An Experimental investigation of chemical mass transfer processes in crystallizing, hydrous silicate magmas: The genesis of ore deposits and metasomatic fluids

This dissertation is comprised of three broadly related experimental petrology projects on phase equilibria and noble metal solubility in hydrous silicate melts. Chapters two and three combine experimental petrology with high precision laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of experimental run products in order to quantitatively constrain the behavior of the investigated metals. Chapter four presents experimental evidence detailing a novel oxidation mechanism for degassing silicate liquids as well as exploring the geochemical consequences of the proposed mechanism. Chapter two presents the results of an experimental study on Au, Pt, and Pd behavior in coexisting silicate melt-sulfide-oxide phase assemblages. Data from this study suggest the combined effect of oxygen and sulfur fugacity dictates the identity of stable magmatic sulfide phase assemblages, as well as dictating the concentration of Pt and Pd in monosulfide solid solution; both of these factors are critical components that determine metal tenor and the ore-deposit forming potential of a given magma. Chapter three presents an experimental study of Au solubility in hydrous, chloride rich basaltic liquids as a function of oxygen fugacity (fO2). LA-ICP-MS determined Au concentrations in the quenched melt do not strictly adhere to the relationship between fO2 and Au solubility predicted for a monovalent Au oxide species. The observed relationship between Au and fO2 suggests the existence of alternative, non-oxide species in the melt. The solubility data presented in this chapter constrain the maximum Au concentration of natural hydrous basaltic liquids to values less than 2 μg g-1. Chapter four presents experimental evidence suggesting a new mechanism for chloride degassing induced auto-oxidation of silicate liquids. The chemical exchange between silicate melts and chloride bearing fluids preferentially removes ferrous iron from the melt relative to ferric iron. The net effect of this preferential scavenging effect is to enrich the residual melt in ferric iron, increasing the melt’s intrinsic fO2. Dynamically changing magmatic oxygen fugacities profoundly affect the stability liquidus silicate phases in addition to potential sulfide phases involved in ore forming processes. (Refer to PDF file for exact formulas.

Exploring the Moon's surface for remnants of the lunar mantle 1. Dunite xenoliths in mare basalts. A crustal or mantle origin?

Remotely sensed observations from recent missions (e.g., GRAIL, Kaguya, Chandrayaan-1) have been interpreted as indicating that the deep crust and upper mantle are close to or at the lunar surface in many large impact basins (e.g., Crisium, Apollo, Moscoviense). If this is correct, the capability of either impact or volcanic processes to transport mantle lithologies to the lunar surface should be enhanced in these regions. Somewhat problematic to these observations and interpretations is that examples of mantle lithologies in the lunar sample collection (Apollo Program, Luna Program, lunar meteorites) are at best ambiguous. Dunite xenoliths in high-Ti mare basalt 74275 are one of these ambiguous examples. In this high-Ti mare basalt, olivine occurs in three generations: olivine associated with dunite xenoliths, olivine megacrysts, and olivine microphenocrysts. The dunite xenoliths are anhedral in shape and are generally greater than 800 μm in diameter. The interior of the xenoliths are fairly homogeneous with regard to many divalent cations. For example, the Mg# (Mg/Mg + Fe × 100) ranges from 82 to 83 in their interiors and decreases from 82 to 68 over the 10–30 μm wide outer rim. Titanium and phosphorus X-ray maps of the xenolith illustrate that these slow diffusing elements preserve primary cumulate zoning textures. These textures indicate that the xenoliths consist of many individual olivine grains approximately 150–200 μm in diameter with low Ti, Al, and P cores. These highly incompatible elements are enriched in the outer Fe-rich rims of the xenoliths and slightly enriched in the rims of the individual olivine grains. Highly compatible elements in olivine such as Ni exhibit a decrease in the rim surrounding the xenolith, an increase in the incompatible element depleted cores of the individual olivine grains, and a slight decrease in the “interior rims” of the individual olivine grains. Inferred melt composition, liquid lines of descent, and zoning profiles enable the reconstruction of the petrogenesis of the dunite xenoliths. Preservation of primary magmatic zoning (Ti, P, Al) and lack of textures similar to high-pressure mineral assemblages exhibited by the Mg-suite (Shearer et al. 2015) indicate that these xenoliths do not represent deep crustal or shallow mantle lithologies. Further, they are chemically and mineralogically distinct from Mg-suite dunites identified from the Apollo 17 site. More likely, they represent olivine cumulates that crystallized from a low-Ti mare basalt at intermediate to shallow crustal levels. The parent basalt to the dunite xenolith lithology was more primitive than low-Ti basalts thus far returned from the Moon. Furthermore, this parental magma and its more evolved daughter magmas are not represented in the basalt sample suite returned from the Taurus-Littrow Valley by the Apollo 17 mission. The dunite xenolith records several episodes of crystallization and re-equilibration. During the last episode of re-equilibration, the dunite cumulate was sampled by the 74275 high-Ti basalt and transported over a period of 30–70 days to the lunar surface

Prescription drug monitoring program data tracking of opioid addiction treatment outcomes in integrated dual diagnosis care involving injectable naltrexone

BACKGROUND AND OBJECTIVES: Fourfold increases in opioid prescribing and dispensations over 2 decades in the U.S. has paralleled increases in opioid addictions and overdoses, requiring new preventative, diagnostic, and treatment strategies. This study examines Prescription Drug Monitoring Program (PDMP) tracking as a novel measure of opioid addiction treatment outcomes in a university-affiliated integrated mental health-addiction treatment clinic. METHODS: Repeated measure parametrics examined PDMP and urine drug screening (UDS) data before and after first injection for all patients (N = 68) who received at least one long-acting naltrexone injection (380 mg/IM) according to diagnostic groupings of having either (i) alcohol (control); (ii) opioid; or (iii) combined alcohol and opioid use disorders. RESULTS: There were no group differences post-injection in treatment days, injections delivered, or treatment service encounters. UDS and PDMP measures of opioid exposures were greater in opioid compared to alcohol-only patients. Post-first injection, UDS's positive for opioids declined (p < .05) along with PDMP measures of opioid prescriptions (p < .001), doses (p < .01), types (p < .001), numbers of dispensing prescribers (p < .001) and pharmacies (p < .001). Opioid patients without alcohol disorders showed the best outcomes with 50% to 80% reductions in PDMP-measures of opioids, down to levels of alcohol-only patients. CONCLUSIONS: This study shows PDMP utility for measuring opioid addiction treatment outcomes, supporting the routine use of PDMPs in clinical and research settings. SCIENTIFIC SIGNIFICANCE: These findings demonstrate that opioid addiction in patients with complex addictions and mental illnesses comorbidities can show effective treatment responses as measured by PDMP tracking of decreases in opioid prescriptions to those patients. (Am J Addict 2016;25:557-564)

The Cr Redox Record of fO2 Variation in Angrites. Evidence for Redox Conditions of Angrite Petrogenesis and Parent Body

Angrites represent some of the earliest stages of planetesimal differentiation. Not surprisingly, there is no simple petrogenetic model for their origin. Petrogenesis has been linked to both magmatic and impact processes. Studies demonstrated that melting of chondritic material (e.g. CM, CV) at redox conditions where pure iron metal is unstable (e.g., IW+1 to IW+2) produced angrite-like melts. Alternatively, angrites were produced at more reducing conditions (<IW) with their exotic melt compositions resulting from carbonates in the source or from nebular condensation. Clearly, understanding what role fO2 plays in producing angrite magmas is critical for deciphering their petrogenesis and extending our understanding of primordial melting of asteroids. Calculations for the fO2 conditions of angrite crystallization are limited, and only preliminary attempts been made to understand the changes in fO2 that occurred during petrogenesis. Many of the angrites have phase assemblages which provide conflicting signals about redox conditions during crystallization (e.g., Fe metal and a Fe-Ti oxide with potential Fe3+. There have been several estimates of fO2 for angrites. Most notably, experiments examined the variation of DEu/DGd with fO2, between plagioclase and fassaitic pyroxene in equilibrium with an angrite melt composition. They used their observations to estimate the fO2 of crystallization to be approximately IW+0.6 for angrite LEW 86010. This estimate is only a "snapshot" of fO2 conditions during co-crystallization of plagioclase and pyroxene. Preliminary XANES analyses of V redox state in pyroxenes from D'Orbigny reported changes in fO2 from IW-0.7 during early pyroxene crystallization to IW+0.5 during latter episodes of pyroxene crystallization [15]. As this was a preliminary report, it presented limited information concerning the effects of pyroxene orientation and composition on the V valence measurements, and the effect of melt composition on valence and partitioning behavior of V. A closer examination of fO2 as recorded by Cr valence state in olivine will allow us to test models for primordial melting of chondritic material to produce the angrite parent melts. Here, we report the our initial stages of examining the origin and conditions of primordial melting on the angrite parent body and test some of the above models by integrating an experimental study of Cr and V valence partitioning between olivine [OL] and an angrite melt, with micro-scale determinations of Cr and V oxidation state in OL in selected "volcanic" angrites

Optimal operation of the Western Link embedded HVDC connection

The Western Link is a new point-to-point embedded HVDC connection due to be commissioned in Great Britain in 2018. This paper investigates the optimal loading of the Western Link with respect to the wider transmission system. The work modelled a representation of behaviour of the wholesale market and system operator actions using mathematical optimisation in the form of an economic dispatch followed by an AC optimal power flow. A range of different system cases was studied using: a representative high voltage transmission network of Great Britain; system planned outages on AC circuits in parallel with the Western Link; system contingencies; and two possible post-contingency Western Link loading rules. It was concluded from the cases studied that the optimal dispatch of power on the Western Link is an affine function of power flow in the parallel AC circuits, modulated by system planned outages and the thermal rating of the Western Link

The Mineralogical Record of Oxygen Fugacity Variation and Alteration in Northwest Africa 8159: Evidence for Interaction Between a Mantle Derived Martian Basalt and a Crustal Component(s)

A prominent geochemical feature of basaltic magmatism on Mars is the large range in initial Sr isotopic ratios (approx. 0.702 - 0.724) and initial epsilon-Nd values (approx. -10 to greater than +50). Within this range, the shergottites fall into three discreet subgroups. These subgroups have distinct bulk rock REE patterns, mineral chemistries (i.e. phosphate REE patterns, Ni, Co, V in olivine), oxygen fugacity of crystallization, and stable isotopes, such as O. In contrast, nakhlites and chassignites have depleted epsilon-Nd values (greater than or equal to +15), have REE patterns that are light REE enriched, and appear to have crystallized near the FMQ buffer. The characteristics of these various martian basalts have been linked to different reservoirs in the martian crust and mantle, and their interactions during the petrogenesis of these magmas. These observations pose interesting interpretive challenges to our understanding of the conditions of the martian mantle (e.g. oxygen fugacity) and the interaction of mantle derived magmas with the martian crust and surface. Martian meteorite NWA 8159 is a unique fine-grained augite basalt derived from a highly depleted mantle source as reflected in its initial epsilon-Nd value, contains a pronounced light REE depleted pattern, and crystallized presumably under very oxidizing conditions. Although considerably older than both shergottites and nahklites, it has been petrogenetically linked to both styles of martian magmatism. These unique characteristics of NWA 8159 may provide an additional perspective for deciphering the petrogenesis of martian basalts and the nature of the crust of Mars

Gravitational Instabilities, Chondrule Formation, and the FU Orionis Phenomenon

Using analytic arguments and numerical simulations, we examine whether chondrule formation and the FU Orionis phenomenon can be caused by the burst-like onset of gravitational instabilities (GIs) in dead zones. At least two scenarios for bursting dead zones can work, in principle. If the disk is on the verge of fragmention, GI activation near $r\sim4$ to 5 AU can produce chondrule-forming shocks, at least under extreme conditions. Mass fluxes are also high enough during the onset of GIs to suggest that the outburst is related to an FU Orionis phenomenon. This situation is demonstrated by numerical simulations. In contrast, as supported by analytic arguments, if the burst takes place close to $r\sim1$ AU, then even low pitch angle spiral waves can create chondrule-producing shocks and outbursts. We also study the stability of the massive disks in our simulations against fragmentation and find that although disk evolution is sensitive to changes in opacity, the disks we study do not fragment, even at high resolution and even for extreme assumptions.Comment: To appear in Ap