The traditional method for sulfur isotope measurement using EA-IRMS commonly requires sulfur content greater than 2 μmol. Such a large sample size limits its application to low-S materials, the size mainly being due ...The traditional method for sulfur isotope measurement using EA-IRMS commonly requires sulfur content greater than 2 μmol. Such a large sample size limits its application to low-S materials, the size mainly being due to ineffective utilization of sample gas, almost 99.7% of which is discarded with carrier gas through the split port of the continuous-flow interface. A modified EA-IRMS system with a gas chromatographic(GC) column and a custom-built cryogenic concentration device is used in this study. We measured six reference materials to test the performance of this method. The results were consistent with those obtained through traditional EA-IRMS. Precisions ranging from ±0.24‰ to ±0.76‰(1σ)can be obtained with samples equivalent to ~80 nmol sulfur, which were similar to results obtained from an alternative method using an absorption column. Our improved method is a powerful tool for sulfur isotope measurement in ultrasmall sulfide and sulfate samples, which can be further applied to carbon, nitrogen and oxygen isotope analyses of samples at about 100 nmol level.展开更多
The analysis of stable isotopes of carbon and oxygen in different carbonate rocks by the phosphoric acid method is not easier than that by the laser sampling method developed in recent years, which optically focuses l...The analysis of stable isotopes of carbon and oxygen in different carbonate rocks by the phosphoric acid method is not easier than that by the laser sampling method developed in recent years, which optically focuses laser beams with sufficient energy on a micro area of a thin section in a vacuum sample box via microscope. CO 2 produced by heating decomposition of carbonate was purified by the vacuum system, and the stable isotopic values of carbon and oxygen were calculated and analyzed on a mass spectrometer. This paper adopted the laser micro-sampling technique to analyze the stable isotopes of carbon and oxygen in dolomite, carbonate cement, stromatolite and different forms of dawsonite (donbassite). Results indicated that the laser micro-sampling method is effective in analyzing carbonate composition and could be a convincing proof for justification on carbonate composition analysis.展开更多
The procedures of sample preparation for isotopic determination of boron in clay sediments is very cumbersome, by far, there haven't been relevant reports on that. In order to establish an effective method for sam...The procedures of sample preparation for isotopic determination of boron in clay sediments is very cumbersome, by far, there haven't been relevant reports on that. In order to establish an effective method for sample preparation, a series of experiments were carried out. In this paper, boron in clay sediments was extracted with HCl solution and purified by two-step ion exchange method. Extracted HCl solution should be adjusted to alkalescency before passing through the Amberlite IRA 743 resin column due to the fact that Amberlite IRA 743 resin absorbs boron only from alkalescent solution. However, a mass of hydroxides of Al and Fe will be precipitated when the extracted HCl solution becomes alkalescent. Hydroxides of Al and Fe have a strong adsorption capacity for boron, which can cause boron isotope fractionation. To treat precipitated hydroxides of Al and Fe, four procedures, namely direct ion exchange (DRIE), decationizing ion exchange (DCIE), once sedimentation ion exchange (OSIE) and repeated sedimentation ion exchange (RSIE) were used and assessed. The influences of the four procedures on separation and extraction and isotopic composition of boron in experimental solutions and clay sediments were also discussed. According to the results, the DRIE, DCIE and OSIE are improper. The result of sample determination indicates that when extracting boron via RSIE, with the increase of precipitation times, there's an obvious decrease in boron content in the precipitated hydroxides while a sharp increase in recovery of boron and it is favorable for weakening the influence of boron isotope fractionation. But the process of RSIE is time consuming and it may introduce boron. It needs further research to establish a more effective sample preparation method for isotopic deter- mination of boron in clay sediments.展开更多
Silicon isotope analysis traditionally uses a standard-sample bracketing(SSB) method that relies upon greater instrument stability than can be consistently expected. The following proposed method reduces the level of ...Silicon isotope analysis traditionally uses a standard-sample bracketing(SSB) method that relies upon greater instrument stability than can be consistently expected. The following proposed method reduces the level of instrumental stability required for the analysis process and provides a valid solution for high-precision and accurate studies of Si isotopic compositions. Rock samples were dissolved by using alkali fusion and acidification.Silicon isotopes were purified with an ion exchange resin.Interfering peaks for isotopes were separated by using a Nu Plasma 1700 multi-collector inductively coupled plasma mass spectrometry(MS) system in high-resolution mode(M/DM [ 8000 RP). Two magnesium isotopes(^(25)Mg and^(26)Mg) and three silicon isotopes(^(28)Si,^(29) Si, and^(30)Si) were analyzed in the same data collection cycle. Mg isotopes were used as an internal standard to calibrate the mass discrimination effects in MS analysis of Si isotopes in combination with the SSB method in order to reduce the effects of MS interference and instrumental mass discrimination on the accuracy of measurements. The conventional SSB method without the Mg internal standard and the proposed SSB method with Mg calibration delivered consistent results within two standard deviations.When Mg was used as an internal standard for calibration,the analysis precision was better than 0.05 % amu.展开更多
Alpha spectrometry using pulse height analysis has been used for the determination of uranium concentrations in different environmental samples. The concentration of 238U was measured by both destructive and non-destr...Alpha spectrometry using pulse height analysis has been used for the determination of uranium concentrations in different environmental samples. The concentration of 238U was measured by both destructive and non-destructive techniques with a detection limit of less than 1.8 mBq/kg. However, because of the extremely low 234U concentrations in environmental samples, it was necessary to use a destructive technique to separate U from the sample matrices as well as remove interfering elements from the sample solution to determine 238U/234U ratio. In this study, the uranium was separated from the environmental samples using anion exchangers in (Dowex 1 × 8 Cl? form) and purified via co-precipitation with Lanthanum fluorides (LaF3) and the alpha source prepared by electrodeposition. The results obtained were validated using some certified reference samples.展开更多
Here we report iron(Fe) isotopic data of three pure Fe solution standards(IRMM-014, GSB Fe, and NIST3126a) and five widely used geological reference materials(RMs) from the United States Geological Survey and Geologic...Here we report iron(Fe) isotopic data of three pure Fe solution standards(IRMM-014, GSB Fe, and NIST3126a) and five widely used geological reference materials(RMs) from the United States Geological Survey and Geological Survey of Japan obtained on a Neptune Plus multi-collector–inductively coupled plasma–mass spectrometer(MC-ICP-MS) in our laboratory over the past 3 years. The instrumental mass bias was corrected by three independent methods: sample-standard bracketing(SSB),Ni doping + SSB, and ^(57)Fe–^(58)Fe double spike + SSB.Measurements reveal that both the Ni doping and double spike methods helped calibrate short-term fluctuations in mass bias. Collectively, almost all measurements of RMs yielded δ^(56)Fe within ± 0.05 of recommended values,provided that each sample was measured four times on MC-ICP-MS. For the first time, new recommended values for NIST SRM3126a are reported(δ^(56)Fe = 0.363 ± 0.006,2SE, 95% CI; and δ^(57)Fe = 0.534 ± 0.010, 2SE).展开更多
Isotope plays an important role in both tracing and dating in earth science, especially 87Rb-86 Sr system. With the development of earth science, whole-rock analysis can＇t sufficiently meet the requirements for scien...Isotope plays an important role in both tracing and dating in earth science, especially 87Rb-86 Sr system. With the development of earth science, whole-rock analysis can＇t sufficiently meet the requirements for scientific research and the micro-analysis becomes more and more significant. Laser ablation multi-collector inductively-coupled plasma mass-spectrometry（LA-MC-ICP-MS） has been extensively applied in micro-zone analysis due to its low sample-consumption, high accuracy, in situ and low requirements on matrix, but it is still difficult to accurately measure Sr isotope compositions especially for the samples with high Rb/Sr ratios and low Sr contents as it is restricted by severe quality discrimination and various types of mass spectrum interferences. Consequently, thermal ionization mass-spectrometry（TIMS）, as the most accurate and precise method to analyze isotopic ratios, is still the most popular method of analyzing Sr ratios, especially for the samples with low Sr contents. This paper makes a systematic review on the high-precision Sr isotope analyses of low-Sr geological samples, including the micro-sampling technique, ultra-low procedural blank chemical method and TIMS measurement technique. The combination of ultra-low procedural blank and TIMS can be used to perform high-precision micro-analysis of the samples with ng magnitude, which will be undoubtedly an important direction for Rb-Sr geochronology, geochemistry and environmental studies.展开更多
A very simple basic equation for the comparator technique is derived for the determination of 13C/12C ratio in biological samples by proton induced gamma- ray emission. On the basis of this treatments a new series of ...A very simple basic equation for the comparator technique is derived for the determination of 13C/12C ratio in biological samples by proton induced gamma- ray emission. On the basis of this treatments a new series of experiments has been made at a 2×1.7 tandem accelerator that proved conclusion about the method.展开更多
Studies of sulfur isotopes of coal or sedimentary rock may not only providesources of sulfur, but also provide some information about sedimentary environment,coalification and diagenesis. Many samples of coal and orga...Studies of sulfur isotopes of coal or sedimentary rock may not only providesources of sulfur, but also provide some information about sedimentary environment,coalification and diagenesis. Many samples of coal and organic-rich sediments, suchas black shale, contain a considerable content of sulfur that exists in several forms,such as pyrite, monosulfides, sulfates and organic sulfurs. For the various sulfurs,their isotopic compositions can be different in a single sample, for example, theisotopic ratios varied by as many as 30‰ in a sample of coal. To展开更多
Acid extraction methods have been used in the last half century to selectively extract the CO_(2)produced from different carbonate minerals in mixed samples.However,these methods are often time-consuming and labor int...Acid extraction methods have been used in the last half century to selectively extract the CO_(2)produced from different carbonate minerals in mixed samples.However,these methods are often time-consuming and labor intensive.Their application to clumped isotope(Δ47)analysis has not been demonstrated.We propose here an acid extraction method with phosphoric acid for bulk stable and clumped isotope analysis that treats mixtures of calcite and dolomite the same regardless of the proportional composition.CO_(2)evolved from calcite is extracted by allowing a reaction with phosphoric acid to proceed for 10 min at 50℃.We then extract CO_(2)evolved from dolomite by rapid ramping the acid temperature from 50 to 90℃and allowing the reaction to complete.The experimental results show that our method yields accurate calcite and dolomiteΔ_(47)values from mixed samples under different proportional compositions.Our method also displays equal or higher accuracy for calciteδ^(13)C and dolomiteδ^(13)C andδ^(18)O values from mixtures when compared to previous studies.Our approach exhibits higher sample throughput than previous methods,is adequate for clumped isotopic analysis and simplifies the reaction progression from over 24 h to less than 2 h,while maintaining relatively high isotopic obtaining accuracy.It yet poorly resolves calciteδ18O values,as found with previous methods.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos. 41627802 and 41973022)the Central Public-interest Scientific Institution Basal Research Fund (Grant No. YYWF201710)。
文摘The traditional method for sulfur isotope measurement using EA-IRMS commonly requires sulfur content greater than 2 μmol. Such a large sample size limits its application to low-S materials, the size mainly being due to ineffective utilization of sample gas, almost 99.7% of which is discarded with carrier gas through the split port of the continuous-flow interface. A modified EA-IRMS system with a gas chromatographic(GC) column and a custom-built cryogenic concentration device is used in this study. We measured six reference materials to test the performance of this method. The results were consistent with those obtained through traditional EA-IRMS. Precisions ranging from ±0.24‰ to ±0.76‰(1σ)can be obtained with samples equivalent to ~80 nmol sulfur, which were similar to results obtained from an alternative method using an absorption column. Our improved method is a powerful tool for sulfur isotope measurement in ultrasmall sulfide and sulfate samples, which can be further applied to carbon, nitrogen and oxygen isotope analyses of samples at about 100 nmol level.
文摘The analysis of stable isotopes of carbon and oxygen in different carbonate rocks by the phosphoric acid method is not easier than that by the laser sampling method developed in recent years, which optically focuses laser beams with sufficient energy on a micro area of a thin section in a vacuum sample box via microscope. CO 2 produced by heating decomposition of carbonate was purified by the vacuum system, and the stable isotopic values of carbon and oxygen were calculated and analyzed on a mass spectrometer. This paper adopted the laser micro-sampling technique to analyze the stable isotopes of carbon and oxygen in dolomite, carbonate cement, stromatolite and different forms of dawsonite (donbassite). Results indicated that the laser micro-sampling method is effective in analyzing carbonate composition and could be a convincing proof for justification on carbonate composition analysis.
基金financially supported by the National Natural Science Foundation of China (Nos. 40976074 and 41173019)project for doctors in the western supported by CAS
文摘The procedures of sample preparation for isotopic determination of boron in clay sediments is very cumbersome, by far, there haven't been relevant reports on that. In order to establish an effective method for sample preparation, a series of experiments were carried out. In this paper, boron in clay sediments was extracted with HCl solution and purified by two-step ion exchange method. Extracted HCl solution should be adjusted to alkalescency before passing through the Amberlite IRA 743 resin column due to the fact that Amberlite IRA 743 resin absorbs boron only from alkalescent solution. However, a mass of hydroxides of Al and Fe will be precipitated when the extracted HCl solution becomes alkalescent. Hydroxides of Al and Fe have a strong adsorption capacity for boron, which can cause boron isotope fractionation. To treat precipitated hydroxides of Al and Fe, four procedures, namely direct ion exchange (DRIE), decationizing ion exchange (DCIE), once sedimentation ion exchange (OSIE) and repeated sedimentation ion exchange (RSIE) were used and assessed. The influences of the four procedures on separation and extraction and isotopic composition of boron in experimental solutions and clay sediments were also discussed. According to the results, the DRIE, DCIE and OSIE are improper. The result of sample determination indicates that when extracting boron via RSIE, with the increase of precipitation times, there's an obvious decrease in boron content in the precipitated hydroxides while a sharp increase in recovery of boron and it is favorable for weakening the influence of boron isotope fractionation. But the process of RSIE is time consuming and it may introduce boron. It needs further research to establish a more effective sample preparation method for isotopic deter- mination of boron in clay sediments.
基金funded by the National Natural Science Foundation of China(Grant Nos.41427804,41421002,41373004)Beijing SHRIMP Center Open Foundation,and Program for Changjiang Scholars and Innovative Research Team in University(Grant No.IRT1281)the MOST Research Foundation from the State Key Laboratory of Continental Dynamics(BJ08132-1)
文摘Silicon isotope analysis traditionally uses a standard-sample bracketing(SSB) method that relies upon greater instrument stability than can be consistently expected. The following proposed method reduces the level of instrumental stability required for the analysis process and provides a valid solution for high-precision and accurate studies of Si isotopic compositions. Rock samples were dissolved by using alkali fusion and acidification.Silicon isotopes were purified with an ion exchange resin.Interfering peaks for isotopes were separated by using a Nu Plasma 1700 multi-collector inductively coupled plasma mass spectrometry(MS) system in high-resolution mode(M/DM [ 8000 RP). Two magnesium isotopes(^(25)Mg and^(26)Mg) and three silicon isotopes(^(28)Si,^(29) Si, and^(30)Si) were analyzed in the same data collection cycle. Mg isotopes were used as an internal standard to calibrate the mass discrimination effects in MS analysis of Si isotopes in combination with the SSB method in order to reduce the effects of MS interference and instrumental mass discrimination on the accuracy of measurements. The conventional SSB method without the Mg internal standard and the proposed SSB method with Mg calibration delivered consistent results within two standard deviations.When Mg was used as an internal standard for calibration,the analysis precision was better than 0.05 % amu.
文摘Alpha spectrometry using pulse height analysis has been used for the determination of uranium concentrations in different environmental samples. The concentration of 238U was measured by both destructive and non-destructive techniques with a detection limit of less than 1.8 mBq/kg. However, because of the extremely low 234U concentrations in environmental samples, it was necessary to use a destructive technique to separate U from the sample matrices as well as remove interfering elements from the sample solution to determine 238U/234U ratio. In this study, the uranium was separated from the environmental samples using anion exchangers in (Dowex 1 × 8 Cl? form) and purified via co-precipitation with Lanthanum fluorides (LaF3) and the alpha source prepared by electrodeposition. The results obtained were validated using some certified reference samples.
基金supported by the National Natural Science Foundation of China(41473016)the State Key Laboratory of Geological Processes and Mineral Resources
文摘Here we report iron(Fe) isotopic data of three pure Fe solution standards(IRMM-014, GSB Fe, and NIST3126a) and five widely used geological reference materials(RMs) from the United States Geological Survey and Geological Survey of Japan obtained on a Neptune Plus multi-collector–inductively coupled plasma–mass spectrometer(MC-ICP-MS) in our laboratory over the past 3 years. The instrumental mass bias was corrected by three independent methods: sample-standard bracketing(SSB),Ni doping + SSB, and ^(57)Fe–^(58)Fe double spike + SSB.Measurements reveal that both the Ni doping and double spike methods helped calibrate short-term fluctuations in mass bias. Collectively, almost all measurements of RMs yielded δ^(56)Fe within ± 0.05 of recommended values,provided that each sample was measured four times on MC-ICP-MS. For the first time, new recommended values for NIST SRM3126a are reported(δ^(56)Fe = 0.363 ± 0.006,2SE, 95% CI; and δ^(57)Fe = 0.534 ± 0.010, 2SE).
基金supported by National Natural Science Foundation of China (Nos. 90914007, 41125013)111 Plan (B07039)+1 种基金special fund of Ministry of Science and Technology,State Key Laboratory of Geological Processes and Mineral Resources (No. MSFGPMR201404)fund of Central University Fundamental Research (No. CUG090105)
文摘Isotope plays an important role in both tracing and dating in earth science, especially 87Rb-86 Sr system. With the development of earth science, whole-rock analysis can＇t sufficiently meet the requirements for scientific research and the micro-analysis becomes more and more significant. Laser ablation multi-collector inductively-coupled plasma mass-spectrometry（LA-MC-ICP-MS） has been extensively applied in micro-zone analysis due to its low sample-consumption, high accuracy, in situ and low requirements on matrix, but it is still difficult to accurately measure Sr isotope compositions especially for the samples with high Rb/Sr ratios and low Sr contents as it is restricted by severe quality discrimination and various types of mass spectrum interferences. Consequently, thermal ionization mass-spectrometry（TIMS）, as the most accurate and precise method to analyze isotopic ratios, is still the most popular method of analyzing Sr ratios, especially for the samples with low Sr contents. This paper makes a systematic review on the high-precision Sr isotope analyses of low-Sr geological samples, including the micro-sampling technique, ultra-low procedural blank chemical method and TIMS measurement technique. The combination of ultra-low procedural blank and TIMS can be used to perform high-precision micro-analysis of the samples with ng magnitude, which will be undoubtedly an important direction for Rb-Sr geochronology, geochemistry and environmental studies.
基金The Project Supported by the National Natural Science Foundation of China
文摘A very simple basic equation for the comparator technique is derived for the determination of 13C/12C ratio in biological samples by proton induced gamma- ray emission. On the basis of this treatments a new series of experiments has been made at a 2×1.7 tandem accelerator that proved conclusion about the method.
文摘Studies of sulfur isotopes of coal or sedimentary rock may not only providesources of sulfur, but also provide some information about sedimentary environment,coalification and diagenesis. Many samples of coal and organic-rich sediments, suchas black shale, contain a considerable content of sulfur that exists in several forms,such as pyrite, monosulfides, sulfates and organic sulfurs. For the various sulfurs,their isotopic compositions can be different in a single sample, for example, theisotopic ratios varied by as many as 30‰ in a sample of coal. To
基金funded by the fellowship of the China Postdoctoral Science Foundation(No.2020M682134)the National Natural Science Foundation of China(Nos.41872149,42076220)the Shandong Postdoctoral Innovation Research Project。
文摘Acid extraction methods have been used in the last half century to selectively extract the CO_(2)produced from different carbonate minerals in mixed samples.However,these methods are often time-consuming and labor intensive.Their application to clumped isotope(Δ47)analysis has not been demonstrated.We propose here an acid extraction method with phosphoric acid for bulk stable and clumped isotope analysis that treats mixtures of calcite and dolomite the same regardless of the proportional composition.CO_(2)evolved from calcite is extracted by allowing a reaction with phosphoric acid to proceed for 10 min at 50℃.We then extract CO_(2)evolved from dolomite by rapid ramping the acid temperature from 50 to 90℃and allowing the reaction to complete.The experimental results show that our method yields accurate calcite and dolomiteΔ_(47)values from mixed samples under different proportional compositions.Our method also displays equal or higher accuracy for calciteδ^(13)C and dolomiteδ^(13)C andδ^(18)O values from mixtures when compared to previous studies.Our approach exhibits higher sample throughput than previous methods,is adequate for clumped isotopic analysis and simplifies the reaction progression from over 24 h to less than 2 h,while maintaining relatively high isotopic obtaining accuracy.It yet poorly resolves calciteδ18O values,as found with previous methods.
