On-line recording of 13C/12C ratios and mass spectra in one gas chromatographic analysis

An isotope ratio mass spectrometer and an ion trap mass spectrometer have been coupled in parallel to one gas chromatograph. Using this arrangement both the ¹³C/¹²C ratio and the mass spectrum of a given compound can be measured simultaneously under identical gas chromatographic conditions. Although column connection fittings are employed to split the capillary eluate, chromatographic performance was barely impaired. Development of the system has been monitored by recording δ¹³C values of the constituents of Grob test mixture no. 2. The accuracy and reliability of system performance has also been tested.     

高纯Tb4O7中痕量杂质元素的火花源质谱测定

本文采用同位素稀释和相对灵敏度因子法相结合，定量分析了高纯Ｔｂ４Ｏ７中的２０多种微量元素的含量，测定检测限０．０ｘ－０．００ｘμｇ／ｇ，大多数元素的相对标准偏差在３０％以内，用同位素稀释法分析了Ｃｕ，Ｂａ，Ｄｙ三元素，其相对标准偏差均在１０％以内。     

Isotope effects and the mechanism of deoxygenation of epoxides with dichlorocarbene

The deoxygenation of styrene oxide with dichlorocarbene is studied by a combination of isotope effects and theoretical calculations. A normal ¹³C isotope effect of 1.016 is observed for the α-carbon of the styrene oxide but a surprising inverse isotope effect of 0.995 is observed at the β-carbon. This is indicative of a highly asynchronous process in which the C_α-O bond is broken without any progress in the breakage of C_β-O bond. Theoretical calculations support this interpretation. This coarctate reaction is formally concerted as it avoids involving a high-energy intermediate, but it appears uninfluenced by transition state aromaticity.     

GC–ICP–MS determination of dimethylselenide in human breath after ingestion of <Superscript>77</Superscript>Se-enriched selenite: monitoring of in-vivo methylation of selenium

The amount of volatile dimethylselenide (DMSe) in breath has been monitored after ingestion of sub-toxic amounts of selenium (300 μg ⁷⁷Se, as selenite) by a healthy male volunteer. The breath samples were collected in Tedlar bags every hour in the first 12 h and then at longer intervals for the next 10 days. The samples were subjected to speciation analysis for volatile selenium compounds by use of cryotrapping–cryofocussing–GC–ICP–MS. Simultaneously, all urine was collected and subjected to total selenium determination by use of ICP–MS. By monitoring m/z 82 and 77, background or dietary selenium and selenium from the administered selenite were simultaneously determined in the urine and in the breath—dietary selenium only was measured by monitoring m/z 82 whereas the amount of spiked ⁷⁷Se (99.1% [enriched spike]) and naturally occurring selenium (7.6% [natural abundance]) were measured by monitoring m/z 77. Quantification of DMSe was performed by using DMSe gas samples prepared in Tedlar bags (linear range 10–300 pg, R ²=0.996, detection limit of Se as DMSe was 10 pg Se, or 0.02 ng L⁻¹, when 0.5 L gas was collected). Dimethylselenide was the only selenium species detected in breath samples before and after the ingestion of ⁷⁷Se-enriched selenite. Additional DM⁷⁷Se was identified as early as 15 min after ingestion of the isotopically-labelled selenite. Although the maximum concentration of ⁷⁷Se in DMSe was recorded 90 min after ingestion, the natural isotope ratio for selenium in DMSe (77/82) was not reached after 20 days. The concentration of DMSe correlated with the total Se concentration in the urine during the experiment (R ²=0.80). Furthermore, the sub-toxic dose of 300 μg selenium led to a significant increase of DMSe and renal excretion of background selenium, confirming that selenium ingested as selenite is homeostatically controlled by excretion. The maximum concentration of DMSe resulting from the spiked selenite was 1.4 ng Se L⁻¹ whereas the dietary background level was less than 0.4 ng Se L⁻¹. Overall excretion as DMSe was calculated to be 11.2% from the ingested selenite within the first 10 days whereas urinary excretion accounts for nearly 18.5%.     

Synthesis of labelled dihydroartemisinic acid

[15-¹³C²H₃]-Dihydroartemisinic acid (2a), [15-C²H₃]-dihydroartemisinic acid (2b) and [15-¹³CH₃]-dihydroartemisinic acid (2c) have been obtained in good yield and high isotopic enrichment by a reconstructive synthesis from artemisinin. These labelled compounds were designed to be used in biosynthetic experiments to determine the origins of artemisinin and other sesquiterpene natural products from Artemisia annua.     

The application of isotope dilution thermal ionization mass spectrometry to traceability of chemical measurement and interlaboratory comparisons

In this work, the method of isotope dilution thermal ionization mass spectrometry able to trace to SI was developed to accurately measure trace amount of Cd, Pb, Zn and Cu in sediment, rice, wine, and human serum samples for interlaboratory comparisons. The research focuses on how to apply the primary method correctly, uncertainty evaluation of measurement results, and how to achieve the meaning of traceability to SI by using ID-TIMS. As a result, the measurement results of Cu and Zn in the human serum 1 and 2 with 0.94, 0.83 and 0.49% combined uncertainty, respectively, were accepted by EC-JRC-IRMM as the certified values of the serum samples. The measurement results of Cd and Pb in CCQM-K13 and CCQM-K24 with 3.96, 1.62 and 1.03% combined uncertainty, respectively, are within the degrees of the equivalence. These comparisons at the highest level of measurement are proof that traceability of chemical measurement can be achieved as the traceability chain of ID-TIMS established in this work was used.     

Investigation of equilibration and uncertainty contributions for the determination of inorganic mercury and methylmercury by isotope dilution inductively coupled plasma mass spectrometry

The mass fractions of Hg and methylmercury, in two certified reference materials, NIST2710 and DORM-2, have been determined by total and species-specific isotope dilution analysis (IDA), respectively, and uncertainty budgets for each analysis calculated. The mass fraction of Hg in NIST2710 was determined by ID using multicollector sector field inductively coupled plasma mass spectrometry (MC-SF-ICP-MS) whilst the mass fraction of methylmercury in DORM-2 was determined using HPLC coupled with quadrupole ICP-MS.

The extent of equilibration between the spike and the particulate bound mercury compounds was studied temporally by monitoring the ²⁰⁰Hg:¹⁹⁹Hg isotope amount ratio and by determining the total amount of Hg in the liquid phase. For the NIST2710 complete equilibration was only achieved when concentrated HNO₃ in combination with a microwave digestion was employed, and good agreement between the found (31.7±4.0 μg g⁻¹, expanded uncertainty k=2) and certified (32.6±1.8 μg g⁻¹) values was obtained. For DORM-2 complete equilibration of methylmercury between the liquid and solid phases was achieved when using 50:50 H₂O:CH₃OH (v/v) and 0.01% 2-mercaptoethanol as the solvent. Even though only 50% of the analyte was extracted into the liquid phase, complete equilibration was achieved, hence, the found methylmercury mass fraction (4.25±0.47 μg g⁻¹, expanded uncertainty k=2) was in good agreement with the certified value (4.47±0.32 μg g⁻¹).     

Discrepancy in infrared measurement results of carbon monoxide in nitrogen mixtures due to variations of the 13C/12C isotope ratio

Significant errors in the non-dispersive infrared (NDIR) analyses of carbon monoxide (CO) can be made when the ¹³C/¹²C isotope ratio in the sample and the calibrant differ significantly. This paper shows that variations in the ¹³C/¹²C isotope ratio of 5×10⁻² mol/mol CO in nitrogen mixtures on three different NDIR CO analysers may lead to serious deviations in the instrument response, whereas the instrument response using GC-TCD is unaffected. The observed deviations in the assigned amount-of-substance fraction CO for a ¹³C depleted mixture vary from +2 to −5% relative to the gravimetric amount-of-substance fraction for different NDIR analysers. A GC-MS method has been developed to perform a pre-screening of the isotopic composition of CO in nitrogen mixtures. This method proved to be an adequate tool to measure differences in the ¹³C/¹²C ratio. Based on the GC-MS results a suitable measurement technique can be selected, or information about a possible error in NDIR analysis can be given to the producer or user of the calibration gas mixture. Presented at 3. International Gas Analysis Symposium, October 6–8, 2004, in Amsterdam     

Peculiarities in the Raman spectra of ZrB12 and LuB12 single crystals

We have measured Raman spectra of high-quality Zr^natB₁₂, Lu^natB₁₂ and Lu¹¹B₁₂ single crystals with high resolution, and the observed strong peaks are attributed to specific vibration modes. Besides, there are a number of additional Raman peaks in spectral ranges, where only Raman-inactive vibrations of the atomic arrangement are expected. Accordingly, it is assumed, that the investigated crystals contain intrinsic structural imperfections or distortions in sufficient concentration and efficiency to initiate the observed breaking of phonon selection rules. We suppose boron vacancies, boron isotope effects and displacements of the metal atoms to be reasons for such imperfections.     

电感耦合等离子体质谱法测定黄沙土壤中铅同位素比

用电感耦合等离子体质谱法（ＩＣＰ—ＭＳ）测定了５个黄沙原土样品中铅同位素比２０７Ｐｂ／２０６Ｐｂ、２０８Ｐｂ／２０６Ｐｂ，样品来自被认为是黄沙气溶胶源地区，为了使铅同位素测量中质量偏差和漂移减至最少，在样品中加入了铊标准溶液，测量２０５Ｔｌ／２０３Ｔｌ比，校正质量数差别选择的影响．同时，采用ＩＣＰ—ＭＳ和电感耦合等离子体原子发射光谱法（ＩＣＰ一ＡｌＳ）测定了随粒径变化样品中１２种元素浓度的变化．