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Geology topics

I-Ming Chou

Publications and source records attributed to I-Ming Chou.

At least 19 recordsLinked to original sources

Coesite in suevites from the Chesapeake Bay impact structure

The occurrence of coesite in suevites from the Chesapeake Bay impact structure is confirmed within a variety of textural domains in situ by Raman spectroscopy for the first time and in mechanically separated grains by X-ray diffraction. Microtextures of coesite identified in situ investigated under transmitted light and by scanning electron microscope reveal coesite as micrometer-sized grains (1–3 μm) within amorphous silica of impact-melt clasts and as submicrometer-sized grains and polycrystalline aggregates within shocked quartz grains. Coesite-bearing quartz grains are present both idiomorphically with original grain margins intact and as highly strained grains that underwent shock-produced plastic deformation. Coesite commonly occurs in plastically deformed quartz grains within domains that appear brown (toasted) in transmitted light and rarely within quartz of spheroidal texture. The coesite likely developed by a mechanism of solid-state transformation from precursor quartz. Raman spectroscopy also showed a series of unidentified peaks associated with shocked quartz grains that likely represent unidentified silica phases, possibly including a moganite-like phase that has not previously been associated with coesite.

Chesapeake Bay

Raman spectroscopic characterization of CH4 density over a wide range of temperature and pressure

The positions of the CH 4 Raman ν 1 symmetric stretching bands were measured in a wide range of temperature (from −180 °C to 350 °C) and density (up to 0.45 g/cm 3 ) using high-pressure optical cell and fused silica capillary capsule. The results show that the Raman band shift is a function of both methane density and temperature; the band shifts to lower wavenumbers as the density increases and the temperature decreases. An equation representing the observed relationship among the CH 4 ν 1 band position, temperature, and density can be used to calculate the density in natural or synthetic CH 4 -bearing inclusions.

Journal of Raman Spectroscopy

Observations on the crystallization of spodumene from aqueous solutions in a hydrothermal diamond-anvil cell

Crystallization experiments were conducted in a new type of hydrothermal diamond-anvil cell (HDAC; type V) using LiAlSi 2 O 6 (S) gel and H 2 O (W) as starting materials. A total of 21 experiments were performed at temperatures up to 950°C and pressures up to 788 MPa. In the samples with relatively low W/S ratios, many small crystals formed in the melt phase during cooling. In those with high W/S ratios, only a few crystals with smooth surfaces crystallized from the aqueous fluid in the presence of melt droplets, which were gradually consumed during crystal growth, indicating rapid transfer of material from the melt to the crystals through the aqueous fluid. The nucleation of crystals started at 710 (±70)°C and 520 (±80) MPa, and crystal growth ended at 570 (±40)°C and 320 (±90) MPa, with the cooling P-T path within the stability field of spodumene + quartz in the S-W system. The observed linear crystal growth rates in the aqueous phase, calculated by dividing the maximum length of a single crystal by the duration of the entire growth step, were 4.7 × 10 −6 and 5.7 × 10 −6 cm s −1 for the cooling rates of 0.5 and 1°C min −1 , respectively. However, a rapid crystal growth rate of 3.6 × 10 −5 cm s −1 in the aqueous fluid was observed when the components were supplied by nearby melt droplets. Our results show that when crystals nucleate in the aqueous fluid instead of the melt phase, there are fewer nuclei formed, and they grow much faster due to the low viscosity of the aqueous fluid, which accelerates diffusion of components for the growth of crystals. Therefore, the large crystals in granitic pegmatite can crystallize directly from aqueous fluids rather than hydrosilicate melt.

Geofluids

Disproportionation and thermochemical sulfate reduction reactions in S-H 2 0-Ch 4 and S-D 2 O-CH 4 systems from 200 to 340 °C at elevated pressures

Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H 2 O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H 2 O-CH 4 , S-D 2 O-CH 4 , and S-CH 4 -1m ZnBr 2 systems in fused silica capillary capsules (FSCC). After a heating period ranging from 24 to 2160 hours (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H 2 O and S-H 2 O-CH 4 systems, our results showed that (1) the disproportionation of sulfur in the S-H 2 O-CH 4 system occurred at temperatures above 200 °C and produced H 2 S, SO 4 2- , and possibly trace amount of HSO 4- ; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO 2 and H 2 S, and these TSR temperatures are much closer to those of the natural system (<200 °C) than those of any previous experiments; (3) the disproportionation and TSR reactions in the S-H 2 O-CH 4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D 2 O-CH 4 , both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures > 200 °C that can be reached by deep drilling for hydrocarbon resources.

Geochimica et Cosmochimica Acta

The stability of sulfate and hydrated sulfate minerals near ambient conditions and their significance in environmental and planetary sciences

Sulfate and hydrated sulfate minerals are abundant and ubiquitous on the surface of the Earth and also on other planets and their satellites. The humidity-buffer technique has been applied to study the stability of some of these minerals at 0.1 MPa in terms of temperature-relative humidity space on the basis of hydration-dehydration reversal experiments. Updated phase relations in the binary system MgSO 4 -H 2 O are presented, as an example, to show how reliable thermodynamic data for these minerals could be obtained based on these experimental results and thermodynamic principles. This approach has been applied to sulfate and hydrated sulfate minerals of other metals, including Fe (both ferrous and ferric), Zn, Ni, Co, Cd, and Cu. Metal-sulfate salts play important roles in the cycling of metals and sulfate in terrestrial systems, and the number of phases extends well beyond the simple sulfate salts that have thus far been investigated experimentally. The oxidation of sulfide minerals, particularly pyrite, is a common process that initiates the formation of efflorescent metal-sulfate minerals. Also, the overall abundance of iron-bearing sulfate salts in nature reflects the fact that the weathering of pyrite or pyrrhotite is the ultimate source for many of these phases. Many aspects of their environmental significance are reviewed, particularly in acute effects to aquatic ecosystems related to the dissolution of sulfate salts during rain storms or snow-melt events. Hydrous Mg, Ca, and Fe sulfates were identified on Mars, with wide distribution and very large quantities at many locations, on the basis of spectroscopic observations from orbital remote sensing and surface explorations by rovers. However, many of these findings do not reveal the detailed information on the degree of hydration that is essential for rigorous interpretation of the hydrologic history of Mars. Laboratory experiments on stability fields, reactions pathways, and reaction rates of hydrous sulfates likely to be found on Mars enhance our understanding of the degrees of hydration of various sulfates that should currently exist on Mars at various seasons and locations and during various atmospheric pressure and obliquity periods. Two sets of systematic experiments were described; one on hydrous Mg sulfates and the other on hydrous Fe 3+ sulfates. Also, their implications to Mars sulfates mineralogy were discussed.

Journal of Asian Earth Sciences

Chapter 7: The hydrothermal diamond anvil cell (HDAC) for Raman spectroscopic studies of geological fluids at high pressures and temperatures

In this chapter, we describe the hydrothermal diamond-anvil cell (HDAC), which is specifically designed for experiments on systems with aqueous fluids to temperatures up to ~1000ºC and pressures up to a few GPa to tens of GPa. This cell permits optical observation of the sample and the in situ determination of properties by ‘photon-in photon-out’ techniques such as Raman spectroscopy. Several methods for pressure measurement are discussed in detail including the Raman spectroscopic pressure sensors a-quartz, berlinite, zircon, cubic boron nitride (c-BN), and 13 C-diamond, the fluorescence sensors ruby (α-Al 2 O 3 :Cr 3+ ), Sm:YAG (Y 3 Al 5 O 12 :Sm 3+ ) and SrB 4 O 7 :Sm 2+ , and measurements of phase-transition temperatures. Furthermore, we give an overview of published Raman spectroscopic studies of geological fluids to high pressures and temperatures, in which diamond anvil cells were applied.

Book chapter

The Hydrothermal Diamond Anvil Cell (HDAC) for raman spectroscopic studies of geologic fluids at high pressures and temperatures

In this chapter, we describe the hydrothermal diamond-anvil cell (HDAC), which is specifically designed for experiments on systems with aqueous fluids to temperatures up to ⬚~1000&ordm;C and pressures up to a few GPa to tens of GPa. This cell permits optical observation of the sample and the in situ determination of properties by &lsquo;photon-in photon-out&rsquo; techniques such as Raman spectroscopy. Several methods for pressure measurement are discussed in detail including the Raman spectroscopic pressure sensors a-quartz, berlinite, zircon, cubic boron nitride (c-BN), and 13C-diamond, the fluorescence sensors ruby (&alpha;-Al2O3:Cr3+), Sm:YAG (Y3Al5O12:Sm3+) and SrB4O7:Sm2+, and measurements of phase-transition temperatures. Furthermore, we give an overview of published Raman spectroscopic studies of geological fluids to high pressures and temperatures, in which diamond anvil cells were applied.

Book chapter

Structural stability of methane hydrate at high pressures

The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil cells. The diffraction data for types II (sII) and H (sH) were refined to the known structures with space groups Fd 3 m and P 6 3 / mmc , respectively. Upon compression, sI methane hydrate transforms to the sII phase at 120 MPa, and then to the sH phase at 600 MPa. The sII methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm 3 m structure and ice VII ( Pn 3 m ). The results highlight the role of guest (CH 4 )-host (H 2 O) interactions in the stabilization of the hydrate structures under pressure.

Geoscience Frontiers

Monoclinic tridymite in clast-rich impact melt rock from the Chesapeake Bay impact structure

X-ray diffraction and Raman spectroscopy confirm a rare terrestrial occurrence of monoclinic tridymite in clast-rich impact melt rock from the Eyreville B drill core in the Chesapeake Bay impact structure. The monoclinic tridymite occurs with quartz paramorphs after tridymite and K-feldspar in a microcrystalline groundmass of devitrified glass and Fe-rich smectite. Electron-microprobe analyses revealed that the tridymite and quartz paramorphs after tridymite contain different amounts of chemical impurities. Inspection by SEM showed that the tridymite crystal surfaces are smooth, whereas the quartz paramorphs contain irregular tabular voids. These voids may represent microporosity formed by volume decrease in the presence of fluid during transformation from tridymite to quartz, or skeletal growth in the original tridymite. Cristobalite locally rims spherulites within the same drill core interval. The occurrences of tridymite and cristobalite appear to be restricted to the thickest clast-rich impact melt body in the core at 1402.02–1407.49 m depth. Their formation and preservation in an alkali-rich, high-silica melt rock suggest initially high temperatures followed by rapid cooling.

American Mineralogist

The speciation of aqueous zinc(II) bromide solutions to 500 °C and 900 MPa determined using Raman spectroscopy

A Raman spectral study was carried out on 3 solutions of varying concentration and bromide/zinc ratios. Spectra were collected at 11 different temperature-pressure conditions ranging from ambient to 500????C-0.9??GPa. Raman band assignments for zinc(II) bromide species reported in previous studies were used to determine the relative concentrations of ZnBr42-, ZnBr3-, ZnBr2, and ZnBr+ species at various temperatures and pressures. Our results are in close agreement with X-ray absorption spectroscopic (XAS) data, and confirm that the tetrabromo zinc(II) complex, ZnBr42-, is the predominant species up to 500????C in solutions having high Zn concentrations (1??m) and high bromide/zinc molar ratios ([Br]/[Zn] = 8). In agreement with previous solubility and Raman spectroscopic experiments, our measurements indicate that species with a lower number of halide ligands and charge are favored with increasing temperature in dilute solutions, and solutions with low bromide/zinc ratios ([Br]/[Zn] < 2.5). The Raman technique provides an independent experimental means of evaluating the quality of XAS analyses of data obtained from high temperature disordered systems. The combination of these two techniques provides complementary data on speciation and the structure of zinc(II) bromide complexes. The preponderance of the ZnBr42- species in highly saline brines at high temperature is consistent with the predominance of ZnCl42- in chloride-rich brines reported in previous XAS studies. Knowledge of Zn complexing in metal-rich highly saline brines is important for numerical models of ore deposition in high temperature systems such as skarns and porphyry-type deposits. ?? 2008 Elsevier B.V.

Chemical Geology

Determination of diffusion coefficients of hydrogen in fused silica between 296 and 523 K by Raman spectroscopy and application of fused silica capillaries in studying redox reactions

Diffusion coefficients ( D ) of hydrogen in fused silica capillaries (FSC) were determined between 296 and 523 K by Raman spectroscopy using CO 2 as an internal standard. FSC capsules (3.25 × 10 −4 m OD, 9.9 × 10 −5 m ID, and ∼0.01 m long) containing CO 2 and H 2 were prepared and the initial relative concentrations of hydrogen in these capsules were derived from the Raman peak-height ratios between H 2 (near 587 cm −1 ) and CO 2 (near 1387 cm −1 ). The sample capsules were then heated at a fixed temperature ( T ) at one atmosphere to let H 2 diffuse out of the capsule, and the changes of hydrogen concentration were monitored by Raman spectroscopy after quench. This process was repeated using different heating durations at 296 (room T ), 323, 375, 430, 473, and 523 K; the same sample capsule was used repeatedly at each temperature. The values of D (in m 2 s −1 ) in FSC were obtained by fitting the observed changes of hydrogen concentration in the FSC capsule to an equation based on Fick’s law. Our D values are in good agreement with the more recent of the two previously reported experimental data sets, and both can be represented by: ln D = - ( 16.471 &#xB1; 0.035 ) - 44589 &#xB1; 139 RT ( R 2 = 0.99991 ) "> lnD=-(16.471±0.035)-44589±139RT(R2=0.99991) where R is the gas constant (8.3145 J/mol K), T in Kelvin, and errors at 1 σ level. The slope corresponds to an activation energy of 44.59 ± 0.14 kJ/mol. The D in FSC determined at 296 K is about an order of magnitude higher than that in platinum at 723 K, indicating that FSC is a suitable membrane for hydrogen at temperature between 673 K and room temperature, and has a great potential for studying redox reactions at these temperatures, especially for systems containing organic material and/or sulphur.

Geochimica et Cosmochimica Acta

Diamond dissolution and the production of methane and other carbon-bearing species in hydrothermal diamond-anvil cells

Raman analysis of the vapor phase formed after heating pure water to near critical (355–374 °C) temperatures in a hydrothermal diamond-anvil cell (HDAC) reveals the synthesis of abiogenic methane. This unexpected result demonstrates the chemical reactivity of diamond at relatively low temperatures. The rate of methane production from the reaction between water and diamond increases with increasing temperature and is enhanced by the presence of a metal gasket (Re, Ir, or Inconel) which is compressed between the diamond anvils to seal the aqueous sample. The minimum detection limit for methane using Raman spectroscopy was determined to be ca . 0.047 MPa, indicating that more than 1.4 nanograms (or 8.6 × 10 −11 mol) of methane were produced in the HDAC at 355 °C and 30 MPa over a period of ten minutes. At temperatures of 650 °C and greater, hydrogen and carbon dioxide were detected in addition to methane. The production of abiogenic methane, observed in all HDAC experiments where a gasket was used, necessitates a reexamination of the assumed chemical systems and intensive parameters reported in previous hydrothermal investigations employing diamonds. The results also demonstrate the need to minimize or eliminate the production of methane and other carbonic species in experiments by containing the sample within a HDAC without using a metal gasket.

Geochimica et Cosmochimica Acta

Spectral reflectance properties (0.4-2.5 um) of secondary Fe-oxide, Fe-hydroxide, and Fe-sulfate-hydrate minerals associated with sulfide-bearing mine waste

Fifteen Fe-oxide, Fe-hydroxide, and Fe-sulphate-hydrate mineral species commonly associated with sulphide bearing mine wastes were characterized by using X-ray powder diffraction and scanning electron microscope methods. Diffuse reflectance spectra of the samples show diagnostic absorption features related to electronic processes involving ferric and/or ferrous iron, and to vibrational processes involving water and hydroxyl ions. Such spectral features enable field and remote sensing based studies of the mineral distributions. Because secondary minerals are sensitive indicators of pH, Eh, relative humidity, and other environmental conditions, spectral mapping of these minerals promises to have important applications to mine waste remediation studies. This report releases digital (ascii) spectra (spectral_data_files.zip) of the fifteen mineral samples to facilitate usage of the data with spectral libraries and spectral analysis software. The spectral data are provided in a two-column format listing wavelength (in micrometers) and reflectance, respectively.

Open-File Report

The stability and Raman spectra of ikaite, CaCO 3 ·6H 2 O, at high pressure and temperature

Raman analyses of single crystals of ikaite, CaCO 3 &middot;6H 2 O, synthesized in a diamond-anvil cell at ambient temperature yield spectra from 0.14 to 4.08 GPa; the most intense peaks are at 228 and 1081 cm &minus;1 corresponding to E g (external) and A 1 g (internal) modes of vibrations in CO 2&minus; 3 ions, respectively. These are in good agreement with Raman spectra previously published for ikaite in powder form at ambient temperature and pressure. Visual observations of a sample consisting initially of a mixture of calcite + water in a hydrothermal diamond-anvil cell yielded a P-T phase diagram up to 2 GPa and 120 &deg;C; the boundary for the reaction ikaite &harr; aragonite + water has a positive slope and is curved convexly toward the aragonite + water field similar to typical melt curves. This curvature can be explained in terms of the Clapeyron equation for a boundary between a solid phase and a more compressible liquid phase or largely liquid phase assemblage.

American Mineralogist

Thermodynamic data for modeling acid mine drainage problems: compilation and estimation of data for selected soluble iron-sulfate minerals

Enthalpy of formation, Gibbs energy of formation, and entropy values have been compiled from the literature for the hydrated ferrous sulfate minerals melanterite, rozenite, and szomolnokite, and a variety of other hydrated sulfate compounds. On the basis of this compilation, it appears that there is no evidence for an excess enthalpy of mixing for sulfate-H2O systems, except for the first H2O molecule of crystallization. The enthalpy and Gibbs energy of formation of each H2O molecule of crystallization, except the first, in the iron(II) sulfate - H2O system is -295.15 and -238.0 kJ?mol-1, respectively. The absence of an excess enthalpy of mixing is used as the basis for estimating thermodynamic values for a variety of ferrous, ferric, and mixed-valence sulfate salts of relevance to acid-mine drainage systems.

Open-File Report