High-pressure Laboratory Research Articles

New Instrument for Time-Resolved OH and HO2 Quantification in High-Pressure Laboratory Kinetics Studies.

We have constructed a new time-resolved high-pressure fluorescence assay by gas expansion (HP-FAGE) apparatus, optimized for the detection of OH and HO2 radicals in complex gas-phase reactions. The new instrument fills a gap in the existing experimental toolkit for chemical kinetics by enabling the quantification of two key reactive species with microsecond time resolution from high-pressure sources, which was previously not attainable. The HP-FAGE is interfaced with a flow reactor, designed for pressures up to 100 bar and temperatures up to 1000 K, in which reactions are initiated by laser photolysis of radical precursors at repetition rates of 1-10 Hz. The HP-FAGE samples gas out of the reactor into a miniature FAGE chamber, where OH is detected by resonant laser-induced fluorescence using a time-delayed probe laser pulse. HO2 is converted to OH via reaction with NO and then detected by OH fluorescence. The novel FAGE design places the probe region very close to the gas expansion, minimizing the transport time of sampled molecules and resulting in time resolution better than 20 μs for both OH and HO2. We calibrate the sensitivity of HP-FAGE, validate its performance with measurements of well-known reaction kinetics (OH + CH4, OH + OH, OH + HO2, and HO2 + HO2), and discuss prospects for its future use.

Joint Research with High Pressure Laboratory at the Institute for Solid State Physics, University of Tokyo

Joint Research with High Pressure Laboratory at the Institute for Solid State Physics, University of Tokyo

“A Cross Sectional Study on Association between Serum Vitamin D Status and Insulin Resistance in Polycystic Ovarian Syndrome”

Polycystic ovarian syndrome is a common cause of ovarian dysfunction in women with anovulation world wide.50-70% of patients with PCOS exhibit metabolic abnormalities, including poor glucose tolerance and hyperinsulinemia. The prevalence of vitamin D deficiency in women with PCOS is about 67-85 per cent, with serum concentrations of 25(OH) D <20 ng/ml. It is suggested that there is an association between serum levels of vitamin D and metabolic parameters in women with PCOS, including fasting glucose levels, fasting insulin, insulin resistance, high blood pressure, lipid disorders, obesity, fertility and other clinical and laboratory- related parameters associated with PCOS. Given the high prevalence of vitamin D deficiency in the south Indian population, less number of studies, inconclusive studies, especially in the population of women with PCOS, as well as evidence from recent studies indicating a link between vitamin D levels with lab parameters, this study aimed to assess the relationship between vitamin D deficiency and insulin resistance in PCOS. Pearsons correlation showed 0.034 between HOMA IR and vitamin d levels indicating that vitamin d deficiency is associated with more HOMA IR values, the more insulin resistance. Pearsons correlation showed 0.05 between fasting insulin levels and vitamin d levels indicating the vitamin d deficiency is associated with more fasting insulin levels, the more insulin resistance. No significant relation is seen with fasting glucose insulin levels (Pearsons correlation value >0.05). In the study, it was found that a high percentage of PCOS women were vitamin D deficient. The study also showed a significant difference in the values of some clinical and metabolic parameters such as waist circumference, fasting insulin, HOMA-IR, BMI between PCOS women with and without vitamin D deficiency; however, no linear correlation was found between serum levels of vitamin D and baseline variables, except for HOMA IR values, fasting insulin levels, BMI, G120. In conclusion, our data confirm an association between vitamin D deficiency and Insulin resistance in patients with PCOS. Thus, vitamin D supplementation could be a beneficial treatment of PCOS women to abolish insulin resistance and regulate menstrual irregularities.

Anaerobic methane-oxidizing activity in a deep underground borehole dominantly colonized by Ca. Methanoperedenaceae.

The family Ca. Methanoperedenaceae archaea mediates the anaerobic oxidation of methane (AOM) in different terrestrial environments. Using a newly developed high-pressure laboratory incubation system, we investigated 214- and 249-m deep groundwater samples at Horonobe Underground Research Laboratory, Japan, where the high and low abundances of Ca. Methanoperedenaceae archaea have been shown by genome-resolved metagenomics, respectively. The groundwater samples amended with 13 C-labelled methane and amorphous Fe(III) were incubated at a pressure of 1.6MPa. After 3-7 days of incubation, the AOM rate was 45.8 ± 19.8nM/day in 214-m groundwater. However, almost no activity was detected from 249-m groundwater. Based on the results from 16S rRNA gene analysis, the abundance of Ca. Methanoperedenaceae archaea was high in the 214-m deep groundwater sample, whereas Ca. Methanoperedenaceae archaea was undetected in the 249-m deep groundwater sample. These results support the in situ AOM activity of Ca. Methanoperedenaceae archaea in the 214-m deep subsurface borehole interval. Although the presence of Fe-bearing phyllosilicates was demonstrated in the 214-m deep groundwater, it needs to be determined whether Ca. Methanoperedenaceae archaea use the Fe-bearing phyllosilicates as in situ electron acceptors by high-pressure incubation amended with the Fe-bearing phyllosilicates.

Pore-scale bubble population dynamics of CO2-foam at reservoir pressure

The flow of CO2 foam for mobility control in porous media is dictated by the foam texture, or bubble density, which is commonly expressed as the number of bubbles per unit of flowing gas. In most high-pressure laboratory studies of foam in porous media, the local foam texture cannot be determined due to opaque flow systems. Here, we unlock real-time foam texture dynamics at high pressure (100 bar) by utilizing a realistic pore network with an extended field of view. We identified snap-off as the dominant foam generation mechanism, with additional fining of foam texture caused by backward foam propagation. Foam coalescence during continuous CO2 injection resulted in large gas channels parallel to the general flow direction that reduced the overall foam apparent viscosity. A large fraction of the CO2 foam remained trapped (Xt > 0.97) and stationary in pores to divert CO2 flow and increase sweep efficiency. The gas mobility was calculated from the fraction of trapped bubbles at the pore-scale, and the apparent foam viscosity agreed with similar injection test performed at core-scale. Hence, improved understanding of CO2 foam texture evolution (nf) can strengthen the validation of numerical foam models for upscaling of flow phenomena, instrumental in the development of field scale implementation of CO2 foam for in carbon utilization and storage applications.

Studying the Stability of the K/Ar Isotopic System of Phlogopites in Conditions of High T, P: 40Ar/39Ar Dating, Laboratory Experiment, Numerical Simulation

Typically, 40Ar/39Ar dating of phlogopites from deep-seated xenoliths of kimberlite pipes produces estimates that suggest much older ages than those when these pipes were intruded. High-pressure (3 GPa) laboratory experiments enabled the authors to explore the behaviour of argon in the phlogopite structure under the conditions that correspond to the mantle, at the temperatures (from 700 to 1000 °С), far exceeding closure temperature of the K/Ar isotopic system. “Volume diffusion” remains foremost for describing the mobility of argon in phlogopite at high pressures. The mantle material age can be estimated through the dating of the phlogopites from deep-seated xenoliths of kimberlites, employing the 40Ar/39Ar method, subject to correction for a partial loss of radiogenic 40Ar when xenolith moves upwards to the Earth’s surface. The obtained data served as the basis for proposing the behaviour model of the K/Ar isotopic system of minerals in conditions of great depths (lower crust, mantle), and when transporting xenoliths in the kimberlite melt.

Mid-infrared reflectance spectroscopy of synthetic glass analogs for Mercury surface studies

We have synthesized and analyzed by mid-infrared reflectance spectroscopy silicate glasses that are representative for the glasses on the surface of Mercury. The glass compositions are based on high-pressure laboratory experiments and the resulting compositions of the glass phase. The spectra are of interest for investigating the surface of Mercury using the MERTIS (Mercury Radiometer and Thermal Infrared Spectrometer) instrument on board of the ESA/JAXA BepiColombo mission.Both powdered fractions and polished blocks have been analyzed. Powdered size fractions of 0–25 μm, 25-63 μm, 63-125 μm, and 125–250 μm were measured in reflectance in the thermal infrared (2–20 μm). Spectra for powdered bulk glasses (1.6 wt% - 19.0 wt% MgO) show a single, dominating Reststrahlenband (RB, 9.3–9.8 μm), a Christiansen Feature (CF; 7.6 μm - 8.1 μm), and a size dependent Transparency Feature (TF; 11.6–11.9 μm). Micro-FTIR analyses of polished blocks of glasses (3.4–26.5 wt% MgO) have characteristic bands at 7.8–8.2 μm (CF), and 9.3–9.9 μm (RB). Only few olivine crystalline features were observed.Spectral features correlate with compositional characteristics, e.g. SiO2 content or SCFM (SiO2/(SiO2 + CaO + FeO + MgO) index. The strongest correlation between band features CF and the strong RB are with Mg/Si. No simple mixture of glass spectra from this study is able to reproduce the entire ground based spectrum of the surface of Mercury. However, Mg-rich glasses reproduce identified features at 8.5 μm, 9.9 μm and 12.4 μm.

Stony Brook’s High-Pressure Laboratory Collaborations with French Scientists

For more than a half century, my colleagues and I in the Stony Brook High Pressure Laboratory have profited from collaborations with French scientists in their laboratories in Orsay, Paris, Toulouse, Lille, Lyon, Strasbourg and Rennes. These interactions have included postdoctoral appointments of French colleagues in our laboratory as well as two année sabbatique by me; in 1983-84, in the Laboratoire de Géophysique et Géodynamique Interne at the Université Paris XI in Orsay and in 2020-2003 in the Laboratoire des Méchanismes et Transfert en Géologie at the Université Paul Sabatier in Toulouse. The objective of this report is to relate this history and to illustrate the scientific advances which resulted from these collaborations.

My Research Collaborations with Chinese Scientists over the Past Three Decades

For more than three decades, I have been fortunate in working with Chinese graduate students and postdoctoral research scientists in our High-Pressure Laboratory at Stony Brook University. These colleagues have conducted a wide variety of experiments at high pressures and temperatures in collaboration with our other students and researchers. These studies utilized transmission electron microscopy, ultrasonic interferometry, X-ray powder diffraction and synchrotron X-radiation to investigate phase transitions, thermal equations of state, sound velocities, atomic diffusion, dislocation dissociation and deviatoric stress in high-pressure apparatus. During this period, I have also visited high-pressure laboratories in the mainland of China and Taiwan on several occasions. The objective of this paper is to relate this history.

Methane Hydrate Formation and Dissociation in Sand Media: Effect of Water Saturation, Gas Flowrate and Particle Size

Assessing the influence of key parameters governing the formation of hydrates and determining the capacity of the latter to store gaseous molecules is needed to improve our understanding of the role of natural gas hydrates in the oceanic methane cycle. Such knowledge will also support the development of new industrial processes and technologies such as those related to thermal energy storage. In this study, high-pressure laboratory methane hydrate formation and dissociation experiments were carried out in a sandy matrix at a temperature around 276.65 K. Methane was continuously injected at constant flowrate to allow hydrate formation over the course of the injection step. The influence of water saturation, methane injection flowrate and particle size on hydrate formation kinetics and methane storage capacity were investigated. Six water saturations (10.8%, 21.6%, 33%, 43.9%, 55% and 66.3%), three gas flowrates (29, 58 and 78 mLn·min−1) and three classes of particle size (80–140, 315–450 and 80–450 µm) were tested, and the resulting data were tabulated. Overall, the measured induction time obtained at 53–57% water saturation has an average value of 58 ± 14 min minutes with clear discrepancies that express the stochastic nature of hydrate nucleation, and/or results from the heterogeneity in the porosity and permeability fields of the sandy core due to heterogeneous particles. Besides, the results emphasize a clear link between the gas injection flowrate and the induction time whatever the particle size and water saturation. An increase in the gas flowrate from 29 to 78 mLn·min−1 is accompanied by a decrease in the induction time up to ~100 min (i.e., ~77% decrease). However, such clear behaviour is less conspicuous when varying either the particle size or the water saturation. Likewise, the volume of hydrate-bound methane increases with increasing water saturation. This study showed that water is not totally converted into hydrates and most of the calculated conversion ratios are around 74–84%, with the lowest value of 49.5% conversion at 54% of water saturation and the highest values of 97.8% for the lowest water saturation (10.8%). Comparison with similar experiments in the literature is also carried out herein.

Noble Gas Reactivity in Planetary Interiors

While the field of noble gas reactivity essentially belongs to chemistry, Earth and planetary sciences have brought a different perspective to the field. Indeed, planetary interiors are natural high pressure (P) and high temperature (T) laboratories, where conditions exist where bonding of the heaviest noble gases may be induced thermodynamically through volume reduction (Le Châtelier’s principle). Earth and planetary sciences besides generate numerous and precise observations such as the depletion of the terrestrial and martian atmospheres in xenon, pointing to the potential for Xe to be sequestered at depth, potentially induced by its reactivity. More generally, this paper will review the advances on noble gas reactivity at the extreme P-T conditions found within planetary interiors from experiments and theoretical investigations. This review will cover the synthesis of cage compounds, stoichiometric oxides and metals, and non-stoichiometric compounds where noble gases are only minor or trace elements but could be essential in solving some Earth and planetary puzzles. An apparent trend in noble gases reactivity with P emerges. In the case of Xe which is the most documented, metals are synthesized above 150 GPa, i.e. at terrestrial core conditions, stoichiometric Xe-oxides between 50 GPa and 100 GPa, i.e. in the P -T range of the Earth’s lower mantle, but Xe-O high energy bonds may also form under the modest pressures of the Earth’s crust (less than 1 GPa) in non-stoichiometric compounds. Most planetary relevant noble gas compounds found are with xenon, with only a few predicted helium compounds, the latter having no or very little charge transfer between helium and neighbouring atoms.

My Career as a Mineral Physicist at Stony Brook: 1976–2019

In 1976, I took up a faculty position in the Department of Geosciences of Stony Brook University. Over the next half century, in collaboration with graduate students from the U.S., China and Russia and postdoctoral colleagues from Australia, France and Japan, we pursued studies of the elastic properties of minerals (and their structural analogues) at high pressures and temperatures. In the 1980s, together with Donald Weidner, we established the Stony Brook High Pressure Laboratory and the Mineral Physics Institute. In 1991, in collaboration with Alexandra Navrotsky at Princeton University and Charles Prewitt at the Geophysical Laboratory, we founded the NSF Science and Technology Center for High Pressure Research.

Table-top nuclear magnetic resonance system for high-pressure studies with in situ laser heating.

High pressure Nuclear Magnetic Resonance (NMR) is known to reveal the behavior of matter under extreme conditions. However, until now, significant maintenance demands, space requirements, and high costs of superconducting magnets render its application unfeasible for regular modern high pressure laboratories. Here, we present a table-top NMR system based on permanent Halbach magnet arrays with a diameter of 25 cm and height of 4 cm. At the highest field of 1013 mT, 1H-NMR spectra of ice VII have been recorded at 25 GPa and ambient temperature. The table-top NMR system can be used together with double sided laser heating setups. Feasibility of high-pressure high-temperature NMR was demonstrated by collecting 1H-NMR spectra of H2O at 25 GPa and 1063(50) K. The change in the signal intensity in a laser-heated NMR diamond anvil cell has been found to yield a convenient way for temperature measurements.

Molecular Dynamics in the Energy Sector: Experiment and Modeling of the CO2/CH4 Mixture

Knowledge of the thermodynamic properties of fluids and their mixtures is fundamental to the design of industrial processes. In the field of tertiary oil and gas production, significant experimental effort to identify properties of compressed gas mixtures has been made worldwide. Often expensive and dangerous high-pressure laboratory methods are used. Consequently, it is important to have a reliable simulation approach that allows exploratory and predictive modeling. In this work, experimental surface tension of a CO2 and CH4 mixture at elevated pressures is presented and discussed. The surface tension is an important quantity in several processes, (e.g., for describing multiphase flow). Molecular dynamics (MD) simulations are utilized to calculate the thermodynamic properties (i.e., surface tension, density, molar fractions, phase diagrams) under process-relevant conditions. MD has the potential to predict the values of these properties and provide insight into the principal behavior of the whole system....

Quantum hydrodynamics for plasmas—Quo vadis?

Quantum plasmas are an important topic in astrophysics and high pressure laboratory physics for more than 50 years. In addition, many condensed matter systems, including the electron gas in metals, metallic nanoparticles, or electron-hole systems in semiconductors and heterostructures, exhibit—to some extent—plasmalike behavior. Among the key theoretical approaches that have been applied to these systems are quantum kinetic theory, Green function theory, quantum Monte Carlo, semiclassical and quantum molecular dynamics, and more recently, density functional theory simulations. These activities are in close contact with the experiments and have firmly established themselves in the fields of plasma physics, astrophysics, and condensed matter physics. About two decades ago, a second branch of quantum plasma theory emerged that is based on a quantum fluid description and has attracted a substantial number of researchers. The focus of these studies has been on collective oscillations and linear and nonlinear waves in quantum plasmas. Even though these papers pretend to address the same physical systems as the more traditional papers mentioned above, the former appear to form a rather closed community that is largely isolated from the rest of the field. The quantum hydrodynamics (QHD) results have—with a few exceptions—not found application in astrophysics or in experiments in condensed matter physics. Moreover, these results practically did not have any impact on the former quantum plasma theory community. One reason is the unknown accuracy of the QHD for dense plasmas. In this paper, we present a novel derivation, starting from reduced density operators that clearly point to the deficiencies of QHD, and we outline possible improvements. It is also to be noted that some of the QHD results have attracted negative attention being criticized as unphysical. Examples include the prediction of “novel attractive forces” between protons in an equilibrium quantum plasma, the notion of “spinning quantum plasmas,” or the new field of “quantum dusty plasmas.” In the present article, we discuss the latter system in some detail because it is a particularly disturbing case of formal theoretical investigations that are detached from physical reality despite bold and unproven claims of importance for, e.g., dense astrophysical plasmas or microelectronics. We stress that these deficiencies are not a problem of QHD itself, which is a powerful and efficient method, but rather are due to ignorance of its properties and limitations. We analyze the common flaws of these works and come up with suggestions to improve the situation of QHD applications to quantum plasmas.

Quantification of oil droplets under high pressure laboratory experiments simulating deep water oil releases and subsea dispersants injection (SSDI)

Limited experimental and field data are available describing oil droplet formation from subsea releases at high pressure. There are also analytical challenges quantifying oil droplets over a wide size and concentrations range at high pressure. This study quantified oil droplets released from an orifice in seawater at low and high pressure (5 m and 1750 m depth). Oil droplet sizes were quantified using a newly developed sensor (Silhouette camera or SilCam).The droplet sizes measured during experiments at low and high pressure, using the same release conditions, showed no significant difference as a function of pressure. This lack of a pressure effect on oil droplet sizes was observed for both untreated oil and for droplet formation during subsea dispersant injection or SSDI. This strongly indicates that the effectiveness of SSDI is not influenced by water depth or pressure, at least for simulated subsea releases of oil alone (no gas).

Lab Scale High-Pressure Equipment for Supercritical Drying

This paper is devoted to the development of high-pressure laboratory equipment for supercritical drying processes. Conducting processes under supercritical conditions requires appropriate high-pressure apparatus. High-pressure apparatus' working part design was developed on the basis of the results of supercritical carbon dioxide hydrodynamics mathematical modeling. To do this, modern computer simulation methods, based on principles of computational fluid dynamics (CFD), were used. Such methods allow to calculate velocity, pressure, physico-chemical properties fields within the apparatus at arbitrary boundary conditions. In addition, it is important to develop process flowsheets that include high-pressure vessels, high-pressure pumps, separators, intermediate tanks, complex shut-off and control valves, a set of instrumentation and automation. The developed laboratory equipment was realized and successfully commissioned. Proposed equipment can be used for studying the kinetics of the supercritical drying process. Such studies are necessary for resource and energy saving, efficiency increasing and scale up.

High Pressure Laboratory, Earth and Planetary Physics Group, Department of Earth and Planetary Systems Science, Hiroshima University

High Pressure Laboratory, Earth and Planetary Physics Group, Department of Earth and Planetary Systems Science, Hiroshima University

The elastic wave velocity response of methane gas hydrate formation in vertical gas migration systems

Knowledge of the elastic wave velocities of hydrate-bearing sediments is important for geophysical exploration and resource evaluation. Methane gas migration processes play an important role in geological hydrate accumulation systems, whether on the seafloor or in terrestrial permafrost regions, and their impact on elastic wave velocities in sediments needs further study. Hence, a high-pressure laboratory apparatus was developed to simulate natural continuous vertical migration of methane gas through sediments. Hydrate saturation (Sh) and ultrasonic P- and S-wave velocities (Vp and Vs) were measured synchronously by time domain reflectometry (TDR) and by ultrasonic transmission methods respectively during gas hydrate formation in sediments. The results were compared to previously published laboratory data obtained in a static closed system. This indicated that the velocities of hydrate-bearing sediments in vertical gas migration systems are slightly lower than those in closed systems during hydrate formation. While velocities increase at a constant rate with hydrate saturation in the closed system, P-wave velocities show a fast–slow–fast variation with increasing hydrate saturation in the vertical gas migration system. The observed velocities are well described by an effective-medium velocity model, from which changing hydrate morphology was inferred to cause the fast–slow–fast velocity response in the gas migration system. Hydrate forms firstly at the grain contacts as cement, then grows within the pore space (floating), then finally grows into contact with the pore walls again. We conclude that hydrate morphology is the key factor that influences the elastic wave velocity response of methane gas hydrate formation in vertical gas migration systems.

東京工業大学 理学院 地球惑星科学系 地球惑星科学コース 太田研究室 (高圧地球科学)

東京工業大学 理学院 地球惑星科学系 地球惑星科学コース 太田研究室 (高圧地球科学)