PreCon: A Fully Automated Interface for the Pre-Gc Concentration of Trace Gases on Air for Isotopic Analysis

Abstract

For the high precision isotope analysis of atmospheric trace gases a computer controlled concentration interface has been developed. From small air samples it collects either N₂O or CO₂ derived from CH₄ at their respective concentrations (0.3 ppm for N₂O, 1.7 ppm for CH₄) into a small diameter cold trap (?196°C) and interfaces via GC and open split to an isotope ratio mass spectrometer (Finnigan MAT 252) for on-line isotope evaluation. External reproducibilities for repeated measurements of 100 ml air samples from the same source of < 0.2° (δ-notation) have been achieved for ¹³C/¹²C from CH₄ and for ¹⁵N/¹⁴N and ¹⁸O/¹⁶O from N₂O. The precision is adequate to monitor the isotopic changes in these gases during a day's course.     

A frequency-modulated quantum-cascade laser for spectroscopy of CH4 and N2O isotopomers

We report the development of a novel laser spectrometer for high-sensitivity detection of methane and nitrous oxide. The system relies on a quantum-cascade laser source emitting wavelength of around 8.06 μm, where strong fundamental absorption bands occur for the considered species and their isotopomers. The detection technique is based on audio-frequency and radio-frequency modulation of laser radiation. First experimental tests have been performed to estimate the achievable detection limits and the signal reproducibility levels in view of possible measurements of ¹³C/¹²C, ¹⁸O/¹⁶O, ¹⁷O/¹⁶O and ¹⁵N/¹⁴N isotope ratios.     

Biomedical Application of an Isotope Selective Nondispersive Infrared Spectrometer for 13CO2 and 12CO2 Concentration Measurements in Breath Samples

A newly developed isotope selective nondispersive infrared (NDIR) spectrometer for the measurement of ¹³CO₂ and ¹²CO₂ concentrations in breath samples was applied as a low cost and very simple to operate alternative to isotope ratio mass spectrometry (IRMS). We used this device for several biomedical applications ([¹³C]urea breath test, [¹³C]leucine metabolism, [¹³C]methacetin catabolism of rats) and found that the results agree very well with IRMS.     

High precision and continuous field measurements of δ 13C and δ 18O in carbon dioxide with a cryogen-free QCLAS

The present paper describes a compact and cryogen-free, quantum cascade laser based absorption spectrometer (QCLAS) designed for in situ, continuous and high precision isotope ratio measurements of atmospheric CO₂. The mobile instrument incorporates several new features including a novel astigmatic multi-pass cell assembly, a quasi-room temperature quantum cascade laser, thermoelectrically cooled detectors as well as a new retrieval approach. The combination of these features now makes it possible to measure isotope ratios of ambient CO₂ with a precision of 0.03 and 0.05‰ for δ¹³C and δ¹⁸O, respectively, using a 100 s integration time. A robust and optimized calibration procedure was developed to bring the retrieved isotope ratios on an absolute scale. This assures an accuracy better than 0.1‰ under laboratory conditions. The instrument performance was also assessed in a field campaign in which the spectrometer operated autonomously and provided mixing ratio values for the main three CO₂ isotopologues at one second time resolution. An accuracy of 0.2‰ was routinely obtained for both isotope ratios during the entire period. The results were in excellent agreement with the standard laboratory-based isotope ratio mass spectrometer measurements made on field-collected flask samples. A few illustrative examples are used to depict the potential of this optical method in atmosphere–biosphere research. PACS  07.57.Ty; 42.62.Fi; 92.60.Kc     

The Position Dependent 15N Enrichment of Nitrous Oxide in the Stratosphere

Abstract

The position dependent ¹⁵N fractionation of nitrous oxide (N₂O), which cannot be obtained from mass spectrometric analysis on molecular N₂O itself, can be determined with high precision using isotope ratio mass spectrometry on the NO⁺ fragment that is formed on electron impact in the source of an isotope ratio mass spectrometer. Laboratory UV photolysis experiments show that strong position dependent ¹⁵N fractionations occur in the photolysis of N₂O in the stratosphere, its major atmospheric sink. Measurements on the isotopic composition of stratospheric N₂O indeed confirm the presence of strong isotope enrichments, in particular the difference in the fractionation constants for ¹⁵N¹⁴NO and ¹⁴N¹⁵NO. The absolute magnitudes of the fractionation constants found in the stratosphere are much smaller, however, than those found in the lab experiments, demonstrating the importance of dynamical and also additional chemical processes like the reaction of N₂O with O(¹D).     

Measurement of the mass of110Pd and114Pd using the (14C,16O) reaction

A measurement of the mass excess of¹¹⁰Pd and¹¹⁴Pd has been made by detecting emergent¹⁶O ions in aQ3D magnetic spectrometer using the¹¹²Cd(¹⁴C,¹⁶O)¹¹⁰Pd and¹¹⁶Cd(¹⁴C,¹⁶O)¹¹⁴Pd reactions at 60 MeV. The results are compared with theoretical predictions.     

A multi-reflection time-of-flight mass separator for isobaric purification of radioactive ion beams

A multi-reflection time-of-flight mass separator (MR-ToF-MS) for the enhancement of the performance of the Penning-trap mass spectrometer ISOLTRAP at the on-line isotope separator ISOLDE/CERN has been built and investigated at an off-line test facility. The MR-ToF-MS consists of two ion-optical mirrors between which oscillating ions are separated according to their different mass-over-charge ratios m/q. Flight paths of several hundreds of meters are folded to an apparatus length of less than one meter. Preliminary tests resulted in a mass-resolving power of up to m/??m????80,000, and the separation was demonstrated for the isobaric ions CO^?+? and $\mathrm{N}_2^+$ . The MR-ToF-MS will support the existing purification methods of ISOLTRAP and will extend the access to nuclides produced with high isobaric contamination yields at the ISOLDE facility.     

First real-time measurement of the evolving 2H/1H ratio during water evaporation from plant leaves

We have studied the temporal behaviour of the deuterium isotope ratio of water vapour emerging from a freshly cut plant leaf placed in a dry nitrogen atmosphere. The leaf material was placed directly inside the sample gas cell of the stable isotope ratio infrared spectrometer. At the reduced pressure (～40 mbar) inside the cell, the appearance of water evaporating from the leaf is easily probed by the spectrometer, as well as the evolving isotope ratios, with a precision of about 1 ‰. The demonstration experiment we describe measures the ²H/¹H isotope ratio only, but the experiment can be easily extended to include the ¹⁸O/¹⁶O and ¹⁷O/¹⁶O isotope ratios. Plant leaf water isotope ratios provide important information towards quantification of the different components in the ecosystem water and carbon dioxide exchange.     

Aerosol source (biomass,traffic and coal emission) apportionment in Lithuania using stable carbon and radiocarbon analysis*

In the present study, a combination of the stable carbon isotope ratio (¹³C/¹²C) with radiocarbon data (¹⁴C) allowed us to perform the aerosol source apportionment. Filter samples of PM₁ were collected during the warm and cold periods in rural and urban sites in Lithuania. The ¹⁴C/¹²C ratio of total carbon (TC) was measured using the single stage accelerator mass spectrometer quantifying of fossil and non-fossil derived aerosol emissions. The δ¹³C value was measured using an elemental analyser interfaced with an isotope ratio mass spectrometer. We have found that the highest fraction of contemporary carbon (f_c?=?0.82) was measured during a warm period in a rural location. A higher fraction of fossil fuel-derived carbon was observed for air masses transported from highly industrialized Western European regions during both seasons. Isotope mass balance calculations revealed that the traffic emissions composed 15 and 25?% in rural and urban sites, respectively, and did not change during either season. Input from coal-derived aerosol particles was estimated to be 15?% at an urban site during the cold period. The combination of the stable carbon isotope ratio with the radiocarbon data allowed us to distinguish coal, liquid fossil fuel combustion, and non-fossil derived aerosol particle emissions.     

High-accuracy mass determination of unstable cesium and barium isotopes

Direct mass measurements of short-lived Cs and Ba isotopes have been performed with the tandem Penning trap mass spectrometer ISOLTRAP installed at the on-line isotope separator ISOLDE at CERN. Typically, a mass resolving power of 600 000 and an accuracy of δm ≈ 13 keV have been obtained. The masses of ^123,124,126Ba and ^122mCs were measured for the first time. A least-squares adjustment has been performed and the experimental masses are compared with theoretical ones, particularly in the frame of a macroscopic-microscopic model.     

Isotopic composition and concentration measurements of atmospheric CO2 with a diode laser making use of correlations between non-equivalent absorption cells

Correlations between a sample and a sealed reference cell of a tunable diode laser spectrometer for the measurement of the isotopic composition (δ ¹³C) and the concentration of atmospheric carbon dioxide in air have been investigated. Likely due to fluctuations of the laser emission profile, these correlations have been used to improve the performance of the instrument. In a comparison with isotope ratio mass spectrometer and gas chromatographic measurements, an accuracy of 0.15‰ for δ ¹³C and 0.05 ppmv for the CO₂ concentration is demonstrated for 40 s integration time. Long-term stability and field deployment of the instrument have been investigated during a few days measurement campaign in Paris.     

15N, 13C-On-line Measurements with an Elemental Analyser (Carlo Erba,NA 1500), a Modified Trapping Box and a Gas Isotope Mass Spectrometer (Finnigan,MAT 251)

Abstract

An on-line method for the determination of ¹⁵N and ¹³C with a gas isotope mass spectrometer (Finnigan, MAT 251) was developed to improve the sensitivity and to reduce measurements time and the cost of the sample analysis. For this purpose an elemental analyser (Carlo Erba, NA 1500) was coupled to the mass spectrometer using parts of the capillary system of a trapping box (Finnigan, type CN). For the determination of samples with natural concentrations of ¹⁵N and ¹³C the uncertainty of the delta value is less than 0.2 δ‰. The detection limit is in the order of 10 μg (total N or total C) and 7 samples can be analysed per hour.     

Isotope-analytical results of a study of gas generation in L/ILW

The paper presents the results of a long-term measurement series using hermetic containers to make more precise quantitative estimation of the generation rates and radioactivity of the gas in a drum of low and intermediate level radioactive waste (L/ILW) packages. Development of special preparation lines and isotope-analytical measurements of the headspace gas samples were performed in the ATOMKI. Stable isotope measurements were executed from the CO₂ and CH₄ fractions by stable isotope ratio mass spectrometer. Noble gas (He) measurements were done by noble gas mass spectrometer. The tritium content of the vapour, H₂ and CH₄ fractions was measured in H₂O chemical form by a low background liquid scintillation counter. The ¹⁴C content of the CO₂ and CH₄ fractions of the headspace gas samples was measured by a low background gas proportional counter system.     

Continuous measurements of stable carbon isotopes in CO2 with a near-IR laser absorption spectrometer

A near-IR laser absorption spectrometer using a technique of wavelength modulation spectroscopy is used to measure stable carbon isotope ratios of ambient CO₂ (δ¹³C) via the absorption lines ¹²CO₂ R(17) (2ν₁ + ν¹₂ − ν¹₂ + ν₃) at 4978.205 cm⁻¹ and ¹³CO₂ P(16) (ν₁ + 2ν₂ + ν₃) at 4978.023 cm⁻¹. The isotope ratios are measured with a reproducibility of 0.02‰ (1σ) in a 130-s integration time over a 12-h period. The humidity effect on δ¹³C values has been evaluated in laboratory experiments. The δ¹³C values of CO₂ in ambient air were measured continuously over 8 days and agreed well with those from isotope ratio mass spectrometry of canister samples. The spectrometer is thus capable of real-time, in situ measurements of stable carbon isotope ratios of CO₂ under ambient conditions.     

Precision Penning trap mass measurements of rare isotopes produced by projectile fragmentation

The low-energy beam and ion trap facility LEBIT at NSCL/MSU is at present the only facility where precision experiments are performed with stopped rare isotope beams produced by fast-beam fragmentation. LEBIT combines high-pressure-gas stopping with advanced ion manipulation techniques to provide brilliant low-energy beams. So far these beams have mainly been used for mass measurements on short-lived rare isotopes with a 9.4T Penning trap mass spectrometer. Recent examples include ^70m Br , located at the proton dripline, ³²Si and the iron isotopes ^63-65Fe . While the measurement of ³²Si helps to solve a long-standing dispute over the validity of the isobaric multiplet mass equation (IMME) for the A = 32 , T = 2 multiplet, the mass measurements of ^65m,g Fe marked the first time a nuclear isomeric state has been discovered by Penning trap mass spectrometry.     

An angular resolved pulsed UV LED photoelectron source for KATRIN

The KArlsruher TRItium Neutrino experiment KATRIN aims to determine the mass of the electron antineutrino with a sensitivity of 0.2 eV/c² on m(ν_e) at 90% confidence level by measuring the kinematics of the tritium beta decay with a spectrometer of MAC-E filter-type. To investigate the properties of the spectrometer, electron sources with special properties are needed. A pulsed UV LED photoelectron source with angular selectivity has been developed for this purpose. The principle has been successfully tested during measurements at the spectrometer of the Mainz neutrino mass experiment.     

Determination of cholesterol absorption in humans: from radiolabel to stable isotope studies

Hypercholesterolemia is a major health risk. Dietary cholesterol absorption is one important factor affecting levels of plasma and tissue cholesterol. Considerable effort has thus been devoted to develop reliable in vivo clinical methodologies to determine dietary cholesterol absorption in humans. The present paper summarises radiolabelled experiments and major advances in stable isotope technologies to determine cholesterol absorption. Initially, direct methods employing gastro-intestinal intubation were developed. Later, indirect methods using oral–faecal cholesterol balance permitted calculation of cholesterol mass absorption. Once the use of radiolabelled [³H, ¹⁴C]cholesterol balance was developed in healthy humans, it was finally possible to distinguish exogenous and endogenous cholesterol. Non-invasive and safer stable isotope (²H, ¹³C, ¹⁸O) labelled cholesterol tracers then replaced radioisotopes for use in infants and adults. Stable isotopes and radioisotopes showed identical cholesterol kinetics. The most promising contemporary stable isotope assessment of cholesterol absorption is a dual stable isotope dual tracer approach based on simultaneous administration of oral and intravenous differentially labelled cholesterol tracers, followed by plasma sampling for 3–4?d. Online GC/Combustion/IRMS and GC/Pyrolysis/IRMS allow minimal amounts of dual stable isotope cholesterol tracers to be detected. Using the dual stable isotope dual tracer approach, the percent cholesterol absorption in adult volunteers has been determined to be 50–70%.     

Selectivity of the 12C(18O, 16O)14C reaction

A study about the ¹²C(¹⁸O, ¹⁶O)¹⁴C two-neutron transfer reaction was performed at the Catania INFN-LNS laboratory at 84 MeV incident energy. The ¹⁶O ejectiles produced in the reactions were momentum analyzed and identified by the MAGNEX spectrometer. The Q-value spectrum of ¹⁴C shows several known bound and resonant states, in particular states with 2p-4h configuration respect to the ¹⁶O core. The integrated cross sections show an enhanced yield for the two-neutron transfer compared to the one-neutron transfer. These results are some experimental evidences that the (¹⁸O, ¹⁶O) reaction proceeds mainly by the direct transfer of the neutron pair, instead of a second order process.     

The mass of 15B via a three-proton stripping reaction

The isotope ¹⁵B was produced via the reaction ⁴⁸Ca(¹⁸O, ¹⁵B)⁵¹V. The Q-value and mass excess were determined to be ?21.76 ± 0.05 MeV and 28.96 ± 0.05 MeV, respectively. A search for the isotope ¹⁴Be was unsuccessful.