Geology topics

William A. Bassett

Publications and source records attributed to William A. Bassett.

10 recordsLinked to original sources

USGS2009

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↗

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↗

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↗

USGS2005

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 ·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 −1 corresponding to E g (external) and A 1 g (internal) modes of vibrations in CO 2− 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 °C; the boundary for the reaction ikaite ↔ 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↗

USGS2003

Relaxation of the structure of simple metal ion complexes in aqueous solutions at up to supercritical conditions

Recently x-ray absorption fine structure (XAFS) studies of various ions in aqueous solutions showed a variation of cation-ligand bond lengths, often coupled with other structure changes, with increasing temperatures. Thus, the variations of the structure of several metal ion complexes with temperature based on observations from the X-ray absorption fine structure (XAFS) studies in the hope that it will stimulate the development of either first- principles theory or molecular dynamics simulations that might adequately describes these results are discussed.

Journal of Chemical Physics↗

USGS2001

Analysis of radiation-induced small Cu particle cluster formation in aqueous CuCl2

Radition-induced small Cu particle cluster formation in aqueous CuCl2 was analyzed. It was noticed that nearest neighbor distance increased with the increase in the time of irradiation. This showed that the clusters approached the lattice dimension of bulk copper. As the average cluster size approached its bulk dimensions, an increase in the nearest neighbor coordination number was found with the decrease in the surface to volume ratio. Radiolysis of water by incident x-ray beam led to the reduction of copper ions in the solution to themetallic state.

Journal of Chemical Physics↗

USGS1999

XAFS measurements on zinc chloride aqueous solutions from ambient to supercritical conditions using the diamond anvil cell

The structure and bonding properties of metal complexes in subcritical and supercritical fluids are still largely unknown. Conventional high pressure and temperature cell designs impose considerable limitations on the pressure, temperature, and concentration of metal salts required for measurements on solutions under supercritical conditions. In this study, we demonstrate the first application of the diamond anvil cell, specially designed for x-ray absorption studies of first-row transition metal ions in supercritical fluids. Zn K-edge XAFS spectra were measured from aqueous solutions of 1-2 m ZnCl 2 and up to 6 m NaCl, at temperatures ranging from 25-660 °C and pressures up to 800 MPa. Our results indicate that the ZnCl 4 2- complex is predominant in the 1 m ZnCl 2 /6 m NaCl solution, while ZnCl 2 (H 2 O) 2 is similarly predominant in the 2 m ZnCl 2 solution, at all temperatures and pressures. The Zn-Cl bond length of both types of chlorozinc(II) complexes was found to decrease at a rate of about 0.01 Å/100 °C.

Journal of Synchrotron Radiation↗

USGS1995

Techniques for determining pressure in the hydrothermal diamond- anvil cell: behavior and identification of ice polymorphs (I, III, V, VI)

For H2O densities > 1.0 g/cm3, a determination of the ice melting temperature provides the density information required to calculate the P-T path that the sample in a hydrothermal diamond-anvil cell follows when the sample is heated isochorically. The principal difficulty is the identification of the polymorph because of metastable behavior of ices in the H2O system. Usually, an accurate identification of the liquidus ice phase can be made without analytical instrumentation and requires only careful observations. -Authors

American Mineralogist↗

USGS1993

A new diamond anvil cell for hydrothermal studies to 2.5 GPa and from -190 to 1200 °C

A new style of diamond anvil cell(DAC) has been designed and built for conducting research in fluids at pressures to 2.5 GPa and temperatures from −190 to 1200 °C. The new DAC has been used for optical microscope observations and synchrotron x‐ray diffraction studies. Fringes produced by interference of laser light reflected from top and bottom anvil faces and from top and bottom sample faces provide a very sensitive means of monitoring the volume of sample chamber and for observing volume and refractive index changes in samples that have resulted from transitions and reactions. X‐ray diffraction patterns of samples under hydrothermal conditions have been made by the energy dispersive method using synchrotron radiation. The new DAC has individual heaters and individual thermocouples for the upper and lower anvils that can be controlled and can maintain temperatures with an accuracy of ±0.5 °C. Low temperatures are achieved by introducing liquid nitrogen directly into the DAC. The equation of state of H 2 O and the α‐β quartz transition are used to determine pressure with an accuracy of ±1% in the aqueous samples. The new DAC has been used to redetermine five isochores of H 2 O as well as the dehydration curves of brucite, Mg(OH) 2 , and muscovite, KAl 2 (Si 3 Al)O 10 (OH) 2 .

Review of Scientific Instruments↗