A new concept for sensitive in situ stable isotope ratio infrared spectroscopy based on sample modulation

Diode-laser absorption spectroscopy finds increasing applications in the emerging field of stable isotope research. To meet the requirements of the water isotopes measurement challenge in environmental research, ways have to be found to cope with the present limitations of spectroscopic systems. In this article, we discuss an approach based on the Stark effect in molecular spectra to reduce the influence of time-dependent, unwanted background structures generally superimposed on the desired signal from the spectral feature under investigation. A road map to high-sensitivity isotopic ratio measurements of water isotopes is presented. On the basis of an Allan Variance analysis of measured data, the detection limits have been calculated as a function of the integration time. To achieve the required optical density of about 6 x 10(-7) for H(2)(17)O measurements, the duty cycle has to be optimized and the implementation of a sample modulation within an optical multipass cell is a promising approach to increase the stability of spectroscopic instrumentation required for ecosystem research and airborne atmospheric platforms.     

Isotope Studies of Hydrogen and Oxygen in Ground Ice - Experiences with the Equilibration Technique

Abstract

Equilibration technique suitable for a large amount ofsamples is described for hydrogen and oxygen isotope analyses of ground ice, especially ice wedges, including the sampling strategy and the analytical procedure as well as the calibration of the Finnigan MAT Delta-S mass spectrometer in June, 1999. Since for future analyses of ice wedges, a higher sampling resolution with limited sample volume is required, the limit of the equliibration technique for small water samples size of between 0.05 and 5 ml was checked. For water samples smaller than 1ml, corresponding to a molar ratio [H₂O]/[H₂] of smaller than 0.994, a balance correction has to be applied. The experimental errors due to partial evaporation during evacuation, the balance calcultion of the isotope equilibration process, the linearity as well as memory effects of the mass spectrometer for smaples with large differences in δ¹⁸O and δD are tackled in this paper. In the polar regions of Northern Siberia without Late Pleistocene and Holocene glaciation, ground ice is used as an archive for paleoclimate studies. First results of stable isotope measurements on ice wedges clearly show a shift towards heavier isotopes and thus warmer winter temperatures as well as a change in the source of the precipitation between Late Pleistocene and Holocene. These results indicate the high potential of ground ice for paleoclimate studies.     

Inner-shell excited quartet states in Li-like O<Superscript>5+</Superscript> and Ne<Superscript>7+</Superscript> ions

First laser spectroscopic measurements of the 6s5d³D₁-6s6p¹P₁ and 6s5d³D₂-6s6p¹P₁ transitions in several isotopes of atomic barium have been performed. The hyperfine structure of these transitions was optically resolved and isotope shifts for even and odd isotopes were determined. The isotope shifts show a deviation from their expected behavior for odd isotopes in an analysis based on King-plots. This observation puts atomic structure calculations at test because available theories do not predict this. A profound understanding of the wavefunctions for heavy alkaline earth systems like barium (Ba) and radium (Ra) is essential for a theoretical evaluation of their sensitivity to fundamental symmetry breaking effects such as they could be observed, e.g., through permanent electric dipole moments. Further the absolute frequency of the 6s^{2 1}S₀-6s6p³P₁ intercombination line in ¹³⁸Ba was determined to be 12 636.6232(1) cm^-1.     

Hyperfine structure and nuclear magnetic moments of some neutron-deficient thallium isotopes

Using the atomic-beam magnetic resonance method, hyperfine structure (h.f.s.) measurements have been performed in the²P_1/2 electronic ground state of the neutron-deficient thallium isotopes^193–202Tl. In the doubly odd isotopes, the magnetic dipole hyperfine interaction constantsa were determined, while in the odd-A isotopes, direct measurements of the nuclearg-factors,g _I , were made. The electronicg-factor was measured in¹⁹⁸Tl. The magnetic dipole moments of the doubly odd isotopes have been evaluated by a direct comparison with known values in the stable isotope²⁰³Tl. The moments of the odd-A isotopes are in agreement with pervious measurements by optical spectroscopy. A discussion of the magnetic dipole moments in terms of different nuclear models is included. The moments of the 2^? nuclear ground states of the doubly odd isotopes may be interpreted as arising from a combination of the configurations 2^? (πs_1/2 vf_5/2) and 2^? (πs_1/2 vp_3/2).     

Paleoclimatology

The Lamas Basin is an area covering ～4400 km² situated on the eastern Mediterranean coast of Turkey covered with highly karstified limestone and dolomitic limestone from the Miocene and Mesozoic age, respectively. Owing to the area’s low karstification basement, groundwater in the karst aquifer circulates deep from the surface towards the springs along the coast as well as to the submarine springs. This study aims working out the salinization level and recharge characteristics of the Lamas Basin using environmental isotopes techniques. In the study, the data collected previously to discover, in general terms, the groundwater characteristics within the area are reanalyzed to fulfil the purpose of the study. In conclusion, it is found that the down gradient karst springs discharging along the Mediterranean coast mostly contain groundwater contributions from higher altitudes with depleted δ¹⁸O and δ²H compositions. The δ¹⁸O-altitude effect was determined as approximately?0.12 ‰/100 m which may indicate sea-spray intrusion towards inland. As a result, the salinization level of coastal springs changes ranging between 1.2 % and 17.0 %. Owing to the seawater encroachment, Ca–HCO₃ water type changes to Na–HCO₃ or Na-Cl water by the cation exchange during the dry period. As the unique freshwater potential extends along the coastal area, the groundwater production should be exploited in a way that seawater encroachment is kept at minimum.     

A study of the odd isotopes of copper using the 58, 60, 62, 64Ni(τ, d) 59, 61, 63, 65Cu and 48Ca(τ, d)49Sc reactions

Experimental measurements are reported for the ^{58, 60, 62, 64}Ni(τ, d) ^{59, 61, 63, 65}Cu and ⁴⁸Ca(τ, d)⁴⁹Sc reactions and for the elastic scattering of ³He particles from ^{58, 60, 62, 64}Ni and ⁴⁸Ca targets at an incident energy of 18 MeV. The (τ, d) angular distributions cover the angular range from approximately θ_c.m. = 5° to 90° and the elastic scattering angular distributions range from θ_c.m. = 12° to 172°. In the (τ, d) reactions several weakly excited states, not previously seen in stripping reactions, have been identified and assignments of the transferred angular momentum made. The ⁴⁸Ca(τ, d)⁴⁹Sc reaction data are used in conjunction with the theoretical sum rules of MacFarlane and French to determine the normalization factors to be used with DWBA calculations for different sets of optical potentials. These normalization factors are used to extract spectroscopic strengths and centroid energies from the Ni(τ, d)Cu data which are compared with published model calculations for the odd copper isotopes. It is concluded that these calculations invariably fail to give a consistent picture of the odd copper isotopes mainly due to the use of centroid energies as variable parameters in the model calculations.     

Tunable diode laser measurement of pressure-induced shift coefficients of CO2 around 2.05 μm for Lidar application

Atmospheric carbon dioxide (CO₂) is one of the main contributors to the greenhouse effect. A global monitoring of CO₂ from space is foreseen as a key issue to quantify its sources and sinks at a regional scale and to better predict future levels of CO₂ and their effect on climate change. Differential Absorption Lidar (DiAL) is a promising and novel spectroscopic technique for remote sensing CO₂ spatial and temporal concentration distribution with a high level of accuracy. However, a precise knowledge of spectroscopic parameters of CO₂ molecular transitions and their dependence with temperature and pressure is required for reducing the uncertainty on DiAl measurements. Hence, to support remote sensing of carbon dioxide in the troposphere, we report on the accurate determination of air pressure-induced shift coefficients for eight absorption lines belonging to the R branch of (20⁰1)_III←(00⁰0)_I band of CO₂ at 2.05 μm. Purposely, a high-resolution tunable diode laser absorption spectrometer (TDLAS) coupled to a cryogenically cooled optical cell was implemented. From these measurements, we have further determined the temperature-dependencies of the air pressure-induced shift coefficients.     

Shell-model calculations on Ni and Cu isotopes

Binding energies, excitation energies and spectroscopic factors have been calculated for^57–67Ni and^58–68Cu in an unrestricted (2p_3/2, lf _5/2,2p_1/2) shell-model space. The effective two-body matrix elements are obtained from the modified surface delta interaction (MSDI) and from a least-squares fit to experimental binding and excitation energies (ASDI). The average deviation between about 100 experimental and calculated energies is 0.14MeV for MSDI and 0.08 MeV for ASDI. Excitation energies of high-spin states are given also. Spectroscopic factors have been calculated for all single-nucleon transfer reactions on stable Ni or Cu targets leading to Ni or Cu isotopes. For spectroscopic factors larger than 0.4 the average deviation between theory and experiment is about 30%. The experimentally observed and calculated spectroscopic strengths are compared by using sum rules and are found to be consistent. An extensive compilation has been made of experimental data on energies,J ^π assignments and spectroscopic factors.     

New data on nuclear subshells obtained from the analysis of the information from the international database on nuclear structure ENSDF

In the last decade, a large amount of experimental nuclear spectroscopy data was obtained. This is good progress really, but a new very serious problem appears. Due to significant systematic errors of the data, one is often forced to deal with very discrepant data and often it is difficult to obtain reliable information from them. To solve this problem and to remove the systematic errors, new technologies in working with the data were developed. Using these new technologies, one can obtain information with a high accuracy and reliability, and in many cases, new information has not been or could not be obtained experimentally. Below, an approach of this kind is presented concerning spectroscopic data on Ca and Zr isotopes. It is shown that the behavior of the energy of the first 2⁺ level in Zr isotopes can be explained in the framework of a shell-model approach. A separation of the 2d_5/2 subshell in ⁹⁶Zr (as is for the 1f_7/2 subshell in ⁴⁸Ca) is found, so that the neutron number N=56 becomes like a magic number for Z=40. To explain a similarity in decaying properties of ⁴⁸Ca and ⁹⁶Zr, an additional interaction between closed structures consisting of 20 and 28 nucleons is proposed. Irregularities of the ground-state spin values in the K isotopic chain are explained in the framework of the shell-model approach by the inversion of the proton 1d_3/2 and 2s_1/2 orbitals.     

Hyperfine splitting constants in the optical transition \boldsymbol{{4{f}^{7}} {6{s}^{2}} \;{^{8}{\rm S}_{7/2}} \to {4{f}^{7}} {6{s}6{p}}\; {^{6}{\rm P}_{5/2}} \ {\rm of} \ {^{151-155}{\rm Eu}}} isotopes and hyperfine anomaly

Using the method of laser-induced fluorescence in an atomic beam we have measured the hyperfine splitting constants, A and B, of the ground and excited states of the optical transition 4f ⁷6s ^{2 8}S $_{1/2}\to 4f^{7}$ 6s6p ⁶P_5/2 (564.58 nm) for ^151???155Eu isotopes. For all isotopes, the magnetic dipole constants of the ⁶P_5/2 atomic level are determined to a precision better than 0.04%. The A and B constants for the ground state ⁸S_7/2 of the radioactive ^152,154,155Eu were obtained for the first time with a precision better than 0.5%. Our data along with previous ground state hyperfine structure measurements for the stable europium isotopes allow us to determine the hyperfine anomaly for mentioned Eu isotopes.     

Experimental and theoretical investigation of the isotope shift of the 4D level in atomic potassium

Doppler-free two-photon laser spectroscopic measurements in the deep red spectral region have been performed on the transition 4² S _1/2→4² D _J in the naturally abundant isotopes 39 and 41 of atomic potassium. The 4D level isotope shift, ?81±12 MHz was obtained by combining the current results with data from Rydberg-state spectroscopy. Many-body perturbation theoretical calculations of the specific mass shift in the measured state are also presented. With the use of Brueckner orbitals the value ?70 MHz was obtained in substantial agreement with the experimental result.     

Thermal stability and UV–Vis-NIR spectroscopy of a new erbium-doped fluorotellurite glass

A new transparent bulk glass from the system 76TeO₂?·?10ZnO?·?9.0PbO?·?1.0PbF₂?·?3.0Na₂O doped with Er³⁺ (TZPPN doped with Er³⁺) has been prepared using the conventional melt-quenching method. Results of differential thermal analysis (DTA) measurements indicate good thermal stability of this glass. The refractive indices at different wavelengths, the optical energy gap, the Sellmeier gap energy and the dispersion energy have been estimated. The Judd–Ofelt parameters, Ω _t (t?=?2,?4,?6) of Er³⁺ were evaluated from optical absorption spectra. Electric dipole, magnetic dipole type transition probabilities, spectroscopic quality factors, branching ratio and radiative lifetimes of several excited states of Er³⁺ have been predicted using intensity Judd–Ofelt parameters. The spectroscopic properties indicate that TZPPN glass doped with Er³⁺ is a promising candidate for laser applications and may be suitable for upconversion fibre optical devices.     

COMPLIS experiments: COllaboration for spectroscopy Measurements using a Pulsed Laser Ion Source

Laser spectroscopy measurements have been carried out on very neutron-deficient isotopes of Au, Pt and Ir, produced as daughter elements from a Hg ISOLDE beam. For these transitional region nuclides, the hyperfine structure (HFS) and isotope shift (IS) were measured by Resonance Ionization Spectroscopy (RIS). Magnetic moments μ, spectroscopic quadrupole moments Q_s and changes of the nuclear mean square charge radius δ〈r_c ²〉along isotopic series have been extracted. For some results, a detailed comparison with theoretical predictions is presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sulphur and oxygen isotopic characters of dissolved sulphate in groundwater from the Pleistocene aquifer in the southern Jordan Valley (Jericho area,Palestine)

Sulphate and chloride concentrations in the shallow Pleistocene aquifer systems in the lower Jordan valley area indicate a general trend of increasing salinity eastward and southward. This study was conducted in one of the important sub-basins feeding the Pleo–Pleistocene aquifer in the Jericho area in the southern part of the valley using S and O isotopes of dissolved sulphate. The results show that sulphate has mainly two contributions to the groundwater. One is the surface seepage, which is present as a salty leachate form with the positive δ³⁴S_sulphate values of primary gypsum in Lisan and Samara formations, and the second is the upwelling saline water which was in contact with a deep secondary gypsum, aragonites and salty rocks and rose up under heavy abstraction with depleted ³⁴S in sulphate and relatively high sulphate and chloride content. The latest was clearly shown in the Arab Project wells to the east that is undergoing a continuous heavy abstraction. The isotopic signatures of S and O in these wells to the east show that this depleted ³⁴S and highly concentrated sulphate might also indicate a dissolved sulphate originating from pyrite oxidation that results from the interaction with a pyrite-rich aquifer, which can well up with salty water under heavy abstraction and is oxidised in the upper aerobic shallow aquifer.     

Lifetime measurements,infrared and photoacoustic spectroscopy of NdP5O14

We have made a series of spectroscopic measurements to better understand the optical properties and concentration quenching characteristics of the stoichiometric laser material NdP₅O₁₄. The results of fluorescence lifetime measurements in the presence of different surface environments indicates that the surface condition affects the concentration quenching whereas lifetime measurements under applied uniaxial stress show that the presence of internal strains in the crystal is not significantly effective in fluorescence quenching. A comparison of the internal reflection spectrum with the normal infrared spectrum did not reveal any significant differences in the Nd³⁺ energy levels. Photoacoustic spectroscopy results proved difficult to interpret but appear to be consistent with the presence of surface quenching of excitons and indicate that the intrinsic quantum efficiency of Nd³⁺ ions in the pentaphosphate host in the absence of concentration quenching is approximately 0.90.     

Nuclear Radiation Detected Optical Pumping of neutron-deficient Hg isotopes

The extension of the Nuclear Radiation Detected Optical Pumping method to mass-separated samples of isotopes far off stability is presented for a series of light Hg isotopes produced at the ISOLDE facility at CERN. The isotope under investigation is transferred by an automatic transfer system into the optical pumping apparatus. Zeeman scanning of an isotopically pure Hg spectral lamp is used to reach energetic coincidence with the hyperfine structure components of the 6s ^{2 1} S ₀6s6p ³P₁,λ=2,537 Å resonance line of the investigated isotope and the Hg lamp. The orientation built up by optical pumping is monitored via the asymmetry or anisotropy of the nuclear radiation. Nuclear spins, magnetic moments, electric quadrupole moments and the isotope shifts are obtained for¹⁸¹Hg-¹⁹¹Hg using theβ asymmetry as detector. The extension of the method using theγ anisotropy is discussed and test measurements on¹⁹³Hg are presented. This paper describes the experimental procedure, results, and discussion are given in a following publication.     

Judd–Ofelt analysis and improvement of thermal and optical properties of tellurite glasses by adding P2O5

Er³⁺ and Er³⁺/Yb³⁺ co-doped tellurite glasses, suitable for developing optical fiber laser and amplifier, have been elaborated from the conventional melt-quenching method. Results of differential scanning calorimetry (DSC) measurements indicate a good thermal stability of tellurite glasses. The DSC measurements show an improvement of thermal stability of glass hosts after adding P₂O₅. Absorption spectrum from near infrared to visible was obtained and the Judd–Ofelt (J–O) intensity parameters (Ω₂, Ω₄, and Ω₆) were determined. Spontaneous emission probabilities of some relevant transitions, branching ratio, and radiative lifetimes of several excited states of Er³⁺ have been predicted using intensity J–O parameters. Absorption cross-section and calculated emission cross-section, using the McCumber method, for the ⁴I_13/2→⁴I_15/2 transition, were determined and compared for the doped and co-doped glasses. Energy transfer (ET) and effect of changing concentration of P₂O₅ and Yb³⁺ ions on spectroscopic properties were investigated. It was found that the addition of P₂O₅ can increase the symmetry of the Er³⁺ ion. As a consequence, PL lifetime becomes more longer.The spectroscopic properties and the efficient infrared luminescence indicate that Er³⁺ doped TeO₂–ZnO–Na₂O–Er₂O₃(TZNE) is a promising laser and amplifier materials and may be a potentially useful material for developing upconversion fiber optical devices.     

Four-nucleon pickup reaction on 12 ⩽ A ⩽ 94 nuclei

The differential cross sections for the (d, ⁶Li) reaction on targets of ¹²C, ¹⁶O, ²⁴Mg, ⁴⁰Ca, ⁵⁸Ni and ⁹⁴Mo have been measured at E_d = 54.2 MeV. The measured angular distributions have been analyzed by finite-range DWBA calculations, and spectroscopic factors for an α-cluster transfer have been extracted. In the DWBA analysis using an optical model with a phenomenological Woods-Saxon potential, the spin-orbit part of the deuteron optical potential played a significant role in reproducing the measured angular distributions but the spin-orbit part of the ⁶Li optical potential had a minor effect. Relative spectroscopic factors extracted from the present data were compared with theoretical predictions together with the results from the (p, pα) reaction. The relative spectroscopic factors for 1p-shell nuclei were in quantitative agreement with theoretical predictions. However, there were certain discrepancies between the spectroscopic factors extracted from the (d, ⁶Li) reaction and those from the (p, pα) reaction, and the discrepancies increased with target mass number.     

On-line nuclear orientation of the deformed neutron-deficient Eu,Sm and Pm isotopes

Low-temperature nuclear orientation measurements made on-line at the SERC Daresbury Laboratory on^142m Eu,^141m Sm, and¹⁴¹Pm, with known magnetic dipole moments, have yielded the magnitude of the hyperfine fields of these isotopes in an iron host lattice. Thus measurements for the isotopes^{139, 138}Eu,^139m Sm, and¹³⁸Pm yielded values for the respective magnetic moments. Limits on the thermal relaxation times of Eu and Sm isotopes in Fe were also deduced. The results for¹³⁸Eu appear to contradict the earlier πh_11/2⊗νh_11/2 ground-state configuration assignment.     

First Measurement of the Nuclear Charge Radii of Short-Lived Lithium Isotopes

A novel method for the determination of nuclear charge radii of lithium isotopes is presented. Precise laser spectroscopic measurements of the isotope shift in the lithium 2s → 3s transition are combined with highly accurate atomic physics calculation of the mass dependent isotope shift to extract the charge-distribution-sensitive information. This approach has been used to determine the charge radii of ^8,9Li for the first time.