An experimental and theoretical determination of oxygen isotope fractionation in the system magnetite-H₂O from 300 to 800°C     

David R. Cole  Juske Horita  John W. Valley  Dorothy W. Coffey 《Geochimica et cosmochimica acta》2004,68(17):3569-3585

Oxygen isotope fractionations have been determined between magnetite and water from 300 to 800°C and pressures between 10 and 215MPa. We selected three reaction pathways to investigate fractionation: (a) reaction of fine-grained magnetite with dilute aqueous NaCl solutions; (b) reduction of fine-grained hematite through reaction with dilute acetic acid; and (c) oxidation of fine iron power in either pure water or dilute NaCl solutions. Effective use of acetic acid was limited to temperatures up to about 400°C, whereas oxide-solution isotope exchange experiments were conducted at all temperatures. Equilibrium ¹⁸O/¹⁶O fractionation factors were calculated from the oxide-water experiments by means of the partial isotope exchange method, where generally four isotopically different waters were used at any given temperature. Each run product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and on a limited basis, high-resolution transmission electron microscopy (HRTEM) and Mössbauer spectroscopy. Results from the microscopic examinations indicate the formation of well-crystallized octahedra and dodecahedra of magnetite where the extent of crystallization, grain size, and grain habit depend on the initial starting material, P, T, solution composition, and duration of the run.The greatest amount of oxygen isotope exchange (∼90% or greater) was observed in experiments where magnetite either recrystallized in the presence of 0.5 m NaCl from 500 to 800°C or formed from hematite reacted with 0.5 m acetic acid at 300, 350 and 400°C. Fractionation factors (10³ ln α_mt-H2O) determined from these partial exchange experiments exhibit a steep decrease (to more negative values) with decreasing temperature down to about 500°C, followed by shallower slope. A least-squares regression model of these partial exchange data, which accounts for analytical errors and errors generated by mass balance calculations, gives the following expression for fractionation that exhibits no minimum: 1000lnα_lmt-lw=−8.984(±0.3803)x+3.302(±0.377)x²—0.426(±0.092)x³ with an R² = 0.99 for 300 ≤ T≤ 800°C (x = 10⁶/T²). The Fe oxidation results also exhibit this type of temperature dependence but shifted to slightly more negative 10³ ln α values; there is the suggestion that a kinetic isotope effect may contribute to these fractionations. A theoretical assessment of oxygen isotope fractionation using β-factors derived from heat capacity and Mössbauer temperature (second-order Doppler) shift measurements combined with known β-factors for pure water yield fractionations that are somewhat more negative compared to those determined experimentally. This deviation may be due to the combined solute effects of dissolved magnetite plus NaCl (aq), as well as an underestimation of β_mt at low temperatures. The new magnetite-water experimental fractionations agree reasonably well with results reported from other experimental studies for temperatures ≥ 500°C, but differ significantly with estimates based on quasi-theoretical and empirical approaches. Calcite-magnetite and quartz-magnetite fractionation factors estimated from the combination of magnetite β’s calculated in this study with those for calcite and quartz reported by Clayton and Kieffer (1991) agree very closely with experimentally determined mineral-pair fractionations.  相似文献   

Passive microwave remote sensing of the historic February 2010 snowstorms in the Middle Atlantic region of the USA     

James L. Foster  Gail Skofronick‐Jackson  Huan Meng  James R. Wang  George Riggs  Paul J. Kocin  Benjamin T. Johnson  Judah Cohen  Dorothy K. Hall  Son V. Nghiem 《水文研究》2012,26(22):3459-3471

The snowfall in the Baltimore/Washington metropolitan area during the winter of 2009/2010 was unprecedented and caused serious snow‐related disruptions. In February 2010, snowfall totals approached 2 m, and because maximum temperatures were consistently below normal, snow remained on the ground the entire month. One of the biggest contributing factors to the unusually severe winter weather in 2009/2010, throughout much of the middle latitudes, was the Arctic Oscillation. Unusually high pressure at high latitudes and low pressure at middle latitudes forced a persistent exchange of mass from north to south. In this investigation, a concerted effort was made to link remotely sensed falling snow observations to remotely sensed snow cover and snowpack observations in the Baltimore/Washington area. Specifically, the Advanced Microwave Scanning Radiometer onboard the Aqua satellite was used to assess snow water equivalent, and the Advanced Microwave Sounding Unit‐B and Microwave Humidity Sounder were employed to detect falling snow. Advanced Microwave Scanning Radiometer passive microwave signatures in this study are related to both snow on the ground and surface ice layers. In regard to falling snow, signatures indicative of snowfall can be observed in high frequency brightness temperatures of Advanced Microwave Sounding Unit‐B and Microwave Humidity Sounder. Indeed, retrievals show an increase in snow water equivalent after the detection of falling snow. Yet, this work also shows that falling snow intensity and/or the presence of liquid water clouds impacts the ability to reliably detect snow water equivalent. Moreover, changes in the condition of the snowpack, especially in the surface features, negatively affect retrieval performance. Copyright © 2011. This article is a U.S. Government work and is in the public domain in the USA.  相似文献   

Quaternary evolution of Cedar Creek alluvial fan, montana   总被引：1，自引：0，他引：1  

J.B Ritter  J.R Miller  Y Enzel  S.D Howes  G Nadon  M.D Grubb  K.A Hoover  T Olsen  S.L Reneau  D Sack  C.L Summa  I Taylor  K.C.N Touysinhthiphonexay  E.G Yodis  N.P Schneider  D.F Ritter  S.G Wells 《Geomorphology》1993,8(4)

Cedar Creek alluvial fan is a textbook example of an alluvial fan because of its fan shape with smooth, concentric contours and excellent symmetry. Similar planimetric shapes have been used to infer uniform fan deposition; however, Cedar Creek alluvial fan is composed of four fan deposits of Quaternary age, Qf1 (oldest) to Qf4 (youngest), indicating that fan deposition was nonuniform in both time and space. Field studies indicate that deposition of Cedar Creek alluvial fan is related to glaciofluvial outwash activity during the Pleistocene and upper-fan entrenchment and lower-fan deposition during the Holocene.Qf1 and Qf2 deposits are sub-horizontally bedded, clast-supported sandy gravels uniformly imbricated upfan. Comparison of soil profiles developed in these deposits to radiogenically-dated chronosequences within the region indicates that Qf1 and Qf2 are correlative with Bull Lake and Pinedale-age deposits, respectively. These relationships are substantiated by physical correlation of Qf1 and Qf2 with Bull Lake and Pinedale moraines, respectively, in the Cedar Creek drainage basin. The sedimentology and timing of Qf1 and Qf2 indicate deposition in high-energy, proglacial, braided streams. Furthermore, the present morphology of Cedar Creek alluvial fan was established largely during aggradation of Qf1 and Qf2 when sediment supply to the fan was sufficient to activate 60% to greater than 90% of the total fan area. During Bull Lake glaciation, the apex of Qf1 deposition formed the apex of Cedar Creek alluvial fan as Qf1 covered more than 90% of the present fan area. During Pinedale glaciation, Qf2 deposition shifted downfan; Qf2 is inset into Qf1 above the intersection point, but below the intersection point it eroded and/or buried Qf1 as it activated as much as 60% of the fan area.Qf3 and Qf4, comprising 21% of the fan area, are inset into Qf2 in the lower fan area. Soil development in Qf3 and Qf4 deposits indicate episodic deposition and entrenchment beginning in early Holocene and continuing to present. A post-glacial decrease in sediment supply to Cedar Creek alluvial fan is indicated by sediment storage within the Cedar Creek drainage basin. Decreased sediment supply to the fan resulted in upper-fan entrenchment of Qf2 and deposition of Qf3 and Qf4 in the lower-fan area.  相似文献   

An internally consistent model for the thermodynamic properties of Fe-Mg-titanomagnetite-aluminate spinels     

Richard O. Sack  Mark S. Ghiorso 《Contributions to Mineralogy and Petrology》1991,107(3):415-415

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Geochemical characteristics of Cocos Plate seamount lavas     

James F. Allan  Rodey Batiza  Richard O. Sack 《Contributions to Mineralogy and Petrology》1994,116(1-2):47-61

A wide compositional continuum of basalts has been erupted from near-ridge seamounts constructed on the Cocos Plate between the Clipperton and Orozco Francture Zones. They range from highly evolved to moderately primitive (3.0–7.8% MgO), LREE-enriched alkali basalts, to moderately evolved to near-primary (5.2–9.5% MgO) tholeiites indistinguishable from N-type MORB. The data set of 159 quench glass analyses exhibits a remarkably consistent variation in both major and trace element composition that is keyed to variations in (La/Sm). Modeling of potential liquid lines of descent at pressures ranging from 1 bar to 8 kbar shows that this covariation is partially due to systematic differences in liquid lines of descent, where the alkaline lavas have undergone substantially more high pressure clinopyroxene fractionation and substantially less low pressure plagioclase fractionation than the tholeiites. In addition, systematic variation in the composition of the more primitive glasses indicates that they were derived from mixing of discrete enriched and depleted melts in the heterogenous seamount mantle source at pressures of 8–10 kbar and greater, and that clinopyroxene may be a residual phase during partial melting. These results show that porous media flow in the seamount mantle source is minor and that melt transport is accomplished primarily through cracking and diking. This study supports suggestions that the general homogeneity of basalt along the EPR is due to mixing in sub-axial magma chambers and mush zones, with additional mixing during partial mantle melting and melt segregation.  相似文献   

Experimental petrology of alkalic lavas: constraints on cotectics of multiple saturation in natural basic liquids     

Richard O. Sack  David Walker  Ian S. E. Carmichael 《Contributions to Mineralogy and Petrology》1987,96(1):1-23

Experimental study of natural alkalic lava compositions at low pressures (pO₂QFM) reveals that crystallization of primitive lavas often occurs in the sequence olivine, plagioclase, clinopyroxene, nepheline without obvious reaction relation. Pseudoternary liquidus projections of multiply saturated liquids coexisting with plagioclase (±olivine±clinopyroxene±nepheline) have been prepared to facilitate graphical analysis of the evolution of lava compositions during hypabyssal cooling. Use of (TiAl₂)(MgSi₂)_–1 and Fe³⁺ (Al)_–1 exchange components is a key aspect of the projection procedure which is succesful in reducing a wide range of compositions to a systematic graphical representation. These projections, and the experiments on which they are based, show that low pressure fractionation plays a significant role in the petrogenesis of many alkalic lava suites from both continental and oceanic settings. However, the role of polybaric fractionation is more evident in the major element chemistry of these lava suites than in many tholeiitic suites of comparable extent. For example, the lavas of Karisimbi, East Africa, show a range of compositions reflecting a polybaric petrogenesis from primitive picrites at 1360° C/18 kb and leading to advanced low pressure differentiates. Evolved leucite-bearing potassic members of this and other suites may be treated in a nepheline-diopside-kspar (+olivine+leucite) projection. Compositional curvature on the plagioclase+clinopyroxene+olivine+leucite cotectic offers a mechanism to explain resorption of plagioclase in alkalic groundmass assemblages and the incompatibility of albite and leucite. This projection is useful for evaluating the extent of assimilation of the alkalic portions of crustal granulites. Assimilation appears to have played some role in the advanced differentiates from Karisimbi.  相似文献   

Sakmarian geography     

Dorothy Hill 《International Journal of Earth Sciences》1959,47(2):590-629

The known palaeontological and stratigraphical evidence is used as a basis for the construction of maps of the continents showing the extent of their inundation by the sea in Sakmarian time in the Upper Palaeozoic. In the northern hemisphere apart from India the evidence is sufficiently reliable to give reasonable maps, and the great extent of the inundations suggests that the climate would be considerably modified from that of today; no undoubted Sakmarian glacials occur there. In Southern continents and India, the Gondwana biogeographical province has made correlation with the northern continents controversial, but reasons are given for assuming that Gondwana glacial deposits were at least in part Sakmarian; the resultant maps show that the Gondwana land surfaces were but little reduced in area, and that the main glacials (except for India) lie within a belt between 40 S and 20 S. Present lack of knowledge of Sakmarian conditions in Antarctica makes reconstructions of climatic belts too hazardous for possible use in enunciating or checking hypotheses of continental drift and polar wandering.  相似文献   

Sedimentary studies in the Shenandoah Valley of Virginia     

Dorothy Carroll 《International Journal of Earth Sciences》1955,43(2):383-384

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Inter-relationships of MnO₂ precipitation, siderophore-Mn complex formation, siderophore degradation, and iron limitation in Mn-oxidizing bacterial cultures     

Dorothy L. Parker  Takami Morita  Rebecca Verity  James K. McCarthy 《Geochimica et cosmochimica acta》2007,71(23):5672-5683

To examine the pathways that form Mn^(III) and Mn^(IV) in the Mn^(II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn^(IV)O₂ formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn^(III) complex or insoluble Mn^(IV)O₂ minerals - but not both simultaneously. PVD-Mn^(III) was present, and MnO₂ precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn^(III) arose by predominantly ligand-mediated air oxidation of Mn^(II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn^(III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn^(III), a process linked to the production of both MnO₂ and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn^(III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO₂ to appear. These results suggest that P. putida cultures produce soluble Mn^(III) or MnO₂ by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO₂ under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn^(III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn^(III) versus MnO₂) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.  相似文献   

Thermodynamics of feldspathoid solutions     

Richard O. Sack  Mark S. Ghiorso 《Contributions to Mineralogy and Petrology》1998,130(3-4):256-274

We have developed models for the thermody-namic properties of nephelines, kalsilites, and leucites in the simple system NaAlSiO₄?KAlSiO₄?Ca_0.5AlSiO₄?SiO₂?H₂O that are consistent with all known constraints on subsolidus equilibria and thermodynamic properties, and have integrated them into the existing MELTS software package. The model for nepheline is formulated for the simplifying assumptions that (1) a molecular mixing-type approximation describes changes in the configurational entropy associated with the coupled exchange substitutions □Si?NaAl and □Ca? Na₂ and that (2) Na⁺ and K⁺ display long–range non-convergent ordering between a large cation and the three small cation sites in the Na₄Al₄Si₄O₁₆ formula unit. Notable features of the model include the prediction that the mineral tetrakalsilite (“panunzite”, sensu stricto) results from anti-ordering of Na and K between the large cation and the three small cation sites in the nepheline structure at high temperatures, an average dT/dP slope of about 55^°/kbar for the reaction over the temperature and pressure ranges 800–1050 ^°C and 500–5000 bars, roughly symmetric (i.e. quadratic) solution behavior of the K–Na substitution along joins between fully ordered components in nepheline, and large positive Gibbs energies for the nepheline reciprocal reactions and and for the leucite reciprocal reaction   相似文献