Theory of interaction intensities,buffer capacities,and pH stability in aqueous systems,with application to the pH of seawater and a heterogeneous model ocean system     

Francois Morel  Russell E. McDuff  James J. Morgan 《Marine Chemistry》1976,4(1):1-28

The choice of convenient basic constituents for evaluating pH stability of aqueous systems is discussed, and two useful interaction parameters are defined and related to the buffer capacity: the interaction capacity, $\text{δ′}{}_{\mathrm{X,Y}}\text{=}\text{?}\text{p}\text{X}\text{?}\text{TOT}\text{Y}$, and the interaction intensity, $\text{δ}{}_{\mathrm{X,\; Y}}\text{=}\text{?}\text{p}\text{X}\text{?}\text{pTOT}\text{Y}$; for pH and TOTH, δ′_{H, H} = ?β_H^?1, where β_H is the pH buffer capacity. A method is presented for the computation of exact values of all interaction capacities and intensities through inversion of the Jacobian matrix of the system of non-linear equations describing the aqueous system. The major species of an aqueous system (H₂O, H⁺, solid phases, gases, and the most abundant solute species) are shown to constitute a useful set of basic constituents for evaluation of approximate pH buffer capacities according to a simple rule: the major-minor species rule for zeroth order pH-TOTH interaction. The concepts of buffering and pH-statting are examined and contrasted; it is demonstrated that the buffer capacity of an aqueous system cannot be infinite: it is limited by the concentration of solutes in solution. The effect upon pH of variations in constituents other than H⁺ is described in terms of first order interactions via complex formation and solid formation; approximate formulas for calculation are derived. Higher order interactions are derived from combinations of first order ones. The pH stability of the ocean system is examined in terms of an aqueous phase model including ion-association reactions and a heterogeneous model incorporating CO₂ in the gas phase, quartz, kaolinite, calcite, chlorite, and illite, in addition to the aqueous phase. There is an approximately three-fold enhancement of buffer capacity in the aqueous model as a consequence of ion-association. Only a few interaction pathways are of quantitative significance in establishing the buffer capacity. Results for the heterogeneous ocean model lend quantitative support to Sillén's notion of pH stability: the buffer capacity is about four hundred times greater than that of the aqueous phase model.  相似文献   

Biotite stability in peraluminous granitic melts: Compositional dependence and application to the generation of two-mica granites in the South Bohemian batholith (Bohemian Massif, Czech Republic)   总被引：2，自引：0，他引：2  

Milo&#x; Ren  Francois Holtz  Cherhui Luo  Oliver Beermann  Jan Stelling 《Lithos》2008,102(3-4):538-553

Crystallization experiments have been conducted in the system Na₂O–K₂O–MgO–FeO–Al₂O₃–SiO₂–H₂O (with 4% normative corundum) in order to constrain the stability of biotite as a function of water activity and the Mg# of biotite [Mg/(Mg +Fe_total)] in equilibrium with peraluminous granitic melts. The temperature at which biotite breakdown starts is strongly dependent on the Mg# of biotite. At 500 MPa, the temperature of biotite breakdown to form orthopyroxene increases from 750 °C to 830 °C, as the Mg# of biotite increases from 0.4 to 0.5. Considering that the system investigated is relevant for Ca-poor peraluminous biotite-bearing rocks (metapelites), the biotite dehydration curves obtained are used to discuss the melting reactions and the temperatures that lead to the formation of two distinct types of two-mica granites found in the South Bohemian batholith (specifically the Eisgarn and Deštná granites). The phase relationships were determined experimentally for the composition of these two granites in order to constrain the composition of the biotite in equilibrium with the melt in the protoliths. We demonstrate that Eisgarn granitic melts may have been generated at temperatures in the range 830–850 °C from melting reactions involving biotite with a Mg# up to 0.5 as a reactant. In contrast, Deštná granitic melts cannot have been generated from dehydration melting reactions involving biotite.  相似文献   

Fractionation vs. magma mixing in the Wangrah Suite A-type granites, Lachlan Fold Belt, Australia: Experimental constraints   总被引：1，自引：0，他引：1  

Kevin Klimm  Francois Holtz  Penelope L. King 《Lithos》2008,102(3-4):415-434

The Wangrah Suite granites (Lachlan Fold Belt, Australia) reflect different stages of differentiation in the magmatic history of an A-type plutonic suite. In this study we use experimentally determined phase equilibria of four natural A-type granitic compositions of the Wangrah Suite to constrain phases and phase compositions involved in fractionation processes. Each composition represents a distinct granite intrusion in the Wangrah Suite. The intrusions are the Danswell Creek (DCG), Wangrah (WG), Eastwood (EG) and Dunskeig Granite (DG), ordered from “most mafic” to “most felsic” by increasing SiO₂ and decreasing FeO_total.

Experimental investigation show that the initial water content in melts from DCG is between 2–3 wt. % H₂O. If the DCG is viewed as the parental magma for the Wangrah Suite, then (1) fractionation of magnetite, orthopyroxene and plagioclase ( 20 wt. %) of the DCG composition, leads to compositions similar to that of the EG; (2) further fractionation of plagioclase, quartz, K-feldspar and biotite ( 40 wt. %) from the EG composition, leads to the DG composition. These fractionation steps can occur nearly isobarically and are confirmed by bulk rock Ba, Sr, Rb and Zr concentrations.

In contrast, the generation of the most abundant WG composition cannot be explained by fractional crystallisation from the DCG at isobaric conditions because of the high K₂O content of this granite. Magma Mixing could be the process to explain the chemical distinctiveness of the Wangrah Granite from all the other granites of the Wangrah Suite.  相似文献   

Assessment of Planetary-Boundary-Layer Schemes in the Weather Research and Forecasting Model Within and Above an Urban Canopy Layer     

Enrico Ferrero  Stefano Alessandrini  Francois Vandenberghe 《Boundary-Layer Meteorology》2018,168(2):289-319

We tested several planetary-boundary-layer (PBL) schemes available in the Weather Research and Forecasting (WRF) model against measured wind speed and direction, temperature and turbulent kinetic energy (TKE) at three levels (5, 9, 25 m). The Urban Turbulence Project dataset, gathered from the outskirts of Turin, Italy and used for the comparison, provides measurements made by sonic anemometers for more than 1 year. In contrast to other similar studies, which have mainly focused on short-time periods, we considered 2 months of measurements (January and July) representing both the seasonal and the daily variabilities. To understand how the WRF-model PBL schemes perform in an urban environment, often characterized by low wind-speed conditions, we first compared six PBL schemes against observations taken by the highest anemometer located in the inertial sub-layer. The availability of the TKE measurements allows us to directly evaluate the performances of the model; results of the model evaluation are presented in terms of quantile versus quantile plots and statistical indices. Secondly, we considered WRF-model PBL schemes that can be coupled to the urban-surface exchange parametrizations and compared the simulation results with measurements from the two lower anemometers located inside the canopy layer. We find that the PBL schemes accounting for TKE are more accurate and the model representation of the roughness sub-layer improves when the urban model is coupled to each PBL scheme.  相似文献   

A numerical study of the influence from pre‐existing cracks on granite rock fragmentation at percussive drilling          下载免费PDF全文

Mahdi Saadati  Pascal Forquin  Kenneth Weddfelt  Per‐Lennart Larsson  Francois Hild 《国际地质力学数值与分析法杂志》2015,39(5):558-570

The aim of this study is to investigate the effect of pre‐existing, or structural, cracks on dynamic fragmentation of granite. Because of the complex behavior of rock materials, a continuum approach is employed relying upon a plasticity model with yield surface locus as a quadratic function of the mean pressure in the principal stress space coupled with an anisotropic damage model. In particular, Bohus granite rock is investigated, and the material parameters are chosen based on previous experiments. The equation of motion is discretized using a finite element approach, and the explicit time integration method is employed. The pre‐existing cracks are introduced in the model by considering sets of elements with negligible tensile strength that leads to their immediate failure when loaded in tension even though they still carry compressive loads as crack closure occurs because of compressive stresses. Previously performed edge‐on impact tests are reconsidered here to validate the numerical model. Percussive drilling is simulated, and the influence of the presence of pre‐existing cracks is studied. The results from the analysis with different crack lengths and orientations are compared in terms of penetration stiffness and fracture pattern. It is shown that pre‐existing cracks in all investigated cases facilitate the drilling process. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

Tracing the evolution and distribution of F and Cl in plutonic systems from volatile-bearing minerals: a case study from the Liujiawa pluton (Dabie orogen, China)   总被引：2，自引：1，他引：1  

Chao Zhang  Francois Holtz  Changqian Ma  Paul Eric Wolff  Xiaoyan Li 《Contributions to Mineralogy and Petrology》2012,164(5):859-879

Fluorine and chlorine play an important role in magmatic differentiation, hydrothermal alteration, and related mineralization processes, but tracing their evolution in magmatic and especially plutonic systems is not an easy task. The F and Cl in melts can be estimated from F and Cl concentrations in minerals, provided that partitioning between minerals and melts are constrained. Based on available partitioning models between mineral/melt, mineral/fluid, and melt/fluid, a set of equations has been derived to determine F and Cl concentrations in melts from the compositions of amphibole, biotite, and apatite. The new calculation procedure has been applied to a plutonic system, the Liujiawa pluton, eastern Dabie orogen (China). Cl and F concentrations in amphiboles, biotites, and apatites from different rock types (gabbronorite, two-pyroxene diorite, clinopyroxene diorite, and hornblende gabbro) have been determined by electron microprobe. Most amphiboles show a negative correlation between log(Cl/OH) and Mg-number and a positive correlation between log(F/OH) and A-site occupation. Biotites from the gabbronorite and two-pyroxene diorite show a slight positive correlation between log(Cl/OH) and Mg, which is however not the case for the clinopyroxene diorite. Apatites from all the samples are rich in F and show negative correlations between Cl and F concentrations. In our case study, we demonstrate that the Cl concentration in melt remains approximately constant at 1,000–2,000?ppm over the major crystallization interval, but decreases strongly at near solidus temperatures as a result of fluid exsolution. The F concentration in melt remains nearly constant at ca. 2,000–3,000?ppm at high temperatures as well as near solidus conditions, indicating that it is not largely affected by fluid exsolution because of its strongly preferred incorporation into melt. Interestingly, the evolution of Cl and F concentrations in melt with magmatic differentiation is similar to that determined in volcanic systems, suggesting that the evolution of Cl and F in melts during crystallization and late magmatic stages at depth (plutonic systems) is similar to that observed in volcanic systems during decompression and degassing.  相似文献   

The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts     

Francesco?VetereEmail author  Francois?Holtz  Harald?Behrens  Roman?E.?Botcharnikov  Sara?Fanara 《Contributions to Mineralogy and Petrology》2014,167(5):1014

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.  相似文献   

How light affect the magnetotactic behavior and reproduction of ellipsoidal multicellular magnetoglobules?     

Qian  Xinxin  Zhao  Yicong  Santini  Claire-Lise  Pan  Hongmiao  Xiao  Tian  Chen  Haitao  Song  Tao  Li  Jinhua  Alberto  Francois  Brustlein  Sophie  Wu  Long-Fei 《中国海洋湖沼学报》2021,39(6):2005-2014

Journal of Oceanology and Limnology - Magnetotactic bacteria (MTB) synthesize intracellular magnetic organelles, magnetosomes, which consist of magnetic crystals that are enveloped in a membrane....  相似文献   

The post-outburst photometric behaviour of V838 Mon     

Lisa A. Crause  Warrick A. Lawson  David Kilkenny  Francois van Wyk  Fred Marang  Albert F. Jones 《Monthly notices of the Royal Astronomical Society》2003,341(3):785-791

  相似文献   

GMRT and VLA observations at 49 cm and 20 cm of the HII region near <Emphasis Type="Italic">l</Emphasis> = 24.8°, <Emphasis Type="Italic">b</Emphasis> = 0.1°     

N. G. Kantharia  W. M. Goss  D. Anish Roshi  Niruj R. Mohan  Francois Viallefond 《Journal of Astrophysics and Astronomy》2007,28(1):41-53

We report multi-frequency radio continuum and hydrogen radio recombination line observations of HII regions near l = 24.8°, b = 0.1° using the Giant Metrewave Radio Telescope (GMRT) at 1.28 GHz (n = 172), 0.61 GHz (n = 220) and the Very Large Array (VLA) at 1.42 GHz (n = 166). The region consists of a large number of resolved HII regions and a few compact HII regions as seen in our continuum maps, many of which have associated infrared (IR) point sources. The largest HII region at l = 24.83° and b = 0.1° is a few arcmins in size and has a shell-type morphology. It is a massive HII region enclosing ∼550 M_⊙ with a linear size of 7 pc and an rms electron density of ∼110 cm⁻³ at a kinematic distance of 6 kpc. The required ionization can be provided by a single star of spectral type O5.5. We also report detection of hydrogen recombination lines from the HII region at l = 24.83° and b = 0.1° at all observed frequencies near V _lsr = 100 km s⁻¹. We model the observed integrated line flux density as arising in the diffuse HII region and find that the best fitting model has an electron density comparable to that derived from the continuum. We also report detection of hydrogen recombination lines from two other HII regions in the field.  相似文献