The Effect of Volatiles (H2O, Cl and CO2) on the Solubility and Partitioning of Platinum and Iridium in Fluid-Melt Systems

Volatiles are a fundamental component of the Magmatic-Hydrothermal model of platinum group element (PGE) ore deposition for PGE deposits in layered mafic intrusions such as Bushveld and Stillwater. Volatiles have the potential to complex with PGEs in silicate melts and hydrothermal fluids, increasing PGE solubility; in order to assess the models of PGE ore deposition reliable estimates on the solubilities in the various magmatic phases must be known. However, experimental studies on the solubility and partitioning behaviour of PGEs in mafic magmatic-hydrothermal systems under relevant conditions are sparse, and the data that do exist produce conflicting results and new or adapted experimental methods must be applied to investigate these systems. Experimental results are presented here, investigating the effect of volatiles (i.e. H2O, Cl and CO2) on Pt and Ir solubility in a haplobasaltic melt and fluid-melt partitioning of Pt between an aqueous fluid and a haplobasaltic melt under magmatic conditions using a sealed-capsule technique. Also included are the details of the development of a novel experimental technique to observe fluid-melt partitioning in mafic systems and application of the method to the fluid-melt partition of Pt. Solubility experiments were conducted to assess the effect of volatiles on Pt and Ir solubility in a haplobasaltic melt of dry diopside-anorthite eutectic composition at 1523K and 0.2GPa. Synthetic glass powder of an anhydrous, 1-atm eutectic, diopside-anorthite (An42-Di58) haplobasalt composition was sealed in a platinum or platinum-iridium alloy capsule and was allowed to equilibrate with the noble metal capsule and a source of volatiles (i.e. H2O, H2O-Cl or H2O-CO2) at experimental conditions. All experiments were run in an internally-heated pressure vessel equipped with a rapid quench device, with oxygen fugacity controlled by the water activity and intrinsic hydrogen fugacity of the autoclave (MnO-Mn3O4). The resultant crystal- and bubble-free run product glasses were analyzed using a combination of laser ablation ICP-MS and bulk solution isotope-dilution ICP-MS to determine equilibrium solubilities of Pt and Ir and investigate the formation and contribution of micronuggets to overall bulk determined concentrations. In water-bearing experiments, it was determined that water content did not have an intrinsic effect on Pt or Ir solubility for water contents between 0.9 wt. % and 4.4 wt. % (saturation). Water content controlled the oxygen fugacity of the experiment and the resulting variations in oxygen fugacity, and the corresponding solubilities of Pt and Ir, indicate that over geologically relevant conditions both Pt and Ir are dissolved primarily in the 2+ valence state. Pt data suggest minor influence of Pt4+ at higher oxygen fugacities; however, there is no evidence of higher valence states for Ir. The ability of the sealed capsule technique to produce micronugget-free run product glasses in water-only experiments, allowed the solubility of Pt to be determined in hydrous haplobasalt at lower oxygen fugacities (and concentrations) then was previously observed. Pt and Ir solubility can be represented as a function of oxygen fugacity (bars) by the following equations: [Pt](ppb)= 1389(fO-sub-2)+7531(fO-sub-2)^(1/2) [Ir](ppb)=17140(fO-sub-2)^(1/2) In Cl-bearing experiments, experimental products from short run duration (<96hrs) experiments contained numerous micronuggets, preventing accurate determination of platinum and iridium solubility. Longer run duration experiments showed decreasing amounts of micronuggets, allowing accurate determination of solubility; results indicate that under the conditions studied chlorine has no discernable effect on Pt solubility in the silicate melt from 0.6 to 2.75 wt. % Cl (saturation). Over the same conditions, a systematic increase in Ir solubility is found with increasing Cl content; however, the observed increase is within the analytical variation/error and is therefore not conclusive. If there is an effect of Cl on PGE solubility the effect is minor resulting in increased Ir solubilities of 60% at chlorine saturation. However, the abundance of micronuggets in short run duration experiments, which decreases in abundance with time and increases with Cl-content, offers compelling evidence that Cl-bearing fluids have the capacity to transport significant amounts of Pt and Ir under magmatic conditions. It is suggested that platinum and iridium dissolved within the Cl-bearing fluid are left behind as the fluid dissolves into the melt during the heating stages of the experiment, leaving small amounts of Pt and Ir along the former particle boundaries. With increasing run duration, the metal migrates back to the capsule walls decreasing the amount of micronuggets contained within the glass. Estimates based on this model, using mass-balance calculations on the excess amount of Pt and Ir in the run product glasses (i.e. above equilibrium solubility) in short duration experiments, indicate estimated Pt and Ir concentrations in the Cl-bearing fluid ranging from tens to a few hundred ppm, versus ppb levels in the melt. Respective apparent (equilibrium has not been established) partition coefficients (D,fluid-melt) of 1x10^3 to 4x10^3 and 300-1100 were determined for Pt and Ir in Cl-bearing fluids; suggesting that Cl-bearing fluids can be highly efficient at enriching and transporting PGE in mafic magmatic-hydrothermal ore-forming systems. Platinum solubility was also determined as a function of CO2 content in a hydrous haplobasalt at controlled oxygen fugacity. Using the same sealed capsule techniques and melt composition as for H2O and Cl, a hydrous haplobasaltic melt was allowed to equilibrate with the platinum capsule and a CO2-source (CaCO3 or silver oxalate) at 1523 K and 0.2 GPa. Experiments were conducted with a water content of approximately 1 wt. %, fixing the log oxygen fugacity (bars) between -5.3 and -6.1 (log NNO = -6.95 @ 1573 K and 0.2 GPa). Carbon dioxide contents in the run product glasses ranged from 800-2500 ppm; and over these conditions, CO2 was found to have a negligible effect on Pt solubility in the silicate melt. Analogous to the Cl-bearing experiments, bulk concentrations of Pt in CO2-bearing experiments increased with increasing CO2 content due to micronugget formation. Apparent Pt concentrations in the H2O-CO2 fluid phase, prior to fluid dissolution, were calculated to be 1.6 to 42 ppm, resulting in apparent partition coefficients(D,fluid-melt) of 1.5 x 10^2 to 4.2 x 10^3, increasing with increasing mol CO2:H2O up to approximately 0.15, after which increasing CO2 content does not further increase partitioning. As well, a novel technique was developed and applied to assess the partitioning of Pt between an aqueous fluid and a hydrous diopside-anorthite melt under magmatic conditions. Building upon the sealed-capsule technique utilized for solubility studies, a method was developed by adding a seed crystal to the capsule along with a silicate melt and fluid. By generating conditions favourable to crystal growth, and growing the crystal from the fluid, it is possible to entrap fluid inclusions in the growing crystal, allowing direct sampling of the fluid phase at the conditions of the experiment. Using a diopside seed crystal with the diopside-anorthite eutectic melt, it was possible to control diopside crystallization by controlling the temperature, thus allowing control of the crystallization and fluid inclusion entrapment conditions. Subsequent laser ablation ICP-MS analysis of the fluid inclusions allowed fluid–melt partition coefficients of Pt to be determined. Synthetic glass powder of an anhydrous, 1-atm eutectic, diopside-anorthite (An42¬Di58) haplobasalt composition (with ppm levels of Ba, Cs, Sr and Rb added as internal standards), water and a diopside seed crystal were sealed in a platinum capsule and were allowed to equilibrate at experimental conditions. Water was added in amounts to maintain a free fluid phase throughout the experiment, and the diopside crystal was separated from the melt. All experiments were run in an internally heated pressure vessel equipped with a rapid-quench device, with oxygen fugacity controlled by the water activity and intrinsic hydrogen fugacity of the autoclave (MnO-Mn3O4). Experiments were allowed to equilibrate (6-48 hrs) at experimental conditions (i.e. 1498K, 0.2 GPa, fluid+melt+diopside stable) before temperature was dropped (i.e. to 1483K) to induce crystallization. Crystals were allowed to grow for a period of 18-61 hours, prior to rapid isobaric quenching to 293K at the conclusion of the experiment. Experimental run products were a crystal- and bubble-free glass and the diopside seed crystal with a fluid-inclusion-bearing overgrowth. Analysis of fluid inclusions provides initial solubility estimates of Pt in a H2O fluid phase at 1488 K and 0.2 GPa at or near ppm levels and fluid melt partition coefficients ranging from 2 – 48. This indicates substantial metal enrichment in the fluid phase in the absence of major ligands such as carbonate or chlorine. The results of this study indicate that the volatiles studied (i.e. H2O, CO2, and Cl) do not have a significant effect on Pt and Ir solubility in a haplobasaltic melt at magmatic conditions. These results suggest that complexing of Pt and Ir by OH, Cl, and carbonate species in a haplobasaltic melt is insignificant and the presence of these volatiles will not result in significantly increased PGE contents over their dry counterparts, as has been suggested. Preliminary evidence of minor Cl-complexing of Ir is presented; however, resulting in only a slight increase (<100%) in Ir solubility at Cl-saturation. Significant partitioning of Pt and Ir into a fluid phase at magmatic conditions has been demonstrated; with estimates of fluid-haplobasaltic melt partition coefficients increasing from 1x10^1 for pure water to up to an apparent 4x10^3 with the addition of Cl or CO2 to the system. This result indicates complexing of Pt and Ir with OH< HxCOy≤ Cl. Using these estimates, Cl- or CO2-bearing magmatic fluids can be highly efficient at enriching and transporting platinum group elements (PGEs) in mafic magmatic-hydrothermal ore-forming systems

Rhythmic Haptic Cueing Using Wearable Devices as Physiotherapy for Huntington Disease: Case Study

Background: Huntington disease (HD) is an inherited genetic disorder that results in the death of brain cells. HD symptoms generally start with subtle changes in mood and mental abilities; they then degenerate progressively, ensuing a general lack of coordination and an unsteady gait, ultimately resulting in death. There is currently no cure for HD. Walking cued by an external, usually auditory, rhythm has been shown to steady gait and help with movement coordination in other neurological conditions. More recently, work with other neurological conditions has demonstrated that haptic (ie, tactile) rhythmic cues, as opposed to audio cues, offer similar improvements when walking. An added benefit is that less intrusive, more private cues are delivered by a wearable device that leaves the ears free for conversation, situation awareness, and safety. This paper presents a case study where rhythmic haptic cueing (RHC) was applied to one person with HD. The case study has two elements: the gait data we collected from our wearable devices and the comments we received from a group of highly trained expert physiotherapists and specialists in HD. Objective: The objective of this case study was to investigate whether RHC can be applied to improve gait coordination and limb control in people living with HD. While not offering a cure, therapeutic outcomes may delay the onset or severity of symptoms, with the potential to improve and prolong quality of life. Methods: The approach adopted for this study includes two elements, one quantitative and one qualitative. The first is a repeated-measures design with three conditions: before haptic rhythm (ie, baseline), with haptic rhythm, and after exposure to haptic rhythm. The second element is an in-depth interview with physiotherapists observing the session. Results: In comparison to the baseline, the physiotherapists noted a number of improvements to the participant’s kinematics during her walk with the haptic cues. These improvements continued in the after-cue condition, indicating some lasting effects. The quantitative data obtained support the physiotherapists’ observations. Conclusions: The findings from this small case study, with a single participant, suggest that a haptic metronomic rhythm may have immediate, potentially therapeutic benefits for the walking kinematics of people living with HD and warrants further investigation

O\u27Brien, M. (Torno - 5 acres tract No. 25, Section 58; Ware - Tract No. 25 in Section 58, 5 acres), 1944-1951

2.4 Real estate, Box 119, Folder 58https://scholarworks.utrgv.edu/johnshary/1107/thumbnail.jp

Evaluating Cumulative Ecosystem Response to Restoration Projects in the Columbia River Estuary, Annual Report 2004

The restoration of wetland salmon habitat in the tidal portion of the Columbia River is occurring at an accelerating pace and is anticipated to improve habitat quality and effect hydrological reconnection between existing and restored habitats. Currently multiple groups are applying a variety of restoration strategies in an attempt to emulate historic estuarine processes. However, the region lacks both a standardized means of evaluating the effectiveness of individual projects as well as methods for determining the cumulative effects of all restoration projects on a regional scale. This project is working to establish a framework to evaluate individual and cumulative ecosystem responses to restoration activities in order to validate the effectiveness of habitat restoration activities designed to benefit salmon through improvements to habitat quality and habitat opportunity (i.e. access) in the Columbia River from Bonneville Dam to the ocean. The review and synthesis of approaches to measure the cumulative effects of multiple restoration projects focused on defining methods and metrics of relevance to the CRE, and, in particular, juvenile salmon use of this system. An extensive literature review found no previous study assessing the cumulative effects of multiple restoration projects on the fundamental processes and functions of a large estuarine system, although studies are underway in other large land-margin ecosystems including the Florida Everglades and the Louisiana coastal wetlands. Literature from a variety of scientific disciplines was consulted to identify the ways that effects can accumulate (e.g., delayed effects, cross-boundary effects, compounding effects, indirect effects, triggers and thresholds) as well as standard and innovative tools and methods utilized in cumulative effects analyses: conceptual models, matrices, checklists, modeling, trends analysis, geographic information systems, carrying capacity analysis, and ecosystem analysis. Potential indicators for detecting a signal in the estuarine system resulting from the multiple projects were also reviewed, i.e. organic matter production, nutrient cycling, sedimentation, food webs, biodiversity, salmon habitat usage, habitat opportunity, and allometry. In subsequent work, this information will be used to calculate the over net effect on the ecosystem. To evaluate the effectiveness of habitat restoration actions in the lower Columbia River and estuary, a priority of this study has been to develop a set of minimum ecosystem monitoring protocols based on metrics important for the CRE. The metrics include a suite of physical measurements designed to evaluate changes in hydrological and topographic features, as well as biological metrics that will quantify vegetation and fish community structure. These basic measurements, intended to be conducted at all restoration sites in the CRE, will be used to (1) evaluate the effectiveness of various restoration procedures on target metrics, and (2) provide the data to determine the cumulative effects of many restoration projects on the overall system. A protocol manual is being developed for managers, professional researchers, and informed volunteers, and is intended to be a practical technical guide for the design and implementation of monitoring for the effects of restoration activities. The guidelines are intended to standardize the collection of data critical for analyzing the anticipated ecological change resulting from restoration treatments. Field studies in 2005 are planned to initiate the testing and evaluation of these monitoring metrics and protocols and initiate the evaluation of higher order metrics for cumulative effects

Evaluating Cumulative Ecosystem Response to Restoration Projects in the Columbia River Estuary, Annual Report 2005

This report is the second annual report of a six-year project to evaluate the cumulative effects of habitat restoration projects in the Columbia River Estuary, conducted by Pacific Northwest National Laboratory's Marine Sciences Laboratory, NOAA's National Marine Fisheries Service Pt. Adams Biological Field Station, and the Columbia River Estuary Study Taskforce for the US Army Corps of Engineers. In 2005, baseline data were collected on two restoration sites and two associated reference sites in the Columbia River estuary. The sites represent two habitat types of the estuary--brackish marsh and freshwater swamp--that have sustained substantial losses in area and that may play important roles for salmonids. Baseline data collected included vegetation and elevation surveys, above and below-ground biomass, water depth and temperature, nutrient flux, fish species composition, and channel geometry. Following baseline data collection, three kinds of restoration actions for hydrological reconnection were implemented in several locations on the sites: tidegate replacements (2) at Vera Slough, near the city of Astoria in Oregon State, and culvert replacements (2) and dike breaches (3) at Kandoll Farm in the Grays River watershed in Washington State. Limited post-restoration data were collected: photo points, nutrient flux, water depth and temperature, and channel cross-sections. In subsequent work, this and additional post-restoration data will be used in conjunction with data from other sites to estimate net effects of hydrological reconnection restoration projects throughout the estuary. This project is establishing methods for evaluating the effectiveness of individual projects and a framework for assessing estuary-wide cumulative effects including a protocol manual for monitoring restoration and reference sites

Evaluating Cumulative Ecosystem Response to Restoration Projects in the Columbia River Estuary, Annual Report 2006

This report is the third annual report of a six-year project to evaluate the cumulative effects of habitat restoration action in the Columbia River Estuary (CRE). The project is being conducted for the U.S. Army Corps of Engineers (Corps) by the Marine Sciences Laboratory of the Pacific Northwest National Laboratory, the Pt. Adams Biological Field Station of the National Marine Fisheries Service, and the Columbia River Estuary Study Taskforce. Measurement of the cumulative effects of ecological restoration projects in the Columbia River estuary is a formidable task because of the size and complexity of the estuarine landscape and the meta-populations of salmonids in the Columbia River basin. Despite the challenges presented by this system, developing and implementing appropriate indicators and methods to measure cumulative effects is the best way to enable estuary managers to track the overall effectiveness of investments in estuarine restoration projects. This project is developing methods to quantify the cumulative effects of multiple restoration activities in the CRE. The overall objectives of the 2006 study were to continue to develop techniques to assess cumulative effects, refine the standard monitoring protocols, and initiate development of an adaptive management system for Corps of Engineers’ habitat restoration monitoring efforts in the CRE. (The adaptive management effort will be reported at a later date.) Field studies during 2006 were conducted in tidal freshwater at Kandoll Farm on the lower Grays River and tidal brackish water at Vera Slough on Youngs Bay. Within each of area, we sampled one natural reference site and one restoration site. We addressed the overall objectives with field work in 2006 that, coupled with previous field data, had specific objectives and resulted in some important findings that are summarized here by chapter in this report. Each chapter of the report contains data on particular monitored variables for pre- and post-restoration conditions at both the Kandoll and Vera study areas

Cerebrospinal fluid proteomics define the natural history of autosomal dominant Alzheimer's disease

Alzheimer's disease (AD) pathology develops many years before the onset of cognitive symptoms. Two pathological processes-aggregation of the amyloid-& beta;(A & beta;) peptide into plaques and the microtubule protein tau into neurofibrillary tangles (NFTs)-are hallmarks of the disease. However, other pathological brain processes are thought to be key disease mediators of A & beta;plaque and NFT pathology. How these additional pathologies evolve over the course of the disease is currently unknown. Here we show that proteomic measurements in autosomal dominant AD cerebrospinal fluid (CSF) linked to brain protein coexpression can be used to characterize the evolution of AD pathology over a timescale spanning six decades. SMOC1 and SPON1 proteins associated with A & beta;plaques were elevated in AD CSF nearly 30 years before the onset of symptoms, followed by changes in synaptic proteins, metabolic proteins, axonal proteins, inflammatory proteins and finally decreases in neurosecretory proteins. The proteome discriminated mutation carriers from noncarriers before symptom onset as well or better than A & beta;and tau measures. Our results highlight the multifaceted landscape of AD pathophysiology and its temporal evolution. Such knowledge will be critical for developing precision therapeutic interventions and biomarkers for AD beyond those associated with A & beta;and tau. Proteomic analysis of cerebrospinal fluid from individuals with autosomal dominant Alzheimer's disease reveals how this complex and chronic disease evolves over many decades

Cerebrospinal fluid proteomics define the natural history of autosomal dominant Alzheimer’s disease

Alzheimer’s disease (AD) pathology develops many years before the onset of cognitive symptoms. Two pathological processes—aggregation of the amyloid- (A ) peptide into plaques and the microtubule protein tau into neurofibrillary tangles (NFTs)—are hallmarks of the disease. However, other pathological brain processes are thought to be key disease mediators of A plaque and NFT pathology. How these additional pathologies evolve over the course of the disease is currently unknown. Here we show that proteomic measurements in autosomal dominant AD cerebrospinal fluid (CSF) linked to brain protein coexpression can be used to characterize the evolution of AD pathology over a timescale spanning six decades. SMOC1 and SPON1 proteins associated with A plaques were elevated in AD CSF nearly 30 years before the onset of symptoms, followed by changes in synaptic proteins, metabolic proteins, axonal proteins, inflammatory proteins and finally decreases in neurosecretory proteins. The proteome discriminated mutation carriers from noncarriers before symptom onset as well or better than A and tau measures. Our results highlight the multifaceted landscape of AD pathophysiology and its temporal evolution. Such knowledge will be critical for developing precision therapeutic interventions and biomarkers for AD beyond those associated with A and tau

Signal Approach

Concerns and approaches shared by art video and independent film as well as the formal and social issues addressed in specific works are examined