Geology topics

I.-M. Chou

Publications and source records attributed to I.-M. Chou.

At least 19 recordsLinked to original sources

USGS2022

Spectral reflectance properties (0.4-2.5 μm) of secondary Fe-oxide, Fe-hydroxide, and Fe-sulphate-hydrate minerals associated with sulphide-bearing mine wastes

Diffuse reflectance spectra of 15 mineral species commonly associated with sulphide-bearing mine wastes show diagnostic absorption bands related to electronic processes involving ferric and/or ferrous iron, and to vibrational processes involving water and hydroxyl. Many of these absorption bands are relatively broad and overlapping; however, spectral analysis methods, including continuum removal and derivative analysis, permit most of the minerals to be distinguished. Key spectral differences between the minerals are illustrated in a series of plots showing major absorption band centres and other spectral feature positions. Because secondary iron minerals are sensitive indicators of pH, Eh, relative humidity, and other environmental conditions, spectral mapping of mineral distributions promises to have important application to mine waste remediation studies.

Geochemistry: Exploration, Environment, Analysis↗

USGS2013

Determination of diffusion coefficients of carbon dioxide in water between 268 and 473 K in a high-pressure capillary optical cell with in situ Raman spectroscopic measurements

Accurate values of diffusion coefficients for carbon dioxide in water and brine at reservoir conditions are essential to our understanding of transport behavior of carbon dioxide in subsurface pore space. However, the experimental data are limited to conditions at low temperatures and pressures. In this study, diffusive transfer of carbon dioxide in water at pressures up to 45 MPa and temperatures from 268 to 473 K was observed within an optical capillary cell via time-dependent Raman spectroscopy. Diffusion coefficients were estimated by the least-squares method for the measured variations in carbon dioxide concentration in the cell at various sample positions and time. At the constant pressure of 20 MPa, the measured diffusion coefficients of carbon dioxide in water increase with increasing temperature from 268 to 473 K. The relationship between diffusion coefficient of carbon dioxide in water [D(CO 2 ) in m 2 /s] and temperature (T in K) was derived with Speedy–Angell power-law approach as: D(CO 2 )=D 0 [T/Ts-1] m where D 0 = 13.942 × 10 −9 m 2 /s, Ts = 227.0 K, and m = 1.7094. At constant temperature, diffusion coefficients of carbon dioxide in water decrease with pressure increase. However, this pressure effect is rather small (within a few percent).

Geochimica et Cosmochimica Acta↗

USGS2011

Stability of Mg-sulfates at-10C and the rates of dehydration/rehydration processes under conditions relevant to Mars

We report the results of low temperature (−10°C) experiments on the stability fields and phase transition pathways of five hydrous Mg-sulfates. A low temperature form of MgSO 4 ·7H 2 O (LT-7w) was found to have a wide stability field that extends to low relative humidity (∼13% RH at −10°C). Using information on the timing of phase transitions, we extracted information on the reaction rates of five important dehydration and rehydration processes. We found that the temperature dependencies of rate constants for dehydration processes differ from those of rehydration, which reflect differences in reaction mechanisms. By extrapolating these rate constants versus T correlations into the T range relevant to Mars, we can evaluate the possibility of occurrence of specific processes and the presence of common Mg-sulfate species present on Mars in different periods and locations. We anticipate in a moderate obliquity period, starkeyite and LH-MgSO 4 ·H 2 O should be two common Mg-sulfates at the surface, another polymorph MH-MgSO 4 ·H 2 O can exist at the locations where hydrothermal processes may have occurred. In polar regions or within the subsurface of other regions, meridianiite (coexisting with water ice, near 100% RH) and LT-7w (over a large RH range) are the stable phases. During a high obliquity period, meridianiite and LT-7w should exhibit widespread occurrence. The correlations of reaction rates versus temperature found in this study imply that dehydration and rehydration of hydrous Mg-sulfates would always be slower than the sublimation and crystallization of water ice, which would be supported by mission observations from Odyssey and by Mars Exploration Rovers.

Journal of Geophysical Research E: Planets↗

USGS2011

Experimental determination of the phase boundary between kornelite and pentahydrated ferric sulfate at 0.1MPa

Recent findings of various ferric sulfates on Mars emphasize the importance of understanding the fundamental properties of ferric sulfates at temperatures relevant to that of Martian surface. In this study, the phase boundary between kornelite (Fe2(SO4)3.7H2O) and pentahydrated ferric sulfate (Fe2(SO4)3.5H2O) was experimentally determined using the humidity-buffer technique together with gravimetric measurements and Raman spectroscopy at 0.1MPa in the 36-56??C temperature range. Through the thermodynamic analysis of our experimental data, the enthalpy change (-290.8??0.3kJ/mol) and the Gibbs free energy change (-238.82??0.02kJ/mol) for each water molecule of crystallization in the rehydration of pentahydrated ferric sulfate to kornelite were obtained. ?? 2011 Elsevier B.V.

Chemical Geology↗

USGS2010

Pressure calibrants in the hydrothermal diamond-anvil cell

Based on the equation of state of water (EOSW), experimental pressure in the hydrothermal diamond-anvil cell (HDAC) using pure water or dilute aqueous solutions as a pressure medium can be accurately determined at each measured temperature. Consequently, meaningful interpretations can be obtained for observations in the HDAC, which has been widely accepted as a versatile, modern apparatus for hydrothermal experiments. However, this is not true when other pressure media were used because there is no reliable way to determine experimental pressure other than the use of in situ pressure sensors. Most of the available pressure sensors are difficult to apply because they either require expensive facilities to perform the measurements or are unable to provide the accuracy needed for the interpretation of hydrothermal experiments. The only exception is to use the interferometric method to detect the ??-?? quartz transition, although such applications are limited to temperatures above 573??C. In this study, three pressure calibrants were calibrated for applications at lower temperatures, and they were based on visual observation of the ferroelastic phase transitions in BaTiO3 (tetragonal/cubic), Pb3(PO4)2 (monoclinic/trigonal), and PbTiO3 (tetragonal/cubic). For the phase transitions in BaTiO3 and Pb3(PO4)2, the temperature at which twinning disappears during heating was taken as the transition temperature (Ttr); the phase transition pressures (Ptr) can be calculated, respectively, from Ptr (MPa; ??3%) = 0.17 - 21.25 [(Ttr) - 115.3], and Ptr (MPa; ??2%) = 1.00 - 10.62 [(Ttr) - 180.2], where Ttr is in ??C. For the phase transition in PbTiO3, the temperature at which the movement of phase front begins (or ends) on heating (or cooling) was taken as the transition temperature (Ttr,h or Ttr,c), and the phase transition pressures on heating (Ptr,h) and cooling (Ptr,c) can be calculated from Ptr,h (MPa; ??4%) = 7021.7 - 14.235 (Ttr,h), and Ptr,c (MPa; ??4%) = 6831.3 - 14.001 (Ttr,c). Phase transitions for these three pressure calibrants are easy to detect visually, and their P-T phase boundaries have negative slopes and intersect isochors of most of the geologic fluids at high angles and, therefore, are easy to apply. Copyright ?? 2007 by V. H. Winston & Son, Inc. All rights reserved.

International Geology Review↗

USGS2009

Steric hindrance and the enhanced stability of light rare-earth elements in hydrothermal fluids

A series of X-ray absorption spectroscopy (XAS) experiments were made to determine the structure and stability of aqueous REE (La, Nd, Gd, and Yb) chloride complexes to 500 ??C and 520 MPa. The REE 3+ ions exhibit inner-sphere chloroaqua complexation with a steady increase of chloride coordination with increasing temperature in the 150 to 500 ??C range. Furthermore, the degree of chloride coordination of REE 3+ inner-sphere chloroaqua complexes decreases significantly from light to heavy REE. These results indicate that steric hindrance drives the reduction of chloride coordination of REE 3+ inner-sphere chloroaqua complexes from light to heavy REE. This results in greater stability and preferential transport of light REE 3+ over heavy REE 3+ ions in saline hydrothermal fluids. Accordingly, the preferential mobility of light REE directly influences the relative abundance of REE in rocks and minerals and thus needs to be considered in geochemical modeling of petrogenetic and ore-forming processes affected by chloride-bearing hydrothermal fluids.

American Mineralogist↗

USGS2009

Mineralogy of mine waste at the Vermont Asbestos Group mine, Belvidere Mountain, Vermont

Samples from the surfaces of waste piles at the Vermont Asbestos Group mine in northern Vermont were studied to determine their mineralogy, particularly the presence and morphology of amphiboles. Analyses included powder X-ray diffraction (XRD), optical microscopy, scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and Raman spectroscopy. Minerals identified by XRD were serpentine-group minerals, magnetite, chlorite, quartz, olivine, pyroxene, and brucite; locally, mica and carbonates were also present. Raman spectroscopy distinguished antigorite and chrysotile, which could not be differentiated using XRD. Long-count, short-range XRD scans of the (110) amphibole peak showed trace amounts of amphibole in most samples. Examination of amphiboles in tailings by optical microscopy, SEM, and EPMA revealed non-fibrous amphiboles compositionally classified as edenite, magnesiohornblende, magnesiokatophorite, and pargasite. No fibrous amphibole was found in the tailings, although fibrous tremolite was identified in a sample of host rock. Knowledge of the mineralogy at the site may lead to better understanding of potential implications for human health and aid in designing a remediation plan.

American Mineralogist↗

USGS2009

The structure and stability of aqueous rare-earth elements in hydrothermal fluids: New results on neodymium(III) aqua and chloroaqua complexes in aqueous solutions to 500 °C and 520 MPa

X-ray absorption spectroscopy (XAS) measurements were made at the Nd L3-edge on neodymium(III) aqua and chloroaqua complexes in low pH aqueous solutions from 25 to 500????C and up to 520??MPa. Analysis of the extended X-ray absorption fine structure of the XAS spectra measured from a 0.07??m Nd/0.16??m HNO3 aqueous solution reveals a contraction of the Nd-O distance of the Nd3+ aqua ion at a uniform rate of ~ 0.013????/100????C and a uniform reduction of the number of coordinated H2O molecules from 10.0 ?? 0.9 to 7.4 ?? 0.9 over the range from 25 to 500????C and up to 370??MPa. The rate of reduction of the first-shell water molecules with temperature for Nd3+ (26%) is intermediate between the rate for the Gd3+ aqua ion (22% from 25 to 500????C) and the rates for the Eu3+ (29% from 25 to 400????C) and the Yb3+ aqua ions (42% from 25 to 500????C) indicating an intermediate stability of the Nd3+ aqua ion consistent with the tetrad effect. Nd L3-edge XAS measurements of 0.05??m NdCl3 aqueous solution at 25 to 500????C and up to 520??MPa show that stepwise inner-sphere complexes most likely of the type Nd(H2O)?? - nCln+3 - n occur in the solution at elevated temperatures, where ?? ??? 9 at 150????C decreasing to ~ 6 at 500????C and the number of chloride ions (n) of the chloroaqua complexes increases uniformly with temperature from 1.2 ?? 0.2 to 2.0 ?? 0.2 in the solution upon increase of temperature from 150 to 500????C. Conversely, the number of H2O ligands of Nd(H2O)?? - nCln+3 - n complexes is uniformly reduced with temperature from 7.5 ?? 0.8 to 3.7 ?? 0.3 in the aqueous solution, in the same temperature range. These data show greater stability of neodymium(III) than gadolinium(III) and ytterbium(III) chloride complexes in low pH aqueous solutions at elevated temperatures. Our data suggest a greater stability of aqueous light REE than that of heavy REE chloride complexes in low pH fluids at elevated temperatures consistent with REE analysis of fluids from deep-sea hydrothermal vents. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS2009

Evolution of crystalline target rocks and impactites in the chesapeake bay impact structure, ICDP-USGS eyreville B core

The 1766-m-deep Eyreville B core from the late Eocene Chesapeake Bay impact structure includes, in ascending order, a lower basement-derived section of schist and pegmatitic granite with impact breccia dikes, polymict impact breccias, and cataclas tic gneiss blocks overlain by suevites and clast-rich impact melt rocks, sand with an amphibolite block and lithic boulders, and a 275-m-thick granite slab overlain by crater-fill sediments and postimpact strata. Graphite-rich cataclasite marks a detachment fault atop the lower basement-derived section. Overlying impactites consist mainly of basement-derived clasts and impact melt particles, and coastal-plain sediment clasts are underrepresented. Shocked quartz is common, and coesite and reidite are confirmed by Raman spectra. Silicate glasses have textures indicating immiscible melts at quench, and they are partly altered to smectite. Chrome spinel, baddeleyite, and corundum in silicate glass indicate high-temperature crystallization under silica undersaturation. Clast-rich impact melt rocks contain α-cristobalite and monoclinic tridymite. The impactites record an upward transition from slumped ground surge to melt-rich fallback from the ejecta plume. Basement-derived rocks include amphibolite-facies schists, greenschist(?)-facies quartz-feldspar gneiss blocks and subgreenschist-facies shale and siltstone clasts in polymict impact breccias, the amphibolite block, and the granite slab. The granite slab, underlying sand, and amphibolite block represent rock avalanches from inward collapse of unshocked bedrock around the transient crater rim. Gneissic and massive granites in the slab yield U-Pb sensitive high-resolution ion microprobe (SHRIMP) zircon dates of 615 ± 7 Ma and 254 ± 3 Ma, respectively. Postimpact heating was <~350 °C in the lower basement-derived section based on undisturbed 40 Ar/ 39 Ar plateau ages of muscovite and <~150 °C in sand above the suevite based on 40 Ar/ 39 Ar age spectra of detrital microcline.

Special Papers of the Geological Society of Americ↗

USGS2009

Producing fired bricks using coal slag from a gasification plant in indiana

Integrated gasification combined cycle (IGCC) is a promising power generation technology which increases the efficiency of coal-to-power conversion and enhances carbon dioxide concentration in exhaust emissions for better greenhouse gas capture. Two major byproducts from IGCC plants are bottom slag and sulfur. The sulfur can be processed into commercially viable products, but high value applications need to be developed for the slag material in order to improve economics of the process. The purpose of this study was to evaluate the technical feasibility of incorporating coal slag generated by the Wabash River IGCC plant in Indiana as a raw material for the production of fired bricks. Full-size bricks containing up to 20 wt% of the coal slag were successfully produced at a bench-scale facility. These bricks have color and texture similar to those of regular fired bricks and their water absorption properties met the ASTM specifications for a severe weathering grade. Other engineering properties tests, including compressive strength tests, are in progress.

Conference Paper↗

USGS2008

A short working distance multiple crystal x-ray spectrometer

For x-ray spot sizes of a few tens of microns or smaller, a millimeter-sized flat analyzer crystal placed ???1 cm from the sample will exhibit high energy resolution while subtending a collection solid angle comparable to that of a typical spherically bent crystal analyzer (SBCA) at much larger working distances. Based on this observation and a nonfocusing geometry for the analyzer optic, we have constructed and tested a short working distance (SWD) multicrystal x-ray spectrometer. This prototype instrument has a maximum effective collection solid angle of 0.14 sr, comparable to that of 17 SBCA at 1 m working distance. We find good agreement with prior work for measurements of the Mn K?? x-ray emission and resonant inelastic x-ray scattering for MnO, and also for measurements of the x-ray absorption near-edge structure for Dy metal using L??2 partial-fluorescence yield detection. We discuss future applications at third- and fourth-generation light sources. For concentrated samples, the extremely large collection angle of SWD spectrometers will permit collection of high-resolution x-ray emission spectra with a single pulse of the Linac Coherent Light Source. The range of applications of SWD spectrometers and traditional multi-SBCA instruments has some overlap, but also is significantly complementary. ?? 2008 American Institute of Physics.

Review of Scientific Instruments↗

USGS2008

Containment of fluid samples in the hydrothermal diamond-anvil cell without the use of metal gaskets: Performance and advantages for in situ analysis

Metal gaskets (Re, Ir, Inconel, or stainless steel) normally used to contain fluid samples in the hydrothermal diamond-anvil cell (HDAC) are sometimes undesirable due to possible contamination and to gasket deformation at high pressures and temperatures resulting in nonisochoric behavior. Furthermore, in x-ray spectroscopic experiments, metal gaskets may attenuate the incident x-ray beam and emitted fluorescence x-rays, and the interaction of scattered radiation with the gasket may produce fluorescence that interferes with the x-ray spectrum of the sample. New arrangements and procedures were tested for the operation of the HDAC without using the metal gaskets. Distilled, de-ionized water was loaded into the sample chamber, a laser-milled recess 300 ??m in diameter and ???50 ??m deep centered in the 1.0 mm face of the lower diamond anvil, and sealed by pressing the top diamond anvil face directly against the lower one without a metal gasket in between. A maximum sample pressure of 202 MPa at 617 ??C was maintained for a duration of 10 min without evidence of leakage. A small change in fluid density was observed in one experiment where the sample was held at 266 MPa at 708 ??C for 10 min. The gasketless HDAC was also employed in x-ray absorption spectroscopy experiments, where, in addition to the sample chamber in the lower diamond, two grooves were milled at a 90?? angle to each other around the sample chamber to minimize the attenuation of incident and fluorescent x rays. With a minimum distance between the sample chamber and the grooves of 80 ??m, a pressure of 76 MPa at 500 ??C was maintained for 2 h with no change in the original fluid density. ?? 2008 American Institute of Physics.

Review of Scientific Instruments↗

USGS2008

In situ Raman spectroscopic investigation of the structure of subduction-zone fluids

In situ Raman spectra of synthetic subduction-zone fluids (KAlSi3O8-H2O system) were measured to 900?? and 2.3 GPa using a hydrothermal diamond-anvil cell. The structures of aqueous fluid and hydrous melt become closer when conditions approach the second critical endpoint. Almost no three-dimensional network was observed in the supercritical fluid above 2 GPa although a large amount of silicate component is dissolved, suggesting that the physical and chemical properties of these phases change drastically at around the second critical endpoint. Our experimental results indicate that the fluids released from a subducting slab change from aqueous fluid to supercritical fluid with increasing depth under the volcanic arcs. Copyright 2008 by the American Geophysical Union.

Journal of Geophysical Research B: Solid Earth↗

USGS2008

Determination of methane concentrations in water in equilibrium with sI methane hydrate in the absence of a vapor phase by in situ Raman spectroscopy

Most submarine gas hydrates are located within the two-phase equilibrium region of hydrate and interstitial water with pressures (P) ranging from 8 to 60 MPa and temperatures (T) from 275 to 293 K. However, current measurements of solubilities of methane in equilibrium with hydrate in the absence of a vapor phase are limited below 20 MPa and 283.15 K, and the differences among these data are up to 30%. When these data were extrapolated to other P-T conditions, it leads to large and poorly known uncertainties. In this study, in situ Raman spectroscopy was used to measure methane concentrations in pure water in equilibrium with sI (structure one) methane hydrate, in the absence of a vapor phase, at temperatures from 276.6 to 294.6 (??0.3) K and pressures at 10, 20, 30 and 40 (??0.4%) MPa. The relationship among concentration of methane in water in equilibrium with hydrate, in mole fraction [X(CH4)], the temperature in K, and pressure in MPa was derived as: X(CH4) = exp [11.0464 + 0.023267 P - (4886.0 + 8.0158 P)/T]. Both the standard enthalpy and entropy of hydrate dissolution at the studied T-P conditions increase slightly with increasing pressure, ranging from 41.29 to 43.29 kJ/mol and from 0.1272 to 0.1330 kJ/K ?? mol, respectively. When compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by sampling and ex situ analysis, (2) it is simple and efficient, and (3) high-pressure data can be obtained safely. ?? 2007 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗

USGS2008

A new method for synthesizing fluid inclusions in fused silica capillaries containing organic and inorganic material

Considerable advances in our understanding of physicochemical properties of geological fluids and their roles in many geological processes have been achieved by the use of synthetic fluid inclusions. We have developed a new method to synthesize fluid inclusions containing organic and inorganic material in fused silica capillary tubing. We have used both round (0.3 mm OD and 0.05 or 0.1 mm ID) and square cross-section tubing (0.3 ?? 0.3 mm with 0.05 ?? 0.05 mm or 0.1 ?? 0.1 mm cavities). For microthermometric measurements in a USGS-type heating-cooling stage, sample capsules must be less than 25 mm in length. The square-sectioned capsules have the advantage of providing images without optical distortion. However, the maximum internal pressure (P; about 100 MPa at 22 ??C) and temperature (T; about 500 ??C) maintained by the square-sectioned capsules are less than those held by the round-sectioned capsules (about 300 MPa at room T, and T up to 650 ??C). The fused silica capsules can be applied to a wide range of problems of interest in fluid inclusion and hydrothermal research, such as creating standards for the calibration of thermocouples in heating-cooling stages and frequency shifts in Raman spectrometers. The fused silica capsules can also be used as containers for hydrothermal reactions, especially for organic samples, including individual hydrocarbons, crude oils, and gases, such as cracking of C18H38 between 350 and 400 ??C, isotopic exchanges between C18H38 and D2O and between C19D40 and H2O at similar temperatures. Results of these types of studies provide information on the kinetics of oil cracking and the changes of oil composition under thermal stress. When compared with synthesis of fluid inclusions formed by healing fractures in quartz or other minerals or by overgrowth of quartz at elevated P-T conditions, the new fused-silica method has the following advantages: (1) it is simple; (2) fluid inclusions without the presence of water can be formed; (3) synthesized inclusions are large and uniform, and they are able to tolerate high internal P; (4) it is suitable for the study of organic material; and (5) redox control is possible due to high permeability of the fused silica to hydrogen.

Geochimica et Cosmochimica Acta↗

USGS2007

Magnesium and calcium sulfate stabilities and the water budget of Mars

Magnesium sulfate probably plays a dominant role in the water cycle of Mars away from the polar ice caps through hydration and dehydration reactions. This prominence is due to its abundance, its occurrence in numerous hydration states, and its ability to hydrate and dehydrate rapidly. New experimental studies on the metastable reaction between hexahydrite (MgSO4??6H2O) and starkeyite (MgSO4-4H2O) as a function of temperature and relative humidity, supplemented by recent investigations of the stable reaction between epsomite (MgSO4??7H2O) and hexahydrite and by phase equilibrium calculations, suggest that the most important magnesium sulfate phases involved in the Martian water cycle are MgSO4??11 H2O, epsomite, starkeyite, and possibly kieserite (MgSO4??H2O). Hexahydrite is not predicted to be stable on the surface of Mars. During diurnal variations in temperature and relative humidity, 1 kg of MgSO4 can release or remove from the atmosphere 1.5 kg of H2O by cycling between kieserite and MgSO4??11 H2O. Despite subequal abundances of calcium sulfate, calcium sulfates are not likely to be important in the water cycle of the planet because of sluggish rates of hydration and dehydration and a more limited range of H2O concentrations per kilogram of CaSO4 (0.00 to 0.26 kg kg-1). Modern or recent erosion on Mars attributed to liquid water may be due to the dehydration Of MgSO4??11 H2O because of the inferred abundance and likelihood of occurrence of this phase and its limited stability relative to known variations in temperature and relative humidity.

Journal of Geophysical Research E: Planets↗

USGS2007

Synchrotron x-ray spectroscopy of EuHN O3 aqueous solutions at high temperatures and pressures and Nb-bearing silicate melt phases coexisting with hydrothermal fluids using a modified hydrothermal diamond anvil cell and rail assembly

A modified hydrothermal diamond anvil cell (HDAC) rail assembly has been constructed for making synchrotron x-ray absorption spectroscopy, x-ray fluorescence, and x-ray mapping measurements on fluids or solid phases in contact with hydrothermal fluids up to ???900??C and 700 MPa. The diamond anvils of the HDAC are modified by laser milling grooves or holes, for the reduction of attenuation of incident and fluorescent x rays and sample cavities. The modified HDAC rail assembly has flexibility in design for measurement of light elements at low concentrations or heavy elements at trace levels in the sample and the capability to probe minute individual phases of a multiphase fluid-based system using focused x-ray microbeam. The supporting rail allows for uniform translation of the HDAC, rotation and tilt stages, and a focusing mirror, which is used to illuminate the sample for visual observation using a microscope, relative to the direction of the incident x-ray beam. A structure study of Eu(III) aqua ion behavior in high-temperature aqueous solutions and a study of Nb partitioning and coordination in a silicate melt in contact with a hydrothermal fluid are described as applications utilizing the modified HDAC rail assembly. ?? 2007 American Institute of Physics.

Review of Scientific Instruments↗

USGS2007

On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 ?? 0.2 to 1.7 ?? 0.3 in the 0.006m chloride solution and from 0.9 ?? 0.7 to 1.8 ?? 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500????C range. Conversely, the number of H2O ligands of Gd(H2O)??-nCln+3-n complexes decreases steadily from 8.9 ?? 0.4 to 5.8 ?? 0.7 in the 0.006m GdCl3 aqueous solution and from 9.0 ?? 0.5 to 5.3 ?? 1.0 in the 0.1m GdCl3 aqueous solution at temperatures from 25 to 500????C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH2 bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction (??? 0.005??A??/100????C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids. ?? 2006 Elsevier B.V. All rights reserved.

Chemical Geology↗