Use of Pitzer Equations to Examine the Formation of Mercury(II) Hydroxide and Chloride Complexes in NaClO<Subscript>4</Subscript> Media     

Melchor González-Dávila  J. Magdalena Santana-Casiano  Frank J. Millero 《Aquatic Geochemistry》2007,13(4):339-355

The thermodynamic stability constants for the hydrolysis and formation of mercury (Hg²⁺) chloride complexes have been used to calculate the activity coefficients for Hg(OH) _n ^(2–n)+ and HgCl _n ^(2–n)+ complexes using the Pitzer specific interaction model. These values have been used to determine the Pitzer parameters for the hydroxide and chloro complexes and C _ML). The values of and have been determined for the neutral complexes (Hg(OH)₂ and HgCl₂). The resultant parameters yield calculated values for the measured values of log to  ±0.01 from I  =  0.1 to 3 m at 25°C. Since the activity coefficients of and are in reasonable agreement with the values for Pb(II), we have estimated the effect of temperature on the chloride constants for Hg(II) from 0 to 300°C and I = 0–6 m using the Pitzer parameters for complexes. The resulting parameters can be used to examine the speciation of Hg(II) with Cl⁻ in natural waters over a wide range of conditions.  相似文献   

The crystal structure of waylandite from Wheal Remfry, Cornwall, United Kingdom     

Stuart J. Mills  Anthony R. Kampf  Mati Raudsepp  William D. Birch 《Mineralogy and Petrology》2010,100(3-4):249-253

Sr- and Ca-rich waylandite, $ {\left( {{\hbox{B}}{{\hbox{i}}_{0.{54}}}{\hbox{S}}{{\hbox{r}}_{0.{31}}}{\hbox{C}}{{\hbox{a}}_{0.{25}}}{{\hbox{K}}_{0.0{1}}}{\hbox{B}}{{\hbox{a}}_{0.0{1}}}} \right)_{\Sigma 1.12}}{{\hbox{H}}_{0.{18}}}{\left( {{\hbox{A}}{{\hbox{l}}_{{2}.{96}}}{\hbox{C}}{{\hbox{u}}_{0.0{2}}}} \right)_{\Sigma 2.98}}{\left[ {{{\left( {{{\hbox{P}}_{0.{97}}}{{\hbox{S}}_{0.0{3}}}{\hbox{S}}{{\hbox{i}}_{0.0{1}}}} \right)}_{\Sigma 1.00}}{{\hbox{O}}_4}} \right]_2}{\left( {\hbox{OH}} \right)_6} $ , from Wheal Remfry, Cornwall, United Kingdom has been investigated by single-crystal X-ray diffraction and electron microprobe analyses. Waylandite crystallises in space group R $ \overline 3 $ ? m, with the cell parameters: a?=?7.0059(7) Å, c?=?16.3431(12) Å and V?=?694.69(11) ų. The crystal structure has been refined to R ₁?=?3.76%. Waylandite has an alunite-type structure comprised of a rhombohedral stacking of (001) composite layers of corner-shared AlO₆ octahedra and PO₄ tetrahedra, with (Bi,Sr,Ca) atoms occupying icosahedrally coordinated sites between the layers.  相似文献   

The origin of mafic rocks in the Naqadeh intrusive complex, Sanandaj-Sirjan Zone, NW Iran     

Seyed Ali Mazhari  Sadraldin Amini  Jalil Ghalamghash  Fernando Bea 《Arabian Journal of Geosciences》2011,4(7-8):1207-1214

The Naqadeh mafic plutonic rocks are located on a plutonic assemblage and include different granitoid rocks related to ～40 Ma. U-Pb SHRIMP data shows different ages of 96?±?2.3 Ma for mafic rocks. Naqadeh mafic plutonic rocks consist of diorite to diorite-gabbros with relatively high contents of incompatible elements, low Na2O, and $ {\hbox{Mg\# }} = \left[ {{\hbox{molar}}\;{100} \times {\hbox{MgO/}}\left( {{\hbox{MgO}} + {\hbox{FeO}}} \right)} \right] > 44.0 $ . These features suggest that the Naqadeh mafic rocks originate from enriched lithospheric mantle above subducted slab during Neotethys subduction under Iranian plate.  相似文献   

Oxidised phase relations of a primitive basalt from Grenada,Lesser Antilles     

C.?C.?StamperEmail author  E.?Melekhova  J.?D.?Blundy  R.?J.?Arculus  M.?C.?S.?Humphreys  R.?A.?Brooker 《Contributions to Mineralogy and Petrology》2014,167(1):954

A series of liquidus determinations is reported for a primitive arc basalt (15.4 wt % MgO, 45.5 wt % SiO₂) from Grenada, Lesser Antilles, at anhydrous, H₂O-undersaturated and H₂O-saturated conditions in the pressure range 1 atm to 1.7 GPa. \(\hbox{Fe}^{3+}/\Upsigma\hbox{Fe}\) of high-pressure experimental glasses as measured by μXANES ranges from 0.44 to 0.86, corresponding to oxygen fugacities (fO₂) between 3.2 and 7.8 log units above the nickel–nickel oxide redox buffer (NNO). 1-atm experiments conducted from NNO ? 2.5 to + 3.8 show that increasing fO₂ mainly increases the forsterite content (Fo) of olivine and has little effect on phase relations. The crystallisation sequence at lower crustal pressures for all water contents is forsteritic olivine + Cr-rich spinel followed by clinopyroxene. The anhydrous liquidus is depressed by 100 and 120 °C in the presence of 2.9 and 3.8 wt % H₂O, respectively. H₂O-undersaturated experiments at NNO + 3.2 to + 4.5 produce olivine of equivalent composition to the most primitive olivine phenocrysts in Grenadan picrites (Fo_91.4). We conclude that direct mantle melts originating beneath Grenada could be as oxidised as ~NNO + 3, consistent with the uppermost estimates from olivine–spinel oxybarometry of high Mg basalts. μXANES analyses of olivine-bearing experimental glasses are used to develop a semi-empirical oxybarometer based on the value of \({{K}_{D}}_{\rm ol-melt}^{\rm Fe-Mg}\) when all Fe is assumed to be in the Fe²⁺ state (\({K}_{D}^{{\rm Fe}_T}\)). The oxybarometer is tested on an independent data set and is able to reproduce experimental fO₂ to ≤1.2 log units. Experiments also show that the geochemically and petrographically distinct M- and C-series lavas on the island can be produced from hydrous melting of a common picritic source. Low pressures expand the olivine stability field at the expense of clinopyroxene, enriching an evolving melt in CaO and forcing differentiation to take place along a C-series liquid line of descent. Higher pressure conditions allow early and abundant clinopyroxene crystallisation, rapidly depleting the melt in both CaO and MgO, and thus creating the M-series.  相似文献   

Experimental study of Fe-Mg distribution between biotite and orthopyroxene at P=490 MPa     

V. I. Fonarev  A. N. Konilov 《Contributions to Mineralogy and Petrology》1986,93(2):227-235

Partitioning of Mg and Fe between coexisting biotite and orthopyroxene has been experimentally determined at temperatures 700, 750 and 800° C and 490 MPa total pressure in the system KAlO₂-MgO-FeO-SiO₂-H₂O. Oxygen fugacity was controlled by the QFM buffer. Starting materials were synthetic minerals of differing Fe/(Fe+Mg) values. Run products were analyzed for partitioning of components by a microprobe. Orthopyroxene was established to be notably inhomogeneous, whereas biotite was essentially homogeneous. To establish equilibrium relations, statistical treatment of the results of each experiment in addition to the whole complex of experimental data was applied. The regression equations for isotherms of the Fe-Mg partitioning between the minerals studied have been obtained. As a result, the equation for a two-dimensional regression may be written as: $$\begin{gathered} Y = (A + A_1 t + A_2 t^2 )(X - X^4 ) + (B + B_1 t + B_1 t^2 )(X^2 - X^4 ) + \hfill \\ (C + C_1 t + C_1 t^2 )(X^3 - X^4 ) + X^4 {\text{ where }}Y = X_{{\text{Opx}}}^{{\text{Fe}}} ;{\text{ X}} = {\text{X}}_{{\text{Bi}}}^{{\text{Fe}}} ; \hfill \\ t = 1000/T,K, \hfill \\ \begin{array}{*{20}c} {A = {\text{ }}4.59398,} & {A_1 = - {\text{ }}8.29838,} & {A_2 = {\text{ }}4.97316,} \\ {B = - 11.13731,} & {B_1 = {\text{ }}28.19304,} & {B_2 = - 20.98240,} \\ {A = {\text{ }}8.25072,} & {C_1 = - 20.80485,} & {C_2 = {\text{ }}15.35967} \\ \end{array} \hfill \\ {\text{ }}\sigma = 0.0143{\text{ }} \hfill \\ \end{gathered}$$ . This equation enables extrapolation of partitioning isotherms over a wide range of temperatures.  相似文献   

An experimental study of Ti and Zr partitioning among zircon, rutile, and granitic melt     

Amy E. Hofmann  Michael B. Baker  John M. Eiler 《Contributions to Mineralogy and Petrology》2013,166(1):235-253

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO₂ and ZrO₂; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO₂ contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO₂ contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO₂ concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO₂ in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.  相似文献