace elements of the most homogeneous spinel LBS13-04 were compared with those measured using X-ray fluorescence and laser ablation inductively coupled plasma mass spectrometry. These values were in good agreement with the uncertainty of the methods. Thus, this spinel is highly suitable as a reference material for in situ microanalysis. The Fe3+/ΣFe ratios of high Cr# (57.7-79.1) spinel standards determined using M?ssbauer spectroscopy varied from 0.07 to 0.27, which were used for secondary standard calibration method to determine the spinel Fe3+/ΣFe ratio with an accuracy of < ± 0.04 (2σ). Our results offer a high-precision EPMA method that can simultaneously determine the major and trace elements together with the Fe3+/ΣFe ratio in spinel. This method provides robust and precise data on spinel for small, precious, and rare terrestrial or extraterrestrial samples, which can be used to understand the formation and evolution of rocky planets.
Spinel, an important mineral in basalts and ultramafic rocks on Earth, Mars, and the Moon, is sensitive to petrologic and geochemical processes, and redox evolution. Due to the small grain size of extraterrestrial samples, investigations on the composition of spinel samples including presence of trace elements and ferric iron have been hindered by the lack of appropriate in-situ analytical techniques with high spatial resolution and the shortage of reference materials. This paper presents a combined method of simultaneously measuring the major and trace elements, and Fe3+/∑Fe ratio in spinel samples using electron probe microanalysis (EPMA). Our new EPMA method is performed under double beam condition at a beam current of 200 nA for trace elements (Ti, V, Mn, Co, Ni, and Zn) and 60 nA for major elements (Mg, Fe, Al, and Cr) with an acceleration voltage of 25 kV. In addition, large analyzing crystals and peak overlap corrections were applied to reduce the detection limits and improve the analytical precision. The detection limits of 16–55 μg/g (3σ) for trace elements were achieved, and the estimated accuracies for the major elements and trace elements were within ± 2 and ± 6% (1σ), respectively. We selected seven spinel samples from the Luobusha and Stillwater intrusions to evaluate the validity of our method. They were sufficiently homogeneous with a relative standard deviation (RSD) of ± 2.0% (1σ) for the major elements (except MgO in 16SW3-9) and ± 7.0% (1σ) for the trace elements. The EPMA results obtained for the major and trace elements of the most homogeneous spinel LBS13-04 were compared with those measured using X-ray fluorescence and laser ablation inductively coupled plasma mass spectrometry. These values were in good agreement with the uncertainty of the methods. Thus, this spinel is highly suitable as a reference material for in situ microanalysis. The Fe3+/ΣFe ratios of high Cr# (57.7-79.1) spinel standards determined using M?ssbauer spectroscopy varied from 0.07 to 0.27, which were used for secondary standard calibration method to determine the spinel Fe3+/ΣFe ratio with an accuracy of < ± 0.04 (2σ). Our results offer a high-precision EPMA method that can simultaneously determine the major and trace elements together with the Fe3+/ΣFe ratio in spinel. This method provides robust and precise data on spinel for small, precious, and rare terrestrial or extraterrestrial samples, which can be used to understand the formation and evolution of rocky planets.
2004, 25(1):13-20.
DOI: 10.46770/AS.2004.01.002
Abstract:
The analytical procedure for the determination of trace rare earth impurities in high purity neodymium oxide (Nd2O3) by ICP-MS is described. The effect of ICP-MS operating parameters on the REO(H)(+)/RE+ production ratio was studied in detail, and the optimal ICP operating conditions were established. In this context, the relationship between REO(H)(+)/RE+ production ratio and the bond strength of the rare earth oxides is also discussed briefly. For the correction of the spectral interference induced by the matrix (neodymium), a simple correction equation was used for correcting the interferences of the polyatomic ions NdO+ and NdOH+ with Tb-159 and Ho-165. The proposed method was applied to the determination of trace rare earth impurities in high purity Nd2O3\, and the analytical results were in good agreement with the recommended reference values.
The analytical procedure for the determination of trace rare earth impurities in high purity neodymium oxide (Nd2O3) by ICP-MS is described. The effect of ICP-MS operating parameters on the REO(H)(+)/RE+ production ratio was studied in detail, and the optimal ICP operating conditions were established. In this context, the relationship between REO(H)(+)/RE+ production ratio and the bond strength of the rare earth oxides is also discussed briefly. For the correction of the spectral interference induced by the matrix (neodymium), a simple correction equation was used for correcting the interferences of the polyatomic ions NdO+ and NdOH+ with Tb-159 and Ho-165. The proposed method was applied to the determination of trace rare earth impurities in high purity Nd2O3\, and the analytical results were in good agreement with the recommended reference values.
2020, 41(3):93-102.
DOI: 10.46770/AS.2020.03.001
Abstract:
Reference materials (RMs) are the foundation in isotopic analysis, and the assignment of reference values of isotope ratios in RMs is a complex process. In this study, we established new isotopic reference values and its uncertainties for the Sr, Nd, Hf and Pb isotope ratios in 18 commonly used pure materials and rock RMs, and for Hf and O isotope ratios in five zircon RMs, following the ISO guidelines and procedures in the IAG Certification Protocol. The original data were collected from the geochemical database “GeoReM”. An estimation method for generating reference values of isotope ratios was developed, including a data filter process, technical criteria assessment and robust statistical calculation. The generated analytical results demonstrate the same instrumental performance with both TIMS and MC-ICP-MS for Sr and Nd isotopic analysis. However, significant discrete data for the Pb isotope ratios obtained by TIMS and MC-ICP-MS are evident, indicating existing challenges for accurate Pb isotopic analysis. It was found that 91500 is not a suitable Hf isotopic RM for micro-analysis due to the heterogeneous Hf isotopic composition and the Ple?ovice zircon may be a more ideal alternative. This study provides a powerful protocol and practical examples for estimating reference values of isotope ratios in frequently used RMs.
Reference materials (RMs) are the foundation in isotopic analysis, and the assignment of reference values of isotope ratios in RMs is a complex process. In this study, we established new isotopic reference values and its uncertainties for the Sr, Nd, Hf and Pb isotope ratios in 18 commonly used pure materials and rock RMs, and for Hf and O isotope ratios in five zircon RMs, following the ISO guidelines and procedures in the IAG Certification Protocol. The original data were collected from the geochemical database “GeoReM”. An estimation method for generating reference values of isotope ratios was developed, including a data filter process, technical criteria assessment and robust statistical calculation. The generated analytical results demonstrate the same instrumental performance with both TIMS and MC-ICP-MS for Sr and Nd isotopic analysis. However, significant discrete data for the Pb isotope ratios obtained by TIMS and MC-ICP-MS are evident, indicating existing challenges for accurate Pb isotopic analysis. It was found that 91500 is not a suitable Hf isotopic RM for micro-analysis due to the heterogeneous Hf isotopic composition and the Ple?ovice zircon may be a more ideal alternative. This study provides a powerful protocol and practical examples for estimating reference values of isotope ratios in frequently used RMs.
2004, 25(4):191-196.
DOI: 10.46770/AS.2004.04.006
Abstract:
A rapid, sensitive, and cost-effective method was developed for the determination of trace mercury in water samples by on-line coupling of flow injection (FI) sorption preconcentration with oxidative elution to cold vapor atomic fluorescence spectrometry (CV-AFS). race Hg(II) in aqueous solution was preconcentrated by on-line formation of mercury diethyldithiocarbamate complex (Hg-DDTC) and adsorption of the resulting neutral complex on the inner walls of a PTFE knotted reactor (KR). A mixture of 16% (v/v) HCl and 10% (v/v) H2O2 was used as the eluent to remove the adsorbed Hg-DDTC from the KR, then convert on-line the Hg-DDTC into Hg(II) prior to its reduction to elemental mercury by KBH4 for subsequent on-line CV-AFS detection. The tolerable concentrations of Cd(II) As(Ill) Se(IV) Fe(III), Co(II), Ni(II), and Cu(II) and Cu(II) for the determination of 0.1 mug L-I Hg(II) were 0.1, 10, 0.1, 0.1, 0.7, 1, 0.3, and 0.2 mg L-1, respectively. With a sample loading flow rate of 3.1 mL, min(-1) for a 60-s preconcentration, a detection limit (3sigma) of 4.4 ng L-I was achieved at a sample throughput of 36 samples h(-1). The precision (RSD, n = 11) was 1.7% at the 1 0, 1-mug L-1 Hg (11) level. The method was successfully applied to the determination of mercury in a certified reference material, GBW(E) 080392, and a number of local natural water samples.
A rapid, sensitive, and cost-effective method was developed for the determination of trace mercury in water samples by on-line coupling of flow injection (FI) sorption preconcentration with oxidative elution to cold vapor atomic fluorescence spectrometry (CV-AFS). race Hg(II) in aqueous solution was preconcentrated by on-line formation of mercury diethyldithiocarbamate complex (Hg-DDTC) and adsorption of the resulting neutral complex on the inner walls of a PTFE knotted reactor (KR). A mixture of 16% (v/v) HCl and 10% (v/v) H2O2 was used as the eluent to remove the adsorbed Hg-DDTC from the KR, then convert on-line the Hg-DDTC into Hg(II) prior to its reduction to elemental mercury by KBH4 for subsequent on-line CV-AFS detection. The tolerable concentrations of Cd(II) As(Ill) Se(IV) Fe(III), Co(II), Ni(II), and Cu(II) and Cu(II) for the determination of 0.1 mug L-I Hg(II) were 0.1, 10, 0.1, 0.1, 0.7, 1, 0.3, and 0.2 mg L-1, respectively. With a sample loading flow rate of 3.1 mL, min(-1) for a 60-s preconcentration, a detection limit (3sigma) of 4.4 ng L-I was achieved at a sample throughput of 36 samples h(-1). The precision (RSD, n = 11) was 1.7% at the 1 0, 1-mug L-1 Hg (11) level. The method was successfully applied to the determination of mercury in a certified reference material, GBW(E) 080392, and a number of local natural water samples.
2004, 25(4):170-176.
DOI: 10.46770/AS.2004.04.003
Abstract:
A method based on?cloud?point?extraction?was developed to determine?cadmium?at?the?nanogram?per?liter?level?in?sea-water?by?graphite?furnace?atomic absorption spectrometry. Diethyldithiocarbamate (DDTC) was used as?the?chelating reagent to form Cd-DDTC complex; Triton X-114 was added as?the?surfactant.?The?parameters affecting sensitivity and?extraction?efficiency (i.e., pH?of?the?solution, concentration?of?DDTC and Triton X-114, equilibration temperature, and centrifugation time) were evaluated and optimized. Under?the?optimum conditions, a preconcentration factor?of?51.6 was obtained for a 20-ml, water sample.?The?detection limit was as low as 2.0 ng L-1 and?the?analytical curve was linear?in?the?10.0-200.0 ng L-1 range with satisfactory precision (RSD < 4.7%).?The?proposed method was successfully applied to?the?trace?determination?of?cadmium?in?seawater.
A method based on?cloud?point?extraction?was developed to determine?cadmium?at?the?nanogram?per?liter?level?in?sea-water?by?graphite?furnace?atomic absorption spectrometry. Diethyldithiocarbamate (DDTC) was used as?the?chelating reagent to form Cd-DDTC complex; Triton X-114 was added as?the?surfactant.?The?parameters affecting sensitivity and?extraction?efficiency (i.e., pH?of?the?solution, concentration?of?DDTC and Triton X-114, equilibration temperature, and centrifugation time) were evaluated and optimized. Under?the?optimum conditions, a preconcentration factor?of?51.6 was obtained for a 20-ml, water sample.?The?detection limit was as low as 2.0 ng L-1 and?the?analytical curve was linear?in?the?10.0-200.0 ng L-1 range with satisfactory precision (RSD < 4.7%).?The?proposed method was successfully applied to?the?trace?determination?of?cadmium?in?seawater.
Shui-Yuan Yang
,
Shao-Yong Jiang
,
Qian Mao
,
Zhen-Yu Chen
,
Can Rao
,
Xiao-Li Li
,
Wan-Cai Li
,
Wen-Qiang Yang
,
Peng-Li He
,
Xiang Li
2022, 43(2):186-200.
DOI: 10.46770/AS.2021.912
Abstract:
Electron probe microanalysis (EPMA) is an in-situ and non-destructive analytical technique with high spatial resolution and an increasingly important analysis tool in materials science and geosciences. This study summarizes the principles and functions of EPMA, and the problems and difficulties, along with the recent advances in quantitative analysis of EPMA. A routine EPMA procedure includes preparing samples, setting analytical conditions, acquiring data, and evaluating results. Caution is required in all steps to obtain high-quality analytical results. The problems and difficulties commonly encountered in EPMA are discussed and the corresponding measures and solutions required to resolve them are proposed. Specific analytical methods are suggested to make accurate analysis of some specific minerals. We also summarized the challenges and solutions in light element analysis, trace element analysis, EPMA U-Th-Pb total dating, combined analysis with wavelength- and energy-dispersive X-ray spectroscopy, submicron spatial resolution analysis at low accelerating voltages, iron oxidation state analysis, and standard reference materials.
Electron probe microanalysis (EPMA) is an in-situ and non-destructive analytical technique with high spatial resolution and an increasingly important analysis tool in materials science and geosciences. This study summarizes the principles and functions of EPMA, and the problems and difficulties, along with the recent advances in quantitative analysis of EPMA. A routine EPMA procedure includes preparing samples, setting analytical conditions, acquiring data, and evaluating results. Caution is required in all steps to obtain high-quality analytical results. The problems and difficulties commonly encountered in EPMA are discussed and the corresponding measures and solutions required to resolve them are proposed. Specific analytical methods are suggested to make accurate analysis of some specific minerals. We also summarized the challenges and solutions in light element analysis, trace element analysis, EPMA U-Th-Pb total dating, combined analysis with wavelength- and energy-dispersive X-ray spectroscopy, submicron spatial resolution analysis at low accelerating voltages, iron oxidation state analysis, and standard reference materials.
2016, 37(6):229-237.
DOI: 10.46770/AS.2016.06.003
Abstract:
Coal fly ash contains several trace elements some of which are toxic such as As, Cr, Pb, etc. Coal ash also contains relatively high amounts of rare earth ele- ments whose recovery from coal ash could be an alternate source for their supply. Although ura- nium and thorium are less chemi- cally toxic than other constituent elements such as arsenic, ques- tions have been raised concern- ing the possible risk from radiation. Hence, the concentration levels of all of these trace toxic elements in fly ash samples have to be assessed to determine whether the ash is hazardous or not, and also to decide the place and method of its disposal or re- utilization. In this study, multi- elemental analysis of some coal ash samples originating from two thermal power plants in southern India has been carried out, employ- ing inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively cou- pled plasma mass spectrometry (ICP-MS), with the focus on some trace toxic elements. The meth- ods employed were validated by analayzing international certified fly ash reference materials. The concentrations of trace-toxic ele- ments in the samples analyzed were: 20-82 μg/g for As, 45-281 μg/g for Cr, 31-607 μg/g for Ba, 21- 865 μg/g for Sr, 8-39 μg/g for Ge, <5-80 μg/g for Ga, <5-100 μg/g for Cu, 19-50 μg/g for Co, 58-258 μg/g for Ni, 8-73 μg/g for Pb, 44-260 μg/g for Zn, 0.6-8.6 μg/g for U, 1-30 μg/g for Th, 6-196 μg/g for La, 14-528 μg/g for Ce, 5-196 μg/g for Y. These results were compared with trace-toxic element concentra- tions in coal ash samples as reported in the literature.
Coal fly ash contains several trace elements some of which are toxic such as As, Cr, Pb, etc. Coal ash also contains relatively high amounts of rare earth ele- ments whose recovery from coal ash could be an alternate source for their supply. Although ura- nium and thorium are less chemi- cally toxic than other constituent elements such as arsenic, ques- tions have been raised concern- ing the possible risk from radiation. Hence, the concentration levels of all of these trace toxic elements in fly ash samples have to be assessed to determine whether the ash is hazardous or not, and also to decide the place and method of its disposal or re- utilization. In this study, multi- elemental analysis of some coal ash samples originating from two thermal power plants in southern India has been carried out, employ- ing inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively cou- pled plasma mass spectrometry (ICP-MS), with the focus on some trace toxic elements. The meth- ods employed were validated by analayzing international certified fly ash reference materials. The concentrations of trace-toxic ele- ments in the samples analyzed were: 20-82 μg/g for As, 45-281 μg/g for Cr, 31-607 μg/g for Ba, 21- 865 μg/g for Sr, 8-39 μg/g for Ge, <5-80 μg/g for Ga, <5-100 μg/g for Cu, 19-50 μg/g for Co, 58-258 μg/g for Ni, 8-73 μg/g for Pb, 44-260 μg/g for Zn, 0.6-8.6 μg/g for U, 1-30 μg/g for Th, 6-196 μg/g for La, 14-528 μg/g for Ce, 5-196 μg/g for Y. These results were compared with trace-toxic element concentra- tions in coal ash samples as reported in the literature.
2021, 42(5):238-246.
DOI: 10.46770/AS.2021.101
Abstract:
The emerging field of matermetallomics refers to all research activities aimed at the clarification of the role and function of metallic elements in materials. This paper discusses the concept of matermetallomics and the related analytical techniques used for probing the interactions between structure-activity relationships. The main object of matermetallomics research is metallic elements in materials, and includes the significance and contributions to materials science. This paper also introduces the analytical approaches used in matermetallomics, which includes the techniques of imaging, spectroscopic, X-ray-based, ion beam, MS-based and atomic spectrometry.
The emerging field of matermetallomics refers to all research activities aimed at the clarification of the role and function of metallic elements in materials. This paper discusses the concept of matermetallomics and the related analytical techniques used for probing the interactions between structure-activity relationships. The main object of matermetallomics research is metallic elements in materials, and includes the significance and contributions to materials science. This paper also introduces the analytical approaches used in matermetallomics, which includes the techniques of imaging, spectroscopic, X-ray-based, ion beam, MS-based and atomic spectrometry.
Vivek K. Singh
,
Neha Sharma
,
Onkar N. Verma
,
Virendra K. Singh
,
Durgesh K. Tripathi
,
Yonghoon Lee
,
Sandeep Kumar
,
Piyush K. Rai
,
M.A. Gondal
2021, 42(2):99-113.
DOI: 10.46770/AS.2020.201
Abstract:
Trace minerals and metallic elements play a key role in plant metabolism and function. Therefore, it is important to understand the movement and distribution of trace minerals within various parts of plants in order to understand their metabolic pathways. Information on the localization of minerals can be utilized in the fields of plant science, agriculture, and food technologies. In this context, herein, we review the feasibility of application of laser-induced breakdown spectroscopy (LIBS) as a technique for trace element detection and mapping in different plant matrices. LIBS is a well-established technique that can be used to perform rapid multi-elemental detection in various types of samples, including plants. Owing to the unique capabilities of LIBS, its field applications are growing rapidly, particularly in the area of plant science. Here, our primary emphasis is on the quantitative and qualitative elemental imaging of different varieties of plant species that are of importance as medicines and foodstuffs. In this review article, we present an exhaustive survey of recent developments, including technical advances and recent work involving the detection of nanoparticles in plant samples and in the monitoring of soil content. The future potential of LIBS and the viability of its possible applications to the detection of essential minerals and heavy metals in plants used as foods or of medicinal importance are also discussed.
Trace minerals and metallic elements play a key role in plant metabolism and function. Therefore, it is important to understand the movement and distribution of trace minerals within various parts of plants in order to understand their metabolic pathways. Information on the localization of minerals can be utilized in the fields of plant science, agriculture, and food technologies. In this context, herein, we review the feasibility of application of laser-induced breakdown spectroscopy (LIBS) as a technique for trace element detection and mapping in different plant matrices. LIBS is a well-established technique that can be used to perform rapid multi-elemental detection in various types of samples, including plants. Owing to the unique capabilities of LIBS, its field applications are growing rapidly, particularly in the area of plant science. Here, our primary emphasis is on the quantitative and qualitative elemental imaging of different varieties of plant species that are of importance as medicines and foodstuffs. In this review article, we present an exhaustive survey of recent developments, including technical advances and recent work involving the detection of nanoparticles in plant samples and in the monitoring of soil content. The future potential of LIBS and the viability of its possible applications to the detection of essential minerals and heavy metals in plants used as foods or of medicinal importance are also discussed.
1999, 20(2):45-52.
DOI: 10.46770/AS.1999.02.001
Abstract:
Theory, design, and operation of a dynamic reaction cell for ICP-MS
Theory, design, and operation of a dynamic reaction cell for ICP-MS
Neha Sharma
,
Yugal Khajuria
,
Virendra K. Singh
,
Sandeep Kumar
,
Yonghoon Lee
,
Piyush K. Rai
,
Vivek K. Singh
2020, 41(3):110-118.
DOI: 10.46770/AS.2020.03.003
Abstract:
Papaya is a tropical fruit of the Carica papaya plant and grown all over the world. Root knot nematodes are one of the major problems in papaya fruit crop production and causes maximum yield loss every year by slowly killing the plant. In this article, we study healthy as well as nematode-infested papaya plants at the atomic and molecular levels to obtain information about the causes and changes occurring in the plant after infestation. Microscopic observations were made to check the presence of pathogens in the plant. Elemental profiling of healthy and infested papaya plants was assessed by using two advanced spectroscopic techniques, namely laser-induced breakdown spectroscopy (LIBS) and wavelength dispersive X-ray fluorescence spectroscopy (WDXRF). The structural changes in the complex bio compounds, such as starch, protein, lipids, fatty acids, and carbohydrates, were assessed by Fourier transform infrared spectroscopy (FTIR). The elemental and molecular profiling results of the infested vs. the healthy papaya plants were compared to establish why the plants die.
Papaya is a tropical fruit of the Carica papaya plant and grown all over the world. Root knot nematodes are one of the major problems in papaya fruit crop production and causes maximum yield loss every year by slowly killing the plant. In this article, we study healthy as well as nematode-infested papaya plants at the atomic and molecular levels to obtain information about the causes and changes occurring in the plant after infestation. Microscopic observations were made to check the presence of pathogens in the plant. Elemental profiling of healthy and infested papaya plants was assessed by using two advanced spectroscopic techniques, namely laser-induced breakdown spectroscopy (LIBS) and wavelength dispersive X-ray fluorescence spectroscopy (WDXRF). The structural changes in the complex bio compounds, such as starch, protein, lipids, fatty acids, and carbohydrates, were assessed by Fourier transform infrared spectroscopy (FTIR). The elemental and molecular profiling results of the infested vs. the healthy papaya plants were compared to establish why the plants die.
2021, 42(4):210-216.
DOI: 10.46770/AS.2021.068
Abstract:
Analysis of the elemental abundance and distribution in biological tissues by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) adds to clarifying the basic questions of metabolic research and enables bioaccumulation and bioavailability studies in ecological and toxicological risk assessment. In this work, a method based on matrix-matched gelatin calibration LA-ICP-MS for the determination of essential and toxic elements in biological samples was developed. By using a mold-prepared procedure, the elemental inhomogeneity distributions in the synthesized gelatin gels were improved, which was verified by using the 3D (surface- and depth-mapping) LA-ICP-MS protocols. The limits of detection (LODs) ranged from 0.014 μg g?1 (Ba) to 48 μg g?1 (K). The results of the analysis of biological reference materials (RMs) were in good agreement with the certified values. Furthermore, a reliable bio-mapping LA-ICP-MS method is proposed for studying the metabolism of heavy metals in rat liver injected with CdS/PbS quantum dots. Our results show that the high concentration of Pb and Cd co-exist (positive correlation as high as 78%) in hepatocytes and sinusoids, which indicates that the PbS/CdS quantum dots are not dissociated into toxic heavy metal ions (i.e., Pb2+, Cd2+) in the metabolic process of the liver.
Analysis of the elemental abundance and distribution in biological tissues by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) adds to clarifying the basic questions of metabolic research and enables bioaccumulation and bioavailability studies in ecological and toxicological risk assessment. In this work, a method based on matrix-matched gelatin calibration LA-ICP-MS for the determination of essential and toxic elements in biological samples was developed. By using a mold-prepared procedure, the elemental inhomogeneity distributions in the synthesized gelatin gels were improved, which was verified by using the 3D (surface- and depth-mapping) LA-ICP-MS protocols. The limits of detection (LODs) ranged from 0.014 μg g?1 (Ba) to 48 μg g?1 (K). The results of the analysis of biological reference materials (RMs) were in good agreement with the certified values. Furthermore, a reliable bio-mapping LA-ICP-MS method is proposed for studying the metabolism of heavy metals in rat liver injected with CdS/PbS quantum dots. Our results show that the high concentration of Pb and Cd co-exist (positive correlation as high as 78%) in hepatocytes and sinusoids, which indicates that the PbS/CdS quantum dots are not dissociated into toxic heavy metal ions (i.e., Pb2+, Cd2+) in the metabolic process of the liver.
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