Deuterated H3+ as a probe of isotope fractionation in star-forming regions

Observations of molecular D/H ratios in the interstellar medium are used to probe the physical conditions, such as temperature, ionization fraction and the importance of gas-grain reactions. In cold, dense regions, such as cores which are collapsing to form stars, the level of deuterium fractionation depends on the conversion of H3+ into its deuterated isotopologues (H2D+, D2H+ and D3+). The relative abundances of these molecules uniquely probe the centres of these cores where other, heavier, species have frozen onto dust grains. We present models of the deuterium chemistry close to the centre of a pre-stellar core, in the last stage before the star forms, showing the dependence of the observable molecular D/H ratios on the physical parameters and rate coefficients that are assumed. We compare model predictions with the latest observations of these regions.     

Using H3+ and H2D+ as probes of star-forming regions

The H3+ and H2D+ ions are important probes of the physical and chemical conditions in regions of the interstellar medium where new stars are forming. This paper reviews how observations of these species and of heavier ions such as HCO+ and H3O+ can be used to derive chemical and kinematic properties of nearby pre-stellar cores and the cosmic ray ionization rate towards more distant regions of high-mass star formation. Future prospects in the field are outlined at the end.     

Dissociative recombination of cold H3+ and its interstellar implications

H3+ plays a key role in interstellar chemistry as the initiator of ion-molecule chemistry. The amount of H3+ observed in dense interstellar clouds is consistent with expectations, but the large abundance of H3+ seen in diffuse clouds is not easily explained by simple chemical models. A crucial parameter in predicting the abundance of H3+ in diffuse clouds is the rate constant for dissociative recombination (DR) with electrons. The value of this constant has been very controversial, because different experimental techniques have yielded very different results, perhaps owing to varying degrees of rotational and vibrational excitation of the H3+ ions. If the value of this rate constant under interstellar conditions were much lower than usually assumed, the large H3+ abundance could be easily explained. In an attempt to pin down this crucial rate constant, we have performed DR measurements at the CRYRING ion storage ring in Stockholm, using a supersonic expansion ion source to produce rotationally cold H3+ ions. These measurements suggest that the DR rate constant in diffuse clouds is not much lower than usually assumed and that the abundant H3+ must be due to either a low electron fraction or a high ionization rate.     

Deuterium enhancement in H3+ in pre-stellar cores

Deuterium enhancement of monodeuterated species has been recognized for more than 30 years as a result of chemical fractionation that results from the difference in zero-point energies of deuterated and hydrogenated molecules. The key reaction is the deuteron exchange in the reaction between HD, the reservoir of deuterium in dark interstellar clouds, and the H3+ molecular ion, leading to the production of H2D+ molecule, and the low temperature in dark interstellar clouds favours this production. Furthermore, the presence of multiply deuterated species have incited our group to proceed further and consider the subsequent reaction of H2D+ with HD, leading to D2H+, which can further react with HD to produce D3+. In pre-stellar cores, where CO was found to be depleted, this production should be increased as CO would normally destroy H3+. The first model including D2H+ and D3+ predicted that these molecules should be as abundant as H2D+. The first detection of the D2H+ was made possible by the recent laboratory measurement for the frequency of the fundamental line of para-D2H+. Here, we present observations of H2D+ and D2H+ towards a sample of dark clouds and pre-stellar cores and show how the distribution of ortho-H2D+ (1(1,0)-1(1,1)) can trace the deuterium factory in pre-stellar cores. We also present how future instrumentation will improve our knowledge concerning the deuterium enhancement of H3+.     

Submillimetre-wave lines of H2D+ and D2H+ as probes into chemistry in cold dark clouds

We discuss past and recent progress of our continuing project of submillimetre-wave spectroscopic investigations of H2D+ and D2H+. Three new lines of H2D+ in the 2.5-3.5 THz range are measured with a tunable far-infrared laser system. Since these molecules are very light asymmetric molecules, analysis based on a conventional effective Hamiltonian is not very useful in predicting the transition frequencies to the accuracy of the order of several MHz or better. In this respect, any addition of new accurate measurements of transition frequencies is important. In this paper, some discussions will be made on H5+ and its deuterated species as probable interstellar species in cold dark clouds. In particular, D3+, which is predicted to be abundant in cold dark clouds, can be (indirectly) detected by observing D3+ x H2.     

Monitoring the speciation of aqueous free chlorine from pH 1 to 12 with Raman spectroscopy to determine the identity of the potent low-pH oxidant

The speciation of aqueous free chlorine above pH 5 is a well-understood equilibrium of H2O + HOCl <==> OCl- + H3O+ with a pKa of 7.5. However, the identity of another very potent oxidant present at low pH (below 5) has been attributed by some researchers to Cl2(aq) and by others to H2OCl+. We have conducted a series of experiments designed to ascertain which of these two species is correct. First, using Raman spectroscopy, we found that an equilibrium of H2O + H2OCl+ <==> HOCl + H3O+ is unlikely because the "apparent pKa" increases monotonically from 1.25 to 2.11 as the analytical concentration is increased from 6.6 to 26.2 mM. Second, we found that significantly reducing the chloride ion concentration changed the Raman spectrum and also dramatically reduced the oxidation potency of the low-pH solution (as compared to solutions at the same pH that contained equimolar concentrations of Cl- and HOCl). The chloride ion concentration was not expected to impact an equilibrium of H2O + H2OCl+ <==> HOCl + H3O+, if it existed. These observations supported the following equilibrium as pH is decreased: Cl2(aq) + 2H2O <==> HOCl + Cl- + H3O+. The concentration-based equilibrium constant was estimated to be approximately 2.56 x 10(-4) M2 in solutions whose ionic strengths were approximately 0.01 M. The oxidative potency of the species in low pH solutions was investigated by monitoring the oxidation of secondary alcohols to ketones. These and other results reported here argue strongly that Cl2(aq) is the correct form of the potent low-pH oxidant in aqueous free-chlorine solutions.     

H3+ towards and within the Galactic centre

High-resolution spectroscopy of bright infrared sources in the centre of the Galaxy has resulted in the detection of H3+ in a remarkable array of dense and diffuse clouds along the 8000 parsec long line of sight, at a wide range of distances from the centre. Most prominent among these is a previously undetected, but very large amount of warm (T approximately 250 K) and diffuse (n approximately 100 cm2) gas within a few hundred parsecs of the centre. The key to understanding the environment of the H3+ in this region is an H3+ absorption line at 3.53 microm from the metastable (3,3) rotational level, which has not been detected in dense or diffuse clouds outside of the Galactic centre (GC). We have used spectroscopy of this line along with other lines of H3+ and CO to characterize all of the clouds along the line of sight to the GC. The high abundance of H3+ in the central few hundred parsecs implies an ionization rate there that is several times larger than estimated for diffuse clouds outside the GC, and nearly two orders of magnitude greater than originally predicted for diffuse clouds.     

Impurity-Helium Solids: Chemistry and Physics at 1.5 K

Impurity-helium solids are porous gel-like materials held together by Van der Waals forces. They consist of impurity atoms, molecules or clusters of atoms and molecules, each surrounded by very thin layers of solid helium. Impurities studied include neon, krypton, and molecular and atomic nitrogen, hydrogen and deuterium. The pore sizes and cluster sizes in impurity-helium solids are determined by ugtrasound attenuation and X-ray diffraction. The ESR technique is employed to study atomic impurities. The tunnelling exchange chemical reactions D+H₂→HD+D and D+HD→D₂+H are observed. Large concentrations of atomic hydrogen (～8?10¹⁷ per cm³) are produced in these reactions.     

Simultaneous determination of dissolved gases and moisture in mineral insulating oils by static headspace gas chromatography with helium photoionization pulsed discharge detection

This paper presents the development of a static headspace capillary gas chromatographic method (HS-GC) for simultaneously determining dissolved gases (H2, O2, N2, CO, CO2, CH4, C2H6, C2H4, C2H2, C3H8) and moisture from a unique 15-mL mineral oil sample. A headspace sampler device is used to equilibrate the sample species in a two-phase system under controlled temperature and agitation conditions. A portion of the equilibrated species is then automatically split-injected into two chromatographic channels mounted on the same GC for their separation. The hydrocarbons and the lighter gases are separated on the first channel by a GS-Q column coupled with a MolSieve 5-A column via a bypass valve, while the moisture is separated on the second channel using a Stabilwax column. The analytes are detected by using two universal pulsed-discharge helium ionization detectors (PDHID). The performance of the method was established using equilibrated vials containing known amounts of gas mixture, water, and blank oil. The signal is linear over the concentration ranges normally found for samples collected from open-breathing power transformers. Determination sensitivity varies with the nature of the species considered with values as high as 21 500 A x 10(-9) s (microg/ g)(-1) for H2O, 46-216 A x 10(-9) s (microL/L)(-1) for the hydrocarbons and carbon oxides, and as low as 8-21 A x 10(-9) s (microL/L)(-1) for the O2 and N2 permanent gases. The detection limit of the method is between 0.08 and 6 microL/L for the dissolved gases, except for O2, N2, and CO2, where higher values are observed due to air intrusion during sampler operations, and 0.1 microg/g for the dissolved water. Ten consecutive measurements in the low and high levels of the calibration curves have shown a precision better than 12% and 6%, respectively, in all cases. A comparison study between the HS-GC method and the ASTM standard procedures on 31 field samples showed a very good agreement of the results. The advantages of configuring the arrangement with two PDHID over the conventional flame ionization and thermal conductivity detectors were clearly demonstrated.     

Direct determination of dibutyl and monobutyl phosphate in a tributyl phosphate/nitric aqueous-phase system by electrospray mass spectrometry

Electrospray ionization mass spectrometry was tested for its potential use in the quantification of monobutyl phosphate (H2MBP) and dibutyl phosphate (HDBP), two degradation products of tributyl phosphate (TBP), the extractant used in the nuclear fuel reprocessing known as the PUREX process. Detection and quantification of these phosphate esters by electrospray in positive and negative ionization mode are reported in this study. This fast and reliable method, which does not require any preliminary sample extraction, appears to be very attractive for process control. Negative ionization mode gave abundant [M - H]- ions for both HDBP and H2MBP products. Thus, the concentration of H2MBP between 0.1 and 10 g/L in concentrated aqueous nitrate solutions can be precisely determined. Moreover, the concentration of HDBP up to 1 g/L in a TBP matrix was evaluated in this mode. For HDBP concentrations below 1 g/L, detection in the positive ionization mode appeared to be attractive. TBP and HDBP cluster detection allowed quantitative HDBP determination. Indeed, small amounts of HDBP in commercial TBP (60 mg/L) could be directly quantified using the specific [2TBP, HDBP + H]+ cluster at m/z 743.     

Spectro-imaging observations of H3+ on Jupiter

Narrow-band filter, high-spectral-resolution (0.2 cm(-1)) spectro-imaging infrared observations of Jupiter's auroral zones, acquired in October 1999 and October 2000 with the FTS/BEAR instrument at the Canada-France-Hawaii Telescope, have provided maps of the emission from the H2 S1(1) quadrupole line and several H3+ lines. H2 and H3+ emissions appear to be morphologically different, especially in the north, where the latter notably exhibits a 'hot spot' near lambdaIII = 150-170 degrees System III longitude. The spectra include a total of 14 H3+ lines, including two hot lines from the 3v2-v2 band, detected on Jupiter for the first time. They can be used to determine H3+ column densities, rotational (Trot) and vibrational (Tvib) temperatures. We find the mean Tvib of the v2 = 3 state to be lower (960 +/- 50 K) than the mean Trot in v2 = 2 (1170 +/- 75 K), indicating an underpopulation of the v2 = 3 level with respect to local thermodynamical equilibrium. Rotational temperatures and associated column densities are generally higher and lower, respectively, than inferred previously from v2 observations. These features can be explained by the combination of both a large positive temperature gradient in the sub-microbar auroral atmosphere and non-local thermal equilibrium effects affecting preferentially hot and combination bands. Spatial variations in line intensities are mostly owing to correlated variations in the H3+ column densities. The thermostatic role played by H3+ at ionospheric levels may provide an explanation. The exception is the northern 'hot spot', which exhibits a Tvib about 250 K higher than other regions.     

Determination of the the H3 factor in hydrogen isotope ratio monitoring mass spectrometry

The H3 factor, K, is a parameter required in high-precision, mass spectrometric analyses of hydrogen isotopic abundances. When H2 is used as the sample gas, R* = R - Ki2, where R* is the true HD/H2 ratio, R is the observed (mass 3)/(mass 2) ion-current ratio, and i2 is the ion current at mass 2. Four different methods for the determination of K were defined and tested under conditions characteristic of isotope ratio monitoring systems. Three of these were peak-based. The fourth employed steady flows of H2 from a conventional inlet system. Results obtained using the latter method were more precise (standard deviation of K = 0.1 versus approximately 0.6 ppm mV(-1) for the peak-based methods). However, use of the resulting values of K for correction of isotope ratio monitoring GC/MS results led to systematic errors as large as 9 per thousand, whereas use of the peak-based values led to no systematic errors. Values of K were only weakly dependent on the pressure of He, declining approximately 5% for each 10-fold increase in P(He). Small variations in partial pressures of H2O and CH4, potential contaminants under isotope ratio monitoring conditions, had no significant effect on values of K.     

Novel active heterogeneous Fenton system based on Fe3-xMxO4 (Fe, Co, Mn, Ni): the role of M2+ species on the reactivity towards H2O2 reactions

In this work, the effect of incorporation of M2+ species, i.e. Co2+, Mn2+ and Ni2+, into the magnetite structure to increase the reactivity towards H2O2 reactions was investigated. The following magnetites Fe3-xMnxO4, Fe3-xCoxO4 and Fe3-xNixO4 and the iron oxides Fe3O4, gamma-Fe2O3 and alpha-Fe2O3 were prepared and characterized by M?ssbauer spectroscopy, XRD, BET surface area, magnetization and chemical analyses. The obtained results showed that the M2+ species at the octahedral site in the magnetite strongly affects the reactivity towards H2O2, i.e. (i) the peroxide decomposition to O2 and (ii) the oxidation of organic molecules, such as the dye methylene blue and chlorobenzene in aqueous medium. Experiments with maghemite, gamma-Fe2O3 and hematite, alpha-Fe2O3, showed very low activities compared to Fe3O4, suggesting that the presence of Fe2+ in the oxide plays an important role for the activation of H2O2. The presence of Co or Mn in the magnetite structure produced a remarkable increase in the reactivity, whereas Ni inhibited the H2O2 reactions. The obtained results suggest a surface initiated reaction involving Msurf2+ (Fe, Co or Mn), producing HO radicals, which can lead to two competitive reactions, i.e. the decomposition of H2O2 or the oxidation of organics present in the aqueous medium. The unique effect of Co and Mn is discussed in terms of the thermodynamically favorable Cosurf3+ and Mnsurf3+ reduction by Femagnetite2+ regenerating the active species M2+.     

Analysis of saturated hydrocarbons by using chemical ionization combined with laser-induced acoustic desorption/Fourier transform ion cyclotron resonance mass spectrometry

Laser-induced acoustic desorption (LIAD), combined with chemical ionization by the cyclopentadienyl cobalt radical cation (CpCo.+), is demonstrated to facilitate the analysis of saturated hydrocarbons by Fourier transform ion cyclotron resonance mass spectrometry. The LIAD/CpCo.+ method produces unique pseudomolecular ions for alkanes from C(24)H(50) to C(50)H(102). These alkanes were tested individually and in artificial mixtures of up to seven components. Only one product ion, [R + CpCo - 2H(2)].+, was detected for each alkane (R). The product ions' relative abundances correspond to the relative molar concentration of each alkane in mixtures. These findings provide a solid groundwork for the future application of this method for hydrocarbon polymer analyses.     

Evaluation of electrospray mass spectrometry as a technique for quantitative analysis of kinetically labile solution species

The extent that a kinetically labile equilibrium reaction was perturbed by passage through the electrospray ion source has been measured. The reaction studied was strontium ion chelation by EDTA (Sr(2+) + Y(4)(-) ? SrY(2)(-)) in 100% aqueous solutions. The forward reaction rate is very fast (10(9) M(-)(1) s(-)(1)) and the reverse rate is very slow (10(0) s(-)(1)) relative to the time scale of the ES process (～10(-2) s). The SrY(2-) detected with the mass spectrometer were expected to be representative of thermodynamic equilibrium within the droplets, but the position of the equilibrium shifted to the right relative to the solution equilibrium position. Given the current status of understanding of the ion generation process in the electrospray ion source, the degree that the [Sr(2+)] changed due to passage through this ion source was smaller than expected, which is fortuitous with respect to the quantitation of such species. The pH of each calibration set determined the fraction of strontium that was uncomplexed in solution. The equilibrium shift induced by passage through the ion source was constant for solutions at constant pH but differed for solutions at different pH. Decreasing the solution pH generated smaller equilibrium shifts as measured by the change in the [Sr(2+)]. In solutions with free Sr(2+) and excess EDTA at equilibrium, the free [Sr(2+)] decreased by ～100 and ～10% in solutions at pH 5.85 and 4.98, respectively. Quantitation of kinetically labile species in complex, multicomponent systems will be straightforward with ES-MS, provided all species involved in the equilibria can be identified and monitored.     

Quantification of nitryl chloride at part per trillion mixing ratios by thermal dissociation cavity ring-down spectroscopy

Nitryl chloride (ClNO(2)) is an important nocturnal nitrogen oxide reservoir species in the troposphere. Here, we report a novel method, thermal dissociation cavity ring-down spectroscopy (TD-CRDS), to quantify ClNO(2) mixing ratios with tens of parts-per-trillion by volume (pptv) sensitivity. The mixing ratios of ClNO(2) are determined by blue diode laser CRDS of NO(2), produced from quantitative thermal dissociation of ClNO(2) in an inlet heated to 450 °C, relative to NO(2) observed in an unheated reference channel. ClNO(2) was generated by passing Cl(2) gas over a slurry containing a 1:10 mixture of NaNO(2) and NaCl. The TD-CRDS response was evaluated using parallel measurements of ClNO(2) by chemical ionization mass spectrometry (CIMS) using I(-) as the reagent ion and NO(y) (= NO + NO(2) + HNO(3) + ΣRO(2)NO(2) + ΣRONO(2) + HONO + 2N(2)O(5) + ClNO(2) + ...) chemiluminescence (CL). The linear dynamic range extends from the detection limit of 20 pptv (1 σ, 1 min) to 30 parts-per-billion by volume (ppbv), the highest mixing ratio tested. The ClNO(2) TD profile overlaps with those of alkyl nitrates, which has implications for nocturnal measurements of total alkyl nitrate (ΣAN = ΣRONO(2)) abundances by thermal dissociation (with detection as NO(2)) in ambient air.     

Comparison of mass spectral techniques using organic peroxides related to artemisinin

The mass spectra of three peroxides related to artemisinin (1) are compared in nine different ionization modes. Ion trap mass spectrometry (MS/MS) spectra reveal numerous pathways for the electron impact (EI) decompositions. In the EI mode, the best spectra are obtained by using the ion trap mass spectrometer at low temperatures. Loss of oxygen is observed with the other EI spectrometers, suggesting catalytic decomposition in the ion source. Methane positive and negative chemical ionization (CI) spectra show considerable fragmentation, while isobutane CI spectra show only (M + H)+ for 1 and (M + H - H2O)+ for dihydroartemisinin (2) and (3). An unusually abundant (2M + H)+ is observed for 1 in both positive-ion plasma desorption and fast atom bombardment mass spectra.     

Development of a chemical ionization ion trap mass spectrometric method for trace level determination of molecular halogens

An ion trap mass spectrometric technique using negative ion chemical ionization has been developed for the quantitative determination of the molecular halogen species Br(2), Cl(2), and BrCl. The technique utilizes NO(2)(-) as a chemical ionization reagent in an electron-transfer reaction to form the corresponding molecular anions of the halogen species, lending excellent selectivity to the measurement. Reaction rate experiments performed in the ion trap yield a rate constant for Br(2) + NO(2)(-) --> Br(2)(-) + NO(2) of (1.4 +/- 0.6) x 10(-)(9) cm(3) molecule(-)(1) s(-)(1), determined relative to published data for Cl(2) + NO(2)(-) --> Cl(2)(-) + NO(2). This paper describes a mass spectrometer pinhole inlet design and cryogenic preconcentration system for detection of the molecular halogens at atmospherically relevant concentrations. Linear calibration curves were obtained for Cl(2) and Br(2) over 3 orders of magnitude and indicate limits of detection of 50 and 8 pmol for 3.8- and 5.1-L samples, respectively, corresponding to 220 and 50 parts per trillion (mole/mole). Quantitation is based on the total signal at m/z values of 70, 72, and 74 for Cl(2) and 158, 160, and 162 for Br(2). The effects of water vapor on the cryogenic preconcentration step are quantitatively assessed.     

An equilibrium partitioning model for predicting response to host-guest complexation in electrospray ionization mass spectrometry

While electrospray ionization mass spectrometry (ESI-MS) has become a powerful technique for analyzing many types of host-guest complexation, questions remain as to just how accurately ion abundances generated by ESI reflect the true distribution of species at equilibrium in solution. To better understand this relationship, an equilibrium partitioning model was developed to explain the various interactions that dictate how much of a particular host-guest complex is transferred from solution into the gas phase in the ESI process. By evaluating the simultaneous equilibria of the complexation reaction and the partitioning of species between the surface and interior of the ESI droplets, one can estimate the ion abundances generated. The predictions of this new model were evaluated and experimentally confirmed through the analysis of the complexes of 18-crown-6 with alkali metal cations in an ESI quadrupole ion trap mass spectrometer, and it was determined that binding constants alone may not give accurate predictions about the observed ESI-MS response to different host-guest complexes.     

Electrochemical studies of the interaction of metal chelates with DNA. 4. Voltammetric and electrogenerated chemiluminescent studies of the interaction of tris(2,2'-bipyridine)osmium(II) with DNA

Cyclic voltammetric and electrogenerated chemiluminescent data were used to study the binding of tris(2,2'-bipyridine)-osmium(II), Os(bpy)3(2+), an electrostatic binder, to calf thymus DNA. The oxidized form of the osmium complex, Os(bpy)3(3+), has a stronger association to DNA than the reduced form, Os(bpy)3(2+), as indicated by the negative shift of E0' of the CV waves (K3+/K2+ = 3.35). The calculated binding constant, K2+, and binding site size, s, for the Os(byp)3(2+)-DNA system depended slightly on whether a mobile or a static equilibrium was assumed. In 10 mM NaCl, 10 mM Tris pH 7, K2+ = (7.3 +/- 0.4) x 10(3) M-1 and s = 3 base pairs (mobile) and K2+ = (5.0 +/- 0.2) x 10(3) M-1 and s = 3 base pairs (static). Electrogenerated chemiluminescence (ECL) was produced upon oxidation of Os(bpy)3(2+) at a Pt electrode in a solution containing 10 mM C2O4(2-) and 10 mM phosphate at pH 5. Addition of DNA caused a decrease in the emission intensity (I); a plot of I vs relative DNA concentration yielded K2+ = (6.5 +/- 0.5) x 10(3) M-1 and s = 3 base pairs. The osmium complex produced ECL when bound to the DNA molecule with an efficiency of 30% that of the unbound chelate.