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     

An off-axis cavity-enhanced absorption spectrometer at 1605 nm for the 12CO2/13CO2 measurement

A distributed feedback diode laser sensor based upon off-axis cavity-enhanced absorption spectroscopy at 1605.5 nm has been developed for ¹³C¹⁶O₂/¹²C¹⁶O₂ isotope ratio measurements in synthetic air and human breath. A noise-equivalent absorption sensitivity of 3.9×10^-10 cm^-1 Hz^-1/2 has been determined for a cavity base length of 28.2 cm and averaging 4000 scans within 8.688 s. For 5% CO₂ concentration measurements, δ¹³C standard deviations of 1.8 ‰ and 3.7 ‰ have been estimated for five successive measurements based on peak height and integrated area estimations at 107.9 Torr, respectively. The contributions of amplified spontaneous emission of the laser and a radiation that is spatially uncoupled into the cavity mode have been described for cavity transmittance measurements. The limitations of the developed sensor and further steps towards precision and accuracy improvements are discussed. PACS 42.55.Px; 39.30.+w; 42.62.Fi; 42.60.-v     

A diode laser spectrometer for symmetry selective detection of ozone isotopomers

A tunable diode laser absorption spectrometer operating in the 10 μm range is described, which for the first time permits simultaneous detection and quantification of the five naturally most abundant ozone isotopomers: ¹⁶O₃, ¹⁶O¹⁶O¹⁸O, ¹⁶O¹⁸O¹⁶O, ¹⁶O¹⁶O¹⁷O, and ¹⁶O¹⁷O¹⁶O. Ozone samples of 25 μmole size are analysed with an estimated accuracy of 6‰ (2σ). This level of accuracy is demonstrated by comparing spectroscopically determined isotopologue enrichments of ¹⁶O₂ ¹⁷O and ¹⁶O₂ ¹⁸O with mass spectrometer measurements. Samples for the comparison were generated from natural oxygen in an electric discharge under two different pressure conditions. The precision obtained is sufficient to study both the isotopic and the symmetry dependence of the unique oxygen isotope anomaly in ozone formation, which shows isotopomer specific fractionation values well in the 10% range. PACS 42.60.By; 42.55.Px; 33.20.Ea     

New low-energy measurement of the 18F(p,α)15O reaction

The ¹⁸F, produced during nova explosions, is the main responsible for the 511 keV γ-ray emitted during the outburst that could be detected with satellite missions or future γ-ray telescopes. In spite of many experimental efforts, the amount of ¹⁸F synthesized still suffers from large uncertainties concerning mainly the ¹⁸F(p,α)¹⁵O reaction. We report here on a new direct measurement of the ¹⁸F(p,α)¹⁵O cross section recently carried out at the RIB facility at Louvain-la-Neuve. Cross section data down to a center-of-mass energy of 400 keV have been obtained using an isobarically pure ¹⁸F beam (averaged intensity of the order of 10⁶ pps) and a thin polyethylene target. The reaction products were detected using the multi-strip detector array LEDA. The cross section data are analysed in the framework of the R-matrix model. Our main aim is to determine the interference sign between three 3/2⁺ resonances above threshold that can significantly affect the extrapolation of the ¹⁸F(p,α)¹⁵O cross section to the energies relevant for novae, and thus, the modeling of nova explosions.     

Laser diode spectroscopy of H2O at 2.63 μm for atmospheric applications

The 2.7 μm spectral range is highly suitable for the in situ monitoring of atmospheric H₂O using compact balloonborne laser diode spectrometers. Water vapour spectroscopic parameters of the 2₀₂   1₀₁ and the 4₁₃   4₁₄ transitions of the ν₃ band are revisited in this spectral region using a new distributed-feedback InGaAsSb laser diode emitting at 2.63 μm. Accurate line strengths are provided which are well adapted for the in situ probing of the middle atmosphere. Our measurements are thoroughly compared to an existing molecular database, laboratory measurements and ab-initio calculations. A laser hygrometer was developed for operation from small stratospheric balloons using this new laser diode technology, with emission at 2.6 μm. The realized sensor is described and results from a recent test-flight are reported. PACS 07.57.Ty; 92.60 Jq     

The temperature dependences of electromechanical properties of PLZT ceramics

The mechanical and electrical properties in lanthanum modified lead zirconate-titanate ceramics of 5/50/50 and 10/50/50 were studied by mechanical loss Q ^{- 1}, Young's modulus E, electric permittivity ε and tangent of dielectric loss of angle tgδ measurements. The internal friction Q ^{- 1} and Young modulus E measured from 290 K to 600 K shows that Curie temperature T_C is located at 574 K and 435 K (1^st cycle of heating) respectively for ceramic samples 5/50/50 and 10/50/50. The movement of T_C in second cycle of heating to lower temperature (561 K for 5/50/50 and 420 K for 10/50/50) has been observed. Together with Q ^{- 1} and E measurements, temperature dependences of ε=f(T) and tgδ=f(T) were determinated in temperature range from 300 K to 730 K. The values of T_C obtained during ε and tgδ measurements were respectively: 560 K for 5/50/50 and 419 K for 10/50/50. These temperatures are almost as high as the temperatures obtained by internal friction Q ^{- 1} measurements in second cycle of heating. In ceramic sample 10/50/50 the additional maximum on internal friction Q ^{- 1} curve at the temperature 316 K was observed.     

A novel multiple species ringdown spectrometer for in situ measurements of methane,carbon dioxide,and carbon isotope

We have developed a standalone, user-friendly, multi-species ringdown spectrometer for in situ measurements of methane (CH₄), carbon dioxide (CO₂), and a carbon dioxide isotope (¹³CO₂). The instrument is based on near-infrared continuous-wave cavity ringdown spectroscopy (NIR cw-CRDS) and engineered to be of approximately 16 kg with dimensions of 50 cm × 40 cm × 15 cm. The instrument design, optical configuration, electronic control, and performance are described. CH₄, CO₂, and ¹³CO₂ are measured at different wavelengths that are obtained through multiplexing two distributed feedback laser diodes with central wavelengths at 1597 and 1650 nm. The spectrometer has low power consumption and runs for 4–6 h when powered by a standard car battery. The instrument is operated either locally by interacting with a 7-inch touch screen or remotely via an Internet connection. The 1-σ detection limits for CH₄ and CO₂ are 0.2 and 120 ppmv, respectively. The measurement uncertainty is better than ±4% of full-scale reading for CH₄ and CO₂ and ±1.5‰ for δ¹³C (part per thousand relative to the Pee Dee Belemnite scale). Measurement of each species is near real-time; switching from measuring one species to another takes less than one minute. This work demonstrates a novel multiple-species CRDS-instrumentation platform, which can be adopted for development of an array of ringdown spectrometers for portable, user-friendly, field analysis of a variety of gases in environmental and industrial applications. Discussion of a future version of the spectrometer with better detection sensitivity, higher accuracy, and a smaller geometry is also presented. PACS  42.62.Fi; 42.55.Px; 33.20.Ea; 07.88.+y; 07.57.Ty     

Spectrofluorimetric Determination of 3-hidroxy-2-naphthoic Acid by Use of Its Ternary Complex with Zirconium (IV) and Beta-Cyclodextrin: Application to Determination in River Water

A spectrofluorimetric method has been developed for the determination of 3-hydroxy-2-naphthoic acid (3H2NA) by formation of a ternary complex with zirconium (IV) and β-cyclodextrin (β-CD). It has been observed that the fluorescence intensity of 3H2NA is greatly enhanced when the ternary complex is formed and is accompanied with shifts in the excitation and emission wavelengths. The conditions for the formation of the ternary complex have been optimized and the stoichiometry has been calculated, resulting a 1:2:1 complex (3H2NA:Zr: β-CD). The linear range was 20–2000 ng mL⁻¹ and the detection and quantification limits calculated were 17 and 58 ng mL⁻¹, respectively. The proposed method was applied to the determination of 3H2NA in river water. To eliminate interferences an off-line solid phase extraction (SPE) procedure using C18 cartridges was used. The extraction procedure was optimized and good recoveries were obtained (around 100%) with relative standard deviations (RSDs) of less than 5%.     

Isovector deformation and its link to the neutron shell closure

DWBA analysis of the inelastic ^30-40S(p,p') and ^18-22O(p,p') scattering data measured in the inverse kinematics has been performed to determine the isoscalar (δ₀) and isovector (δ₁) deformation lengths of the 2⁺₁ excitations in the Sulfur and Oxygen isotopes using a compact folding approach. A systematic N-dependence of δ₀ and δ₁ has been established which shows a link between δ₁ and the neutron-shell closure. Strong isovector deformations were found in several cases, e.g., the 2⁺₁ state in ²⁰O where δ₁ is nearly three times larger than δ₀. These results confirm the relation δ₁>δ₀ anticipated from the core polarization by the valence neutrons in the open-shell (neutron rich) nuclei. The effect of neutron shell closure at N=14 or 16 has been discussed based on the folding model analysis of the inelastic ²²O+p scattering data at 46.6 MeV/u measured recently at GANIL.     

Ionic conductivity and structural properties of MnO-doped Bi4V2O11 system

Bi₄V₂O₁₁ exists in three phases viz. α, β, and γ. High temperature γ-phase can be stabilized to room temperature owing to its higher conductivity by the partial substitution of metallic cations for vanadium in Bi₄V₂O₁₁. Phase transitions from α → β and β → γ are composition and temperature-dependent. Mn²⁺-doped compounds Bi₄V_2−x Mn _x O_{11− δ} (0 ≤ x ≤ 0.4) have been synthesized by solid state reaction technique and investigated by X-ray diffraction and ionic conductivity measurement. High ionic conducting γ-phase is stabilized for x ≥ 0.2. The ionic conductivity of the series of Bi₄V_2−x Mn _x O_{11− δ} samples has been measured by using ac impedance spectroscopy technique. The conductivity data do show departure from its simple Arrhenius behavior for all of the compositions. The highest conductivity observed for x = 0.2 sample can be attributed to lower activation energy.     

New method for isotopic ratio measurements of atmospheric carbon dioxide using a 4.3 μm pulsed quantum cascade laser

We present a new approach to the measurement of stable isotopic ratios of carbon dioxide using a near-room-temperature pulsed quantum cascade laser and a spectral ratio method based upon dual multiple pass absorption cells. The spectral ratio method improves precision and accuracy by reducing sensitivity to variations in the laser tuning rate, power and line width. The laser is scanned across three spectral lines (near 2310 cm^-1) quantifying three CO₂ isotopologues: ¹²C¹⁶O₂, ¹³C¹⁶O₂ and ¹²C¹⁶O¹⁸O. Isotopic ratios are determined simultaneously with a precision of 0.2δ for each ratio with a one-second measurement. Signal averaging for 400 s improves the precision to better than 0.03δ for both isotopic ratios (¹³ R and ¹⁸ R). Long-term accuracy of 0.2 to 0.3δ is demonstrated with replicate measurements of the same sample over a one-month period. The fast time response of this instrument is suitable for eddy flux measurements. PACS 07.57.Ty; 42.62.Fi; 92.70.Cp; 91.67.Rx     

Resonance photoacoustic spectroscopy and gas analysis of gaseous flow at reduced pressure

The results of theoretical and experimental studies of sensitivity of a resonant photoacoustic Helmholtz resonator detector for gas flowing through a photoacoustic cell under reduced pressure are presented. The measurements of the sensitivity and ultimate sensitivity of the differential photoacoustic cell were performed with a near-IR room-temperature diode laser using the well-known H₂O absorption line (12496.1056 cm^-1) as a reference. The measured value of the sensitivity (6–17 Pa W m^-1) is in satisfactory agreement with the calculated one, which equals 6–35 Pa W m^-1. The obtained value of the ultimate sensitivity ((3–5)×10^-7 W m^-1 Hz^-1/2) provides measurements of the concentration of molecules at the ppb–ppm level. Received: 19 April 2001 / Revised version: 18 September 2001 / Published online: 7 November 2001     

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) in a ring cavity

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) has been demonstrated by coupling a distributed feedback diode laser to a ring cavity. Frequency-selected light decaying from the ring cavity is retro-reflected, inducing a counter-propagating intra-cavity beam, and providing optical feedback to the laser. At specific laser-to-cavity distances, all cavity mode frequencies return to the diode laser with the same phase, allowing spectra to be accumulated across the range of frequencies of the current-tuned laser. OF-CEAS has been used to measure very weak oxygen isotopologue (¹⁶O¹⁸O and ¹⁶O¹⁷O) absorptions in ambient air at wavelengths near 762 nm using the electric-dipole forbidden O₂ A-band. A bandwidth reduced minimum detectable absorption coefficient of 2.2×10⁻⁹ cm⁻¹ Hz^−1/2 is demonstrated.     

The 5v 3 bands of 18O enriched ozone: line positions of 16O16O18O, 16O18O16O, 16O18O18O and 18O16O18O

The four 5v ₃ bands of ¹⁸O enriched ozone have been observed and analysed for the first time. Two species (¹⁶O¹⁸O¹⁶O and ¹⁸O¹⁶O¹⁸O) belong to the C_2v symmetry group and two other (¹⁸O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O) to the C_s symmetry group. They have been recorded at a resolution of 0.008 cm^?1 with a pathlength of 32.16 m. Despite the very weak absorptions observed, almost 250 energy levels have been derived for each of the 4 species, with J ? 35 and K _a ? 13, and suitable sets of Hamiltonian parameters have been determined. For 3 species it has been necessary to account for the resonance between the (005) and (311) states to correctly reproduce the spectra observed. These resonances, anharmonic for C_2v, and hybrid (both anhar-monic and Coriolis) for C_s symmetry confirm the accidentally extremely strong coupling between the (005) and (311) states for ¹⁶O₃, due in that case to the very close distance between unperturbed energy levels. This work also confirms the excellent prediction of band centres of these four species derived from the recently determined isotopically invariant molecular potential function.     

Hyperfine interactions of 19O in TiO2 and quadrupole moments of 13,19O

The electric quadrupole interaction of ¹⁹O(I^π=(5/2)⁺, T_1/2=27.0 s) in TiO₂ single crystal was studied in detail by means of the β-NQR to determine the electric quadrupole moments Q of short-lived β-emitting nuclei ¹⁹O and ¹³O(I^π=(3/2)^-, T_1/2=8.6 ms). Two implantation sites were found for the implanted O nucleus and the quadrupole coupling constants of ¹⁹O at these sites were determined. We observed FT-NMR of the enriched stable isotope ¹⁷O in TiO₂ and obtained the electric field gradient (EFG) at the oxygen substitutional site. With this knowledge, we have determined Q(¹³O)=11.0 ± 1.3 mb and Q(¹⁹O)=3.7 ± 0.4 mb. The present results are compared with the theoretical values calculated by the shell model code, OXBASH and by the Hartree–Fock calculation with the realistic potential. This revised version was published online in August 2006 with corrections to the Cover Date.     

Calculated spin-spin coupling surfaces in the water molecule; prediction and analysis of J (O,H), J (O,D) and J (H,D) in water isotopomers

Ab initio symmetry and internal valence coordinate oxygen–proton and proton–proton spin–spin coupling surfaces for the water molecule have been computed for the first time. Calculations have been performed at the SOPPA (CCSD) level using a large basis set and a grid of forty-nine geometries on the two surfaces. Equilibrium values differ significantly from some other calculated values especially for the Fermi contact terms. The bond length dependence of J(O, H) is ‘normal’ i.e. J(O, H₁) is much more sensitive to stretching the O–H₁ bond than the O–H₂ bond. This contrasts greatly with the corresponding situation in methane.

The surfaces have been averaged over the nuclear motion using a recent highly accurate force field to give values of J (O, H) and J (O, D) for H₂ ¹⁷O, HD¹⁷O and D₂ ¹⁷O and J(H, D) for HD¹⁶O, HD¹⁷O and HD¹⁸O over a range of temperatures. For J (O, H) and J (O, D) bond stretching at first order is the dominant part of the nuclear motion correction with second order bending making an important contribution. For J (H, D) the second order bending is by far the largest contribution to the nuclear motion corrections although the other terms partially cancel this contribution. Non-additivity can be largely attributed to the bending term for J (O, H). As expected, the bending terms also contribute relatively more to the temperature dependence of the couplings for J (O, H), J (O, D) and J (H, D). Our calculated J (O, H) in H₂ ¹⁷O of -77.22Hz at 293K is in very good agreement with Wasylishen and Friedrich's observed value of -78.70 (±0.02) Hz in cyclohexane at this temperature. Our calculated J(H, D) in HD ¹⁶O at 323K of -1.233Hz is close to a recent experimental value of -1.114 (±0.003) Hz in nitromethane-d ₃ observed by Sergeyev et al. at that temperature.     

Halo Structure of 19C via the (p,d) Reaction

 We have investigated the heaviest one-neutron halo candidate, the ¹⁹C nucleus. Few-body model calculations of cross-section angular distributions for the ¹⁹C(p,d)¹⁸C reaction together with test calculations carried out for the ¹⁷C(p,d)¹⁶C reaction at a low incident energy are presented for different possible halo-neutron configurations. We show that there is a clear distinction in particular between l _n  = 0 and l _n  = 2 halo transfers. The sensitivity of the cross sections to the assumed ¹⁹C single-neutron separation energy is discussed. Received October 13, 1999; revised November 25, 1999; accepted for publication April 29, 2000     

Observation of 18O/16O isotope effects at the cathode of a polymer electrolyte membrane fuel cell

¹⁸O/¹⁶O isotope effects were observed at the cathode of a polymer electrolyte membrane fuel cell at 25 and 35°C. Results of experiments in which the ¹⁸O/¹⁶O isotope ratios of the oxygen gases supplied to and exhausted from the cell were measured revealed that the lighter isotope ¹⁶O reacted more preferentially to form water molecules at the cathode than the heavier one, ¹⁸O. The value of the oxygen isotope separation factor, S₁, defined as the ratio of the ¹⁸O/¹⁶O isotope ratios of the oxygen gases supplied to and exhausted from the cell, ranged from 1.0030 to 1.0139, and tended to decrease with decreasing rate of oxygen utilisation (θ) and with increasing flow rate of the feed oxygen gas (D_F). The value of another separation factor, S₂, defined as the ratio of the ¹⁸O/¹⁶O isotope ratios of the exhausted oxygen gas and oxygen having reacted to form water molecules at the cathode, ranged from 1.0049 to 1.0304. The S₂ value was much less affected by the change in θ and D_F than the S₁ value with the majority of the S₂ value being in the range of 1.0240–1.0304.     

The assignment of quantum numbers in the theoretical spectra of the H2 16O, H2 17O, and H2 18O molecules calculated by variational methods in the region 0–26000 cm−1

Quantum numbers have been assigned in the theoretical spectra of three isotopologues of the water molecule: H₂ ¹⁶O, H₂ ¹⁷O, and H₂ ¹⁸O. The spectra were calculated by variational methods in the region 0–26000 cm^?1 at a temperature of 296 K. For each molecule, the quantum numbers are assigned to more than 28000 levels. The quantum numbers are assigned to 216766, 210679, and 211073 spectral lines of the H₂ ¹⁶O, H₂ ¹⁷O, H₂ ¹⁸O molecules, respectively. The theoretical spectra with the assigned quantum numbers are available in the Internet.     

Identification of the 109Xe and 105Te α-decay chain

The α-decay chain ¹⁰⁹Xe → ¹⁰⁵Te → ¹⁰¹Sn was identified at the Holifield Radioactive Ion Beam Facility. Advances in digital electronics have made possible the identification of both alpha emitters in the same experiment despite the disparate half-lives of 13 ±2 ms and 620 ±70 ns for ¹⁰⁹Xe and ¹⁰⁵Te, respectively. Two α-decay transitions were observed from ¹⁰⁹Xe with Q_α values of 4067 ±10 and 4217 ±8 keV. One transition between the ground states of ¹⁰⁵Te and ¹⁰¹Sn was observed with a Q_α value of 4889 ±6 keV. Using the measured half-lives, branching ratios, and Q_α values the reduced α-decay widths, δ², were determined. Comparison of the δ² value for ¹⁰⁵Te with ²¹³Po indicates a “superallowed" character in the α emission of ¹⁰⁵Te.