Geochemistry and resonance ionization of platinum-group elements

Experimental studies were conducted with the goals of 1) determining the origin of Pt- group element (PGE) alloys and associated mineral assemblages in refractory inclusions from meteorites and 2) developing a new ultrasensitive method for the in situ chemical and isotopic analysis of PGE. A general review of the geochemistry and cosmochemistry of the PGE is given, and specific research contributions are presented within the context of this broad framework.

An important step toward understanding the cosmochemistry of the PGE is the determination of the origin of POE-rich metallic phases (most commonly εRu-Fe) that are found in Ca, AJ-rich refractory inclusions (CAI) in C3V meteorites. These metals occur along with γNi-Fe metals, Ni-Fe sulfides and Fe oxides in multiphase opaque assemblages. Laboratory experiments were used to show that the mineral assemblages and textures observed in opaque assemblages could be produced by sulfidation and oxidation of once homogeneous Ni-Fe-PGE metals. Phase equilibria, partitioning and diffusion kinetics were studied in the Ni-Fe-Ru system in order to quantify the conditions of opaque assemblage formation. Phase boundaries and tie lines in the Ni-Fe-Ru system were determined at 1273, 1073 and 873K using an experimental technique that allowed the investigation of a large portion of the Ni-Fe-Ru system with a single experiment at each temperature by establishing a concentration gradient within which local equilibrium between coexisting phases was maintained. A wide miscibility gap was found to be present at each temperature, separating a hexagonal close-packed εRu-Fe phase from a face-centered cubic γNi-Fe phase. Phase equilibria determined here for the Ni-Fe-Ru system, and phase equilibria from the literature for the Ni-Fe-S and Ni-Fe-O systems, were compared with analyses of minerals from opaque assemblages to estimate the temperature and chemical conditions of opaque assemblage formation. It was determined that opaque assemblages equilibrated at a temperature of ~770K, a sulfur fugacity 10 times higher than an equilibrium solar gas, and an oxygen fugacity 10⁶ times higher than an equilibrium solar gas.

Diffusion rates between -γNi-Fe and εRu-Fe metal play a critical role in determining the time (with respect to CAI petrogenesis) and duration of the opaque assemblage equilibration process. The diffusion coefficient for Ru in Ni (D^Ru_Ni) was determined as an analog for the Ni-Fe-Ru system by the thin-film diffusion method in the temperature range of 1073 to 1673K and is given by the expression:

D^Ru_Ni (cm² sec^-1) = 5.0(±0.7) x 10^-3 exp(-2.3(±0.1) x 10¹² erg mole^-1/RT) where R is the gas constant and T is the temperature in K. Based on the rates of dissolution and exsolution of metallic phases in the Ni-Fe-Ru system it is suggested that opaque assemblages equilibrated after the melting and crystallization of host CAI during a metamorphic event of ≥ 10³ years duration. It is inferred that opaque assemblages originated as immiscible metallic liquid droplets in the CAI silicate liquid. The bulk compositions of PGE in these precursor alloys reflects an early stage of condensation from the solar nebula and the partitioning of V between the precursor alloys and CAI silicate liquid reflects the reducing nebular conditions under which CAI were melted. The individual mineral phases now observed in opaque assemblages do not preserve an independent history prior to CAI melting and crystallization, but instead provide important information on the post-accretionary history of C3V meteorites and allow the quantification of the temperature, sulfur fugacity and oxygen fugacity of cooling planetary environments. This contrasts with previous models that called upon the formation of opaque assemblages by aggregation of phases that formed independently under highly variable conditions in the solar nebula prior to the crystallization of CAI.

Analytical studies were carried out on PGE-rich phases from meteorites and the products of synthetic experiments using traditional electron microprobe x-ray analytical techniques. The concentrations of PGE in common minerals from meteorites and terrestrial rocks are far below the ~100 ppm detection limit of the electron microprobe. This has limited the scope of analytical studies to the very few cases where PGE are unusually enriched. To study the distribution of PGE in common minerals will require an in situ analytical technique with much lower detection limits than any methods currently in use. To overcome this limitation, resonance ionization of sputtered atoms was investigated for use as an ultrasensitive in situ analytical technique for the analysis of PGE. The mass spectrometric analysis of Os and Re was investigated using a pulsed primary Ar⁺ ion beam to provide sputtered atoms for resonance ionization mass spectrometry. An ionization scheme for Os that utilizes three resonant energy levels (including an autoionizing energy level) was investigated and found to have superior sensitivity and selectivity compared to nonresonant and one and two energy level resonant ionization schemes. An elemental selectivity for Os over Re of ≥ 10³ was demonstrated. It was found that detuning the ionizing laser from the autoionizing energy level to an arbitrary region in the ionization continuum resulted in a five-fold decrease in signal intensity and a ten-fold decrease in elemental selectivity. Osmium concentrations in synthetic metals and iron meteorites were measured to demonstrate the analytical capabilities of the technique. A linear correlation between Os⁺ signal intensity and the known Os concentration was observed over a range of nearly 10⁴ in Os concentration with an accuracy of ~ ±10%, a millimum detection limit of 7 parts per billion atomic, and a useful yield of 1%. Resonance ionization of sputtered atoms samples the dominant neutral-fraction of sputtered atoms and utilizes multiphoton resonance ionization to achieve high sensitivity and to eliminate atomic and molecular interferences. Matrix effects should be small compared to secondary ion mass spectrometry because ionization occurs in the gas phase and is largely independent of the physical properties of the matrix material. Resonance ionization of sputtered atoms can be applied to in situ chemical analysis of most high ionization potential elements (including all of the PGE) in a wide range of natural and synthetic materials. The high useful yield and elemental selectivity of this method should eventually allow the in situ measurement of Os isotope ratios in some natural samples and in sample extracts enriched in PGE by fire assay fusion.

Phase equilibria and diffusion experiments have provided the basis for a reinterpretation of the origin of opaque assemblages in CAI and have yielded quantitative information on conditions in the primitive solar nebula and cooling planetary environments. Development of the method of resonance ionization of sputtered atoms for the analysis of Os has shown that this technique has wide applications in geochemistry and will for the first time allow in situ studies of the distribution of PGE at the low concentration levels at which they occur in common minerals.

Stopping power of gases for heavy ions

Pulse-height and time-of-flight methods have been used to measure the electronic stopping cross sections for projectiles of ¹²C, ¹⁶O, ¹⁹F, ²³Na, ²⁴Mg, and ²⁷Al, slowing in helium, neon, argon, krypton, and xenon. The ion energies were in the range 185 keV ≤ E ≤ 2560 keV.

A semiempirical calculation of the electronic stopping cross section for projectiles with atomic numbers between 6 and 13 passing through the inert gases has been performed using a modification of the Firsov model. Using Hartree-Slater-Fock orbitals, and summing over the losses for the individual charge states of the projectiles, good agreement has been obtained with the experimental data. The main features of the stopping cross section seen in the data, such as the Z₁ oscillation and the variation of the velocity dependence on Z₁ and Z₂, are present in the calculation. The inclusion of a modified form of the Bethe-Bloch formula as an additional term allows the increase of the velocity dependence for projectile velocities above v_o to be reproduced in the calculation.

Application of microwave diagnostics to copper chloride and carbon dioxide lasers

Part A

A problem restricting the development of the CuCl laser has been the decrease in output power with increases of tube temperature above 400°C. At that temperature the CuCl vapor pressure is about .1 torr. This is a small fraction of the buffer gas pressure (He at 10 torr).

The aim of the project was to measure the peak radiation temperature (assumed related to the mean energy of electrons) in the laser discharge as a function of the tube temperature. A 24 gHz gated microwave radiometer was used.

It was found that at the tube temperatures at which the output power began to deteriorate, the electron radiation temperature showed a sharp increase (compared with radiation temperature in pure buffer).

Using the above result, we have postulated that this sudden increase is a result of Penning ionization of the Cu atoms. As a consequence of this process the number of Cu atoms available for lasing decrease.

PART B

The aim of the project was to study the dissociation of CO₂ in the glow discharge of flowing CO₂ lasers.

A TM₀₁₁ microwave (3 gHz) cavity was used to measure the radially averaged electron density n_e and the electron-neutral collision frequency in the laser discharge. An estimate of the electric field is made from these two measurements. A gas chromatograph was used to measure the chemical composition of the gases after going through the discharge. This instrument was checked against a mass spectrometer for accuracy and sensitivity.

Several typical laser mixtures were .used: CO₂-N₂-He (1,3,16), (1,3,0), (1,0,16), (1,2,10), (1,2,0), (1,0,10), (2,3,15), (2,3,0), (2,0,15), (1,3,16)+ H₂O and pure CO₂. Results show that for the conditions studied the dissociation as a function of the electron density is uniquely determined by the STP partial flow rate of CO₂, regardless of the amount of N₂ and/or He present. The presence of water vapor in the discharge decreased the degree of dissociation.

A simple theoretical model was developed using thermodynamic equilibrium. The electrons were replaced in the calculations by a distributed heat source.

The results are analyzed with a simple kinetic model.

Oxidation of Volatile Organic Compounds in Aqueous Solution and at the Air-water Interface of Aqueous Microdroplets

Isoprene (ISO),the most abundant non-methane VOC, is the major contributor to secondary organic aerosols (SOA) formation. The mechanisms involved in such transformation, however, are not fully understood. Current mechanisms, which are based on the oxidation of ISO in the gas-phase, underestimate SOA yields. The heightened awareness that ISO is only partially processed in the gas-phase has turned attention to heterogeneous processes as alternative pathways toward SOA.

During my research project, I investigated the photochemical oxidation of isoprene in bulk water. Below, I will report on the λ > 305 nm photolysis of H₂O₂ in dilute ISO solutions. This process yields C₁₀H₁₅OH species as primary products, whose formation both requires and is inhibited by O₂. Several isomers of C₁₀H₁₅OH were resolved by reverse-phase high-performance liquid chromatography and detected as MH⁺ (m/z = 153) and MH⁺-18 (m/z = 135) signals by electrospray ionization mass spectrometry. This finding is consistent with the addition of ·OH to ISO, followed by HO-ISO· reactions with ISO (in competition with O₂) leading to second generation HO(ISO)₂· radicals that terminate as C₁₀H₁₅OH via β-H abstraction by O₂.

It is not generally realized that chemistry on the surface of water cannot be deduced, extrapolated or translated to those in bulk gas and liquid phases. The water density drops a thousand-fold within a few Angstroms through the gas-liquid interfacial region and therefore hydrophobic VOCs such as ISO will likely remain in these relatively 'dry' interfacial water layers rather than proceed into bulk water. In previous experiments from our laboratory, it was found that gas-phase olefins can be protonated on the surface of pH < 4 water. This phenomenon increases the residence time of gases at the interface, an event that makes them increasingly susceptible to interaction with gaseous atmospheric oxidants such as ozone and hydroxyl radicals.

In order to test this hypothesis, I carried out experiments in which ISO(g) collides with the surface of aqueous microdroplets of various compositions. Herein I report that ISO(g) is oxidized into soluble species via Fenton chemistry on the surface of aqueous Fe(II)Cl₂ solutions simultaneously exposed to H₂O₂(g). Monomer and oligomeric species (ISO)1-8H⁺ were detected via online electrospray ionization mass spectrometry (ESI-MS) on the surface of pH ~ 2 water, and were then oxidized into a suite of products whose combined yields exceed ~ 5% of (ISO)1-8H⁺. MS/MS analysis revealed that products mainly consisted of alcohols, ketones, epoxides and acids. Our experiments demonstrated that olefins in ambient air may be oxidized upon impact on the surface of Fe-containing aqueous acidic media, such as those of typical to tropospheric aerosols.

Related experiments involving the reaction of ISO(g) with ·OH radicals from the photolysis of dissolved H₂O₂ were also carried out to test the surface oxidation of ISO(g) by photolyzing H₂O₂(aq) at 266 nm at various pH. The products were analyzed via online electrospray ionization mass spectrometry. Similar to our Fenton experiments, we detected (ISO)1-7H⁺ at pH < 4, and new m/z⁺ = 271 and m/z^- = 76 products at pH > 5.

Experimental chemical physics of droplets and clusters

Time-of-flight measurements of energetic He atoms, field ionization of cryogenic liquid helium clusters, and time-of-flight and REMPI spectroscopy of radical salt clusters were investigated experimentally. The excited He atoms were generated in a corona discharge. Two strong neutral peaks were observed, accompanied by a prompt photon peak and a charged peak. All peaks were correlated with the pulsing of the discharge. The neutral hyperthermal and metastable atoms were formed by different mechanisms at different stages of the corona discharge. Positively charged helium droplets were produced by ionization of liquid helium in an electrostatic spraying experiment. The fluid emerging from a thin glass capillary was ionized by a high voltage applied to a needle inside the capillary. Fine droplets (less than 10 µm in diameter) were produced in showers with currents as high as 0.4 µA at 2-4 kV. The high currents resulting from field ionization in helium and the low surface tension of He I, led to charge densities that greatly exceeded the Rayleigh limit, thus resulting in coulombic explosion of the liquid. In contrast, liquid nitrogen formed a well-defined Taylor cone with droplets having diameters comparable to the jet (≈100 µm) at lower currents (10 nA) and higher voltages (8 kV). The metal-halide clusters of calcium and chlorine were generated by laser ablation of calcium metal in a Ar/CCl₄ expansion. A visible spectrum of the Ca₂Cl₃ cluster was observed from 651 to 630 nm by 1 +1' REMPI. The spectra were composed of a strong origin band at 15 350.8 cm^-1 and several weak vibronic bands. Density functional calculations predicted three minimum energy isomers. The spectrum was assigned to the ²B₂ ← X ²A₁ transition of a planar C_2V structure having a ring of two Cl and two Ca atoms and a terminal Cl atom. The ring isomer of Ca₂Cl₃ has the unpaired electron localized on one Ca²⁺ ion to form a Ca⁺ chromophore. A second electronic band of Ca₂Cl₃ was observed at 720 nm. The band is sharply different from the 650 nm band and likely due to a different isomer.

The equivalent conductance of solutions of picric acid

Picric acid possesses the property, which is rare among strong electrolytes, of having a convenient distribution ratio between water and certain organic solvents such as benzene, chloroform, etc. Because of this property, picric acid offers peculiar advantages for studying the well known deviations of strong electrolytes from the law of mass action, for; by means of distribution experiments, the activities of picric acid in various aqueous solutions may be compared.

In order to interpret the results of such distribution experiments, it is necessary to know the degree of ionization of picric acid in aqueous solutions.

At least three series of determinations of the equivalent conductance of picric acid have been published, but the results are not concordant; and therefore, the degree of ionization cannot be calculated with any degree of certainty.

The object of the present investigation was to redetermine the conductance of picric acid solutions in order to obtain satisfactory data from which the degrees of ionization of its solutions might be calculated.

Dynamics of rotationally resolved multiphoton ionization processes in molecules

This dissertation presents the results of studies of several rotationally- resolved resonance enhanced multiphoton ionization (REMPI) processes in some simple molecular systems. The objective of these studies is to quantitatively identify the underlying dynamics of this highly state-specific process which utilizes the narrow bandwidth radiation of a laser to ionize a molecule by first preparing an excited state via multiphoton absorption and subsequently ionizing that state before it can decay. Coupled with high-resolution photoelectron spectroscopy, REMPI is clearly an important probe of molecular excited states and their photoioniza tion dynamics.

A key feature of our studies is that they are carried out using accurate Hartree-Fock orbitals to describe the photoelectron orbitals of the molecular ions. The use of such photoelectron orbitals is important in rotationally-resolved studies where the angular momentum coupling in the photoelectron orbital plays a significant role in the photoionization dynamics. In these studies the Hartree-Fock molecular molecular photoelectron orbitals are obtained by numerical solution of a Lippmann-Schwinger integral equation.

Studies reported here include investigations of (i) ionic rotational branching ratios and their energy dependence for REMPI via the A^2Σ^+(3sσ) and D^2Σ^+(3pσ)states of NO, (ii) the influence of angular momentum constraints on branching ratios at low photoelectron energies for REMPI via low-J levels of the resonant intermediate state, (iii) the strong dependence of photoelectron angular distributions on final ionic rotational state and on the alignment in REMPI of the A^2Σ^+ state of NO, (iv) vibrational state dependence of ionic rotational branching ratios arising from rapid orbital evolution in resonant states (E'^2Σ^+(3pσ) of CH), (v) the influence of rovibronic interactions on the rotational branching ratios seen in REMPI via the D^2Σ^+(3pσ) state of NO, and (vi) effects of laser intensity on the photoionization dynamics of REMPI.

I. Spectroscopic observation of discrete sites in simple liquids. II. Infrared intensity perturbations of hydrogen halide fundamentals in liquid xenon. III. Rotation of HCl in solid rare gases.

Part I

The spectrum of dissolved mercury atoms in simple liquids has been shown to be capable of revealing information concerning local structures in these liquids.

Part II

Infrared intensity perturbations in simple solutions have been shown to involve more detailed interaction than just dielectric polarization. No correlation has been found between frequency shifts and intensity enhancements.

Part III

Evidence for perturbed rotation of HCl in rare gas matrices has been found. The magnitude of the barrier to rotation is concluded to be of order of 30 cm^(-1).

The separation of atomic and molecular gases from helium by cataphoresis

The cataphoretic purification of helium was investigated for binary mixtures of He with Ar, Ne, N₂, O₂, CO, and CO₂ in DC glow discharge. An experimental technique was developed to continuously measure the composition in the anode end-bulb without sample withdrawal. Discharge currents ranged from 10 ma to 100 ma. Total gas pressure ranged from 2 torr to 9 torr. Initial compositions of the minority component in He ranged from 1.2 mole percent to 7.5 mole percent.

The cataphoretic separation of Ar and Ne from He was found to be in agreement with previous investigators. The cataphoretic separation of N₂, O₂, and CO from He was found to be similar to noble gas systems in that the steady-state separation improved with (1) increasing discharge current, (2) increasing gas pressure, and (3) decreasing initial composition of the minority component. In the He-CO₂ mixture, the CO₂ dissociated to CO plus O₂. The fraction of CO₂ dissociated was directly proportional to the current and pressure and independent of initial composition.

The experimental results for the separation of Ar, Ne, N₂, O₂, and CO from He were interpreted in the framework of a recently proposed theoretical model involving an electrostatic Peclet number. In the model the electric field was assumed to be constant. This assumption was checked experimentally and the maximum variation in electric field was 35% in time and 30% in position. Consequently, the assumption of constant electric field introduced no more than 55% variation in the electrostatic Peclet number during a separation.

To aid in the design of new cataphoretic systems, the following design criteria were developed and tested in detail: (1) electric field independent of discharge current, (2) electric field directly proportional to total pressure, (3) ion fraction of impurity directly proportional to discharge current, and (4) ion fraction of impurity independent of total pressure. Although these assumptions are approximate, they enabled the steady-state concentration profile to be predicted to within 25% for 75% of the data. The theoretical model was also tested with respect to the characteristic time associated with transient cataphoresis. Over 80% of the data was within a factor of two of the calculated characteristic times.

The electrostatic Peclet number ranged in value from 0.13 to 4.33. Back-calculated ion fractions of the impurity component ranged in value from 4.8x10^-6 to 178x10^-6.

Studies of noble gases in meteorites and in the earth

The isotopic and elemental abundances of noble gases in the solar system are investigated, using simple mixing models and mass-spectrometric measurements of the noble gases in meteorites and terrestrial rocks and minerals.

Primordial neon is modeled by two isotopically distinct components from the interstellar gas and dust. Neon from the gas dominates solar neon, which contains about ten times more ²⁰Ne than ²²Ne. Neon from the dust is represented in meteorites by neon-E, with ²⁰Ne/²²Ne less than 0.6. Isotopic variations in meteorites require neon from both dust and gas to be present. Mixing dust and gas without neon loss generates linear correlation lines on three-isotope and composition-concentration diagrams. A model for solar wind implantation predicts small deviations from linear mixing, due to preferential sputtering of the lighter neon isotopes.

Neon in meteorites consists of galactic cosmic ray spallation neon and at least two primordial components, neon-E and neon-S. Neon was measured in several meteorites to investigate these end- members. Cosmogenic neon produced from sodium is found to be strongly enriched in ²²Ne. Neon measurements on sodium-rich samples must be interpreted with care so not to confuse this source of ²²Ne with neon-E, which is also rich in ²²Ne.

Neon data for the carbonaceous chondrite Mokoia show that the end member composition of neon-Si in meteorites is ²⁰Ne/²²Ne = 13.7, the same as the present solar wind. The solar wind composition evidently has remained constant since before the compaction of Mokoia.

Ca, Al-rich inclusions from the Allende meteorite were examined for correlation between neon-E and oxygen or magnesium isotopic anomalies. ²²Ne and ³⁶Ar enrichments found in some inclusions are attributed to cosmic- ray-induced reactions on Na and Cl, not to a primordial component. Neon-E is not detectably enriched in Allende.

Measurements were made to determine the noble gas contents of various terrestrial rocks and minerals, and to investigate the cycling of noble gases between different terrestrial reservoirs. Beryl crystals contain a characteristic suite of magmatic gases including nucleogenic ²¹Ne and ²²Ne from (α,n) reactions, radiogenic ⁴⁰Ar, and fissiogenic ^131-136Xe from the decay of K and U in the continental crust. Significant concentrations of atmospheric noble gases are also present in beryl.

Both juvenile and atmospheric noble gases are found in rocks from the Skaergaard intrusion. The ratio ⁴⁰Ar/³⁶Ar (corrected for in situ decay of ⁴⁰K) correlates with δ¹⁸O in plagioclase. Atmospheric argon has been introduced into samples that have experienced oxygen-isotope exchange with circulating meteoric hydrothermal fluids. Unexchanged samples contain juvenile argon with ⁴⁰Ar/³⁶Ar greater than 6000 that was trapped from the Skaergaard magma.

Juvenile and atmospheric gases have been measured in the glassy rims of mid-ocean ridge (MOR) pillow basalts. Evidence is presented that three samples contain excess radiogenic ¹²⁹Xe and fission xenon, in addition to the excess radiogenic ⁴⁰Ar found in all samples. These juvenile gases are being outgassed from the upper-mantle source region of the MOR magma. No isotopic evidence has been found here for juvenile primordial noble gases accompanying the juvenile radiogenic gases in the MOR glasses. Large argon isotopic variations in a single specimen provide a clear indication of the late-stage addition of atmospheric argon, probably from seawater.

The Skaergaard data demonstrate that atmospheric noble gases dissolved in ground water can be transferred into crustal rocks. Subduction of oceanic crust altered by seawater can transport atmospheric noble gases into the upper mantle. A substantial portion of the noble gases in mantle derived rocks may represent subducted gases, not a primordial component as is often assumed.