EA-IRMS法测定不同类型土壤有机碳稳定性同位素组成

利用元素分析仪-稳定同位素比例质谱仪(EA-IRMS)分析系统,以国际标准物质Urea为基准,标定了高纯钢瓶CO2参考气,其δ13CvsPDB值为(-29.523±0.181)‰。通过试验对比检验了EA-IRMS分析系统的稳定性、线性,测定δ13C值的样品分析精度,建立了测定土壤中有机碳稳定性同位素的分析方法。其离子强度在1.0~7.0V之间具有良好的线性,在1.5~5.0V内的线性优于总体线性;样品分析精度优于0.15‰;样品含碳量大于5μg即可满足测定δ13C的分析要求。应用此方法实测了18份不同类型土壤的有机碳稳定同位素组成,获得其13C天然丰度平均值为1.082%;不同类型的土壤有机碳稳定同位素组成存在较大的差异。

大气CH_4中碳稳定同位素组成的PreCon-GC/C-IRMS系统测定

利用预浓缩装置-气相色谱/燃烧-同位素比值质谱仪(PreCon-GC/C-IRMS)联用系统,建立了就采样、浓缩和在线质谱分析大气CH4中稳定碳同位素组成的测定方法。通过多组试验对比,分析并讨论了利用PreCon-GC/C-IRMS联用技术测定大气CH4中碳稳定同位素比值的试验条件、系统线性、稳定性及准确度和精密度等。结果表明,在本研究方法条件下,当离子流强度在1.0~20 V时,系统线性良好(斜率S=0.04‰/V),在4.0~15 V内其线性(斜率S=0.03‰/V)优于总体线性;系统测量稳定性可靠,δ13C值的测定结果的S.D<0.3‰,最大偏差<0.5‰,回收率达99.99%,准确度和精度均符合分析与研究要求。利用该系统对室内和室外草坪地空气中CH4的碳稳定同位素组成做初步测试,其碳同位素的平均值分别为-31.358‰和-33.085‰,且相同地点区域空气中CH4的1δ3C值,在1 d内和不同日期间的变化均在0.5‰以内,重现性良好。

针式微萃取结合GC-IRMS测定水溶液中甲酸、乙酸的稳定碳同位素组成

甲酸和乙酸稳定碳同位素组成（δ^13C）的分析对环境、食品、制药和自然产品等的研究具有重要的应用价值。但目前尚缺乏有效的测定方法。本研究利用最近出现的针式固相微萃取技术（NeedlEX），以吹扫．捕集方式对水溶液中的有机酸进行了萃取，然后利用气相色谱．同位素比值质谱联用仪（GC—IRMS）对所萃取的有机酸分子进行了占δ^13C的测定。结果显示，质谱计的信号强度与水溶液中有机酸的浓度存在显著的线性相关关系（R^2〉0．99，P〈0．05），表明Needl EX对水溶液中有机酸具有稳定的萃取能力。在甲酸与乙酸含量分别不低于300μg／mL与200μg／mL的水溶液中，1000mL的吹扫体积可以使两者δ^13C多次分析结果的相对误差分别保持在3％和1％左右，且整个实验流程没有造成可检测的碳同位素分馏作用。低于这两个浓度界线，则分析误差随浓度的降低迅速增加。本研究虽然是针对水溶液中有机酸δ^13C的测定，其萃取方法对其他水溶性挥发和半挥发有机物δ^13C的分析也同样具有应用价值.

Pyrohydrolysis-IRMS determination of silicate chlorine stable isotope compositions. Application to oceanic crust and meteorite samples

This contribution describes the optimization of chlorine extraction from silicate samples by pyrohydrolysis prior to the precise determination of Cl stable-isotope compositions (637 Cl) by gas source, dual inlet Isotope Ratio Mass Spectrometry (IRMS) on CH(3)Clg. The complete method was checked on three international reference materials for Cl-content and two laboratory glass standards. Whole procedure blanks are lower than 0. 5 mu mol, corresponding to less than 10 wt.% of most of the sample chloride analysed. In the absence of international chlorine isotope rock, we report here Cl extracted compared to accepted Cl contents and reproducibilities on Cl and delta Cl-37 measurements for the standard rocks. After extraction, the Cl contents of the three international references compared within error with the accepted values (mean yield = 94 +/-10%) with reproducibilities better than 12% (10). The laboratory glass standards - andesite SO100DS92 and phonolite S9(2) - were used specifically to test the effect of chloride amount on the measurements. They gave Cl extraction yields of 100 +/-6% (1 sigma-; n = 15) and 105 +/- 8% (1 sigma-; n = 7), respectively, with delta Cl-37 values of -0.51 0.14%o and -0.39 0.17%o (1g). In summary, for silicate samples with Cl contents between 39 and 9042 ppm, the Pyrohydrolysis/HPLC method leads to overall CI extraction yields of 100 8%, reproducibilities on Cl contents of 7% and on delta Cl-37 measurements of 0.12%o (all 1 sigma). The method was further applied to ten silicate rocks of various mineralogy and chemistry (meteorite, fresh MORB glasses, altered basalts and setpentinized peridotites) chosen for their large range of Cl contents (70-2156 ppm) and their geological significance. delta Cl-37 values range between -2.33 and -0.50%o. These strictly negative values contrast with the large range and mainly positive values previously reported for comparable silicate samples and shown here to be affected by analytical problems. Thus we propose a preliminary, revised terrestrial CI cycle, mainly dominated by negative and zero delta Cl-37 values. (C) 2007 Elsevier B.V. All rights reserved.

Valor de corte para teste respiratório com isótopos estáveis (Carbono 13) no diagnóstico do Helicobacter pylori utilizando IRMS para análise do sopro

After the isolation of Helicobacter pylori from an injury at the stomach mucosa by Marshall and Wareen, work that was recognized with the Nobel Prize of Medicine or Physiology in 2005, many other works showed the relationship between the presence of H. pylori and diseases at the digestive system, such as gastritis, gastric, duodenal and peptic ulcer, and stomach cancer. The 13C-Urea Breath Test - 13C-UBT is a non-invasive diagnostic method that utilizes the breath of a patient to determine the presence of H. pylori through stable isotopes. This work aimed to find an ideal 13C-UBT Isotopic Ratio Mass Spectroscopy cut-off value (a threshold between positive and negative) to diagnose H. pylori infection at Brazilian population. Patients were selected at the UNESP-Botucatu Clinical Hospital Endoscopy Section. With these results it was possible to indicate that the best cut-off value is between 2.5 to 6 ‰ of Delta Over Baseline (DOB)