Wastewater Electrolysis Cell for Environmental Pollutants Degradation and Molecular Hydrogen Generation

This study proposes a wastewater electrolysis cell (WEC) for on-site treatment of human waste coupled with decentralized molecular H₂ production. The core of the WEC includes mixed metal oxides anodes functionalized with bismuth doped TiO₂ (BiO_x/TiO₂). The BiO_x/TiO₂ anode shows reliable electro-catalytic activity to oxidize Cl- to reactive chlorine species (RCS), which degrades environmental pollutants including chemical oxygen demand (COD), protein, NH4⁺, urea, and total coliforms. The WEC experiments for treatment of various kinds of synthetic and real wastewater demonstrate sufficient water quality of effluent for reuse for toilet flushing and environmental purposes. Cathodic reduction of water and proton on stainless steel cathodes produced molecular H2 with moderate levels of current and energy efficiency. This thesis presents a comprehensive environmental analysis together with kinetic models to provide an in-depth understanding of reaction pathways mediated by the RCS and the effects of key operating parameters. The latter part of this thesis is dedicated to bilayer hetero-junction anodes which show enhanced generation efficiency of RCS and long-term stability.

Chapter 2 describes the reaction pathway and kinetics of urea degradation mediated by electrochemically generated RCS. The urea oxidation involves chloramines and chlorinated urea as reaction intermediates, for which the mass/charge balance analysis reveals that N₂ and CO₂ are the primary products. Chapter 3 investigates direct-current and photovoltaic powered WEC for domestic wastewater treatment, while Chapter 4 demonstrates the feasibility of the WEC to treat model septic tank effluents. The results in Chapter 2 and 3 corroborate the active roles of chlorine radicals (Cl•/Cl₂^-•) based on iR-compensated anodic potential (thermodynamic basis) and enhanced pseudo-first-order rate constants (kinetic basis). The effects of operating parameters (anodic potential and [Cl^-] in Chapter 3; influent dilution and anaerobic pretreatment in Chapter 4) on the rate and current/energy efficiency of pollutants degradation and H₂ production are thoroughly discussed based on robust kinetic models. Chapter 5 reports the generation of RCS on Ir_0.7Ta_0.3O_y/Bi_xTi_1-xO_z hetero-junction anodes with enhanced rate, current efficiency, and long-term stability compared to the Ir_0.7Ta_0.3O_y anode. The effects of surficial Bi concentration are interrogated, focusing on relative distributions between surface-bound hydroxyl radical and higher oxide.

Combustion of CS₂/O₂ in a laminar mixing layer and processes in the CO chemical laser

The combustion of CS₂ and O₂ in a free burning laminar mixing layer at low pressure was investigated using emission spectroscopy. The temperature fields, CO vibrational distributions, and CO concentrations were measured. The data indicate that vibration ally excited CO was produced in the mixing layer flames, but that there were no vibrational population inversions. In comparison with the CS₂/O₂ premixed flames, the mixing layer flames favored greater production of COS and CO₂. Computer modeling was used to study the mechanisms responsible for the production of COS and CO₂, and to study how the branching chain mechanism responsible for production of CO affects the behavior of the mixing layer flame. The influences of the gas additives, N₂O, COS, and CNBr, were also investigated.

Oxygen isotopes and volatiles in martian meteorites

Oxygen isotopes were measured in mineral separates from martian meteorites using laser fluorination and were found to be remarkably uniform in both δ18O and Δ17O, suggesting that martian magmas did not assimilate aqueously altered crust regardless of any other geochemical variations.

Measurements of Cl, F, H, and S in apatite from martian meteorites were made using the SIMS and NanoSIMS. Martian apatites are typically higher in Cl than terrestrial apatites from mafic and ultramafic rocks, signifying that Mars is inherently higher in Cl than Earth. Apatites from basaltic and olivine-phyric shergottites are as high in water as any terrestrial apatite from mafic and utramafic rocks, implying the possibility that martian magmas may be more similar in water abundance to terrestrial magmas than previously thought. Apatites from lherzolitic shergottites, nakhlites, chassignites, and ALH 84001 (all of which are cumulate rocks) are all lower in water than the basaltic and olivine-phyric shergottites, indicating that the slow-cooling accumulation process allows escape of water from trapped melts where apatite later formed. Sulfur is only high in some apatites from basaltic and olivine-phyric shergottites and low in all other SNCs from this study, which could mean that cumulate SNCs are low in all volatiles and that there are other controlling factors in basaltic and olivine-phyric magmas dictating the inclusion of sulfur into apatite.

Sulfur Kα X-rays were measured in SNC apatites using the electron probe. None of the peaks in the SNC spectra reside in the same position as anhydrite (where sulfur is 100% sulfate) or pyrite (where sulfur is 100% sulfide), but instead all SNC spectra peaks lie in between these two end member peaks, which implies that SNC apatites may be substituting some sulfide, as well as sulfate, into their structure. However, further work is needed to verify this hypothesis.

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.

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.

Solubility and Diffusivity of Water in Lunar Basalt, and Chemical Zonation in Olivine-Hosted Melt Inclusions

I report the solubility and diffusivity of water in lunar basalt and an iron-free basaltic analogue at 1 atm and 1350 °C. Such parameters are critical for understanding the degassing histories of lunar pyroclastic glasses. Solubility experiments have been conducted over a range of fO₂ conditions from three log units below to five log units above the iron-wüstite buffer (IW) and over a range of pH₂/pH₂O from 0.03 to 24. Quenched experimental glasses were analyzed by Fourier transform infrared spectroscopy (FTIR) and secondary ionization mass spectrometry (SIMS) and were found to contain up to ~420 ppm water. Results demonstrate that, under the conditions of our experiments: (1) hydroxyl is the only H-bearing species detected by FTIR; (2) the solubility of water is proportional to the square root of pH₂O in the furnace atmosphere and is independent of fO₂ and pH₂/pH₂O; (3) the solubility of water is very similar in both melt compositions; (4) the concentration of H₂ in our iron-free experiments is <3 ppm, even at oxygen fugacities as low as IW-2.3 and pH₂/pH₂O as high as 24; and (5) SIMS analyses of water in iron-rich glasses equilibrated under variable fO₂ conditions can be strongly influenced by matrix effects, even when the concentrations of water in the glasses are low. Our results can be used to constrain the entrapment pressure of the lunar melt inclusions of Hauri et al. (2011).

Diffusion experiments were conducted over a range of fO₂ conditions from IW-2.2 to IW+6.7 and over a range of pH₂/pH₂O from nominally zero to ~10. The water concentrations measured in our quenched experimental glasses by SIMS and FTIR vary from a few ppm to ~430 ppm. Water concentration gradients are well described by models in which the diffusivity of water (D^*_water) is assumed to be constant. The relationship between D^*_water and water concentration is well described by a modified speciation model (Ni et al. 2012) in which both molecular water and hydroxyl are allowed to diffuse. The success of this modified speciation model for describing our results suggests that we have resolved the diffusivity of hydroxyl in basaltic melt for the first time. Best-fit values of D^*_water for our experiments on lunar basalt vary within a factor of ~2 over a range of pH₂/pH₂O from 0.007 to 9.7, a range of fO₂ from IW-2.2 to IW+4.9, and a water concentration range from ~80 ppm to ~280 ppm. The relative insensitivity of our best-fit values of D^*_water to variations in pH₂ suggests that H₂ diffusion was not significant during degassing of the lunar glasses of Saal et al. (2008). D^*_water during dehydration and hydration in H₂/CO₂ gas mixtures are approximately the same, which supports an equilibrium boundary condition for these experiments. However, dehydration experiments into CO₂ and CO/CO₂ gas mixtures leave some scope for the importance of kinetics during dehydration into H-free environments. The value of D^*_water chosen by Saal et al. (2008) for modeling the diffusive degassing of the lunar volcanic glasses is within a factor of three of our measured value in our lunar basaltic melt at 1350 °C.

In Chapter 4 of this thesis, I document significant zonation in major, minor, trace, and volatile elements in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (MgO, FeO, Cr₂O₃, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H₂O, and F, components with a lower concentration in the host olivine than in the melt (Al₂O₃, SiO₂, Na₂O, K₂O, TiO₂, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions concurrent with diffusive propagation of the boundary layer toward the inclusion center.

Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na₂O, K₂O) by coupling to slow diffusing components such as SiO₂ and Al₂O₃. Concentrations of H2O and F decrease towards the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects.

A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C hr^-1 from the liquidus down to ~1000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1000 °C is 40 s to just over one hour.

Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization.

All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

Oxygen relationships in intermittent sand filtration of wastewaters

A model for some of the many physical-chemical and biological processes in intermittent sand filtration of wastewaters is described and an expression for oxygen transfer is formulated.

The model assumes that aerobic bacterial activity within the sand or soil matrix is limited, mostly by oxygen deficiency, while the surface is ponded with wastewater. Atmospheric oxygen reenters into the soil after infiltration ends. Aerobic activity is resumed, but the extent of penetration of oxygen is limited and some depths may be always anaerobic. These assumptions lead to the conclusion that the percolate shows large variations with respect to the concentration of certain contaminants, with some portions showing little change in a specific contaminant. Analyses of soil moisture in field studies and of effluent from laboratory sand columns substantiated the model.

The oxygen content of the system at sufficiently long times after addition of wastes can be described by a quasi-steady-state diffusion equation including a term for an oxygen sink. Measurements of oxygen content during laboratory and field studies show that the oxygen profile changes only slightly up to two days after the quasi-steady state is attained.

Results of these hypotheses and experimental verification can be applied in the operation of existing facilities and in the interpretation of data from pilot plant-studies.