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1.
The ferrozine wet chemical method was optimised for the determination of the total iron content and speciation in small geological samples. The ferrozine micro‐method involves dissolution by a mixture of HF and H2SO4 followed by spectrophotometric analysis using the complexing agent ferrozine. The method was tested for twenty‐one replicates of eight rock RMs using test portions of 5–14 mg and containing 0.37–5.45 mg total Fe and more than 0.29 mg Fe(II). The optimised ferrozine method was accurate to within 0.23% m/m FeO and 0.34% m/m total Fe, which compares favourably to other wet chemical methods.  相似文献   

2.
The preparation and characterisation of four chromium ore reference materials are described in this paper. The sample material for GCr‐1, GCr‐3 and GCr‐4 was collected from chromite deposits in Tibet, Qinghai province and Inner Mongolia. GCr‐2 is a composite sample from GCr‐1 and GCr‐4. Sample homogeneity was tested by WD‐XRF and the relative standard deviations were < 1.0%. An F‐test showed that all four materials were homogeneous. Thirteen laboratories involved in the inter‐laboratory programme provided 672 determinations (eighteen oxides and elements). Sixteen components were characterised as certified values, of which Cr2O3 ranged from 17.59 to 57.80% m/m. The contents of FeO and CO2 were taken as reference values.  相似文献   

3.
Analytical methods used for determining dissolved Fe(II) often yield inaccurate results in the presence of high Fe(III) concentrations. Accurate analysis of Fe(II) in solution when it is less than 1% of the total dissolved Fe concentration (FeT) is sometimes required in both geochemical and environmental studies. For example, such analysis is imperative for obtaining the ratio Fe(II)/Fe(III) in rocks, soils and sediments, for determining the kinetic constants of Fe(II) oxidation in chemical or biochemical systems operating at low pH, and is also important in environmental engineering projects, e.g. for proper control of the regeneration step (oxidation of Fe(II) into Fe(III)) applied in ferric-based gas desulphurization processes. In this work a method capable of yielding accurate Fe(II) concentrations at Fe(II) to FeT ratios as low as 0.05% is presented. The method is based on a pretreatment procedure designed to separate Fe(II) species from Fe(III) species in solution without changing the original Fe(II) concentration. Once separated, a modified phenanthroline method is used to determine the Fe(II) concentration, in the virtual absence of Fe(III) species. The pretreatment procedure consists of pH elevation to pH 4.2–4.65 using NaHCO3 under N2(g) environment, followed by filtration of the solid ferric oxides formed, and subsequent acidification of the Fe(II)-containing filtrate. Accuracy of Fe(II) analyses obtained for samples (Fe(II)/FeT ratios between 2% and 0.05%) to which the described pretreatment was applied was >95%. Elevating pH to above 4.65 during pretreatment was shown to result in a higher error in Fe(II) determination, likely resulting from adsorption of Fe(II) species and their removal from solution with the ferric oxide precipitate.  相似文献   

4.
Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe2O3 in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al2O3–Fe2O3–SiO2–H2O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe3+ content and a high XMg= (Mg/ (Mg+Fe2+)) under these P–T conditions.  相似文献   

5.
The Neoarchean Bundelkhand greenstone sequences at Mauranipur and Babina areas within the Bundelkhand Gneissic Complex preserve a variety of magmatic rocks such as komatiitic basalts, basalts,felsic volcanic rocks and high-Mg andesites belonging to the Baragaon, Raspahari and Koti Formations.The intrusive and extrusive komatiitic basalts are characterized by low SiO_2(39-53 wt.%), high MgO(18-25 wt.%).moderately high Fe_2O_3(7.1-11.6 wt.%), Al_2O_3(4.5-12.0 wt.%), and TiO_2(0.4-1.23 wt.%)with super to subchondritic(Gd/Yb)N ratios indicating garnet control on the melts. The intrusive komatiitic suite of Ti-enriched and Al-depleted type possesses predominant negative Eu and positive Nb, Ti and Y anomalies. The chemical composition of basalts classifies them into three types with varying SiO_2, TiO_2, MgO, Fe_2O_3, Al_2O_3 and CaO. At similar SiO_2 content of type Ⅰ and Ⅲ basalts, the type II basalts show slightly high Al_2O_3 and Fe_2O_3 contents. Significant negative anomalies of Nb, Zr, Hf and Ti, slightly enriched LREE with relatively flat HREE and low ∑REE contents are observed in type Ⅰ and Ⅱ basalts. TypeⅢ basalts show high Zr/Nb ratios(9.8-10.4), TiO_2(1.97-2.04 wt.%), but possess strikingly flat Zr, Hf, Y and Yb and are uncontaminated. Andesites from Agar and Koti have high SiO_2(55-64 wt.%), moderate TiO_2(0.4-0.7 wt.%), slightly low Al_2O_3(7-11.9 wt.%), medium to high MgO(3-8 wt.%) and CaO contents(10-17 wt.%). Anomalously high Cr, Co and Ni contents are observed in the Koti rhyolites. Tholeiitic to calc alkaline affinity of mafic-felsic volcanic rocks and basalt-andesite dacite-rhyolite differentiation indicate a mature arc and thickened crust during the advanced stage of the evolution of Neoarchean Bundelkhand greenstone belt in a convergent tectonic setting where the melts were derived from partial melting of thick basaltic crust metamorphosed to amphibolite-eclogite facies. The trace element systematics suggest the presence of arc-back arc association with varying magnitudes of crust-mantle interaction. La/Sm, La/Ta,Nb/Th, high MgO contents(20 wt.%), CaO/Al_2O_3 and(Gd/Yb)_N 1 along with the positive Nb anomalies of the komatiite basalts reflect a mantle plume source for their origin contaminated by subductionmetasomatized mantle lithosphere. The overall geochemical signatures of the ultramafic-mafic and felsic volcanic rocks endorse the Neoarchean plume-arc accretion tectonics in the Bundelkhand greenstone belt.  相似文献   

6.
Using the thermodynamic algorithm of Sugawara (Contributions to Mineralogy and Petrology 141, 2001, p. 659–686), FeO and Fe2O3 concentrations in plagioclase were computed for 420 published experiments on tholeiitic, FeTi-tholeiite, calc-alkaline, and alkaline magma compositions. Estimates of the partition coefficient between plagioclase and liquid range from 0.19 to 0.92 for Fe2O3 and from 0.008 to 0.050 for FeO, i.e. ca. twenty times greater for Fe2O3 than for FeO. Partitioning of Fe2O3 and FeO is independent of both oxygen fugacity and plagioclase composition, contradicting the common assumption that partitioning of Fe2O3 correlates positively with the amount of aluminium in plagioclase. In contrast, the SiO2-content of the magma correlates positively with the partition coefficients for Fe2O3 and FeO. This is ascribed to increasing activity of iron in polymerised SiO2-rich magma. Advances of micro-beam Fe-XANES techniques allow the determination of Fe3+/Fe in plagioclase. Using such plagioclase data and the partition coefficients for Fe2O3 and FeO, the Fe2O3/FeO and oxygen fugacity of equilibrium magma may be estimated. As petrological examples, we estimate that the oxygen fugacity of the Palisades sill ranged from the QFM buffer to 0.5 log unit below it (QFM to QFM –0.5), the Lake County basalt from QFM to QFM –2, and Upper Zone a of the Skaergaard intrusion from QFM –1 to QFM –1.5.Editorial responsibility: I. Parsons  相似文献   

7.
Hydrothermal synthesis of Fe-pum-pellyites was conducted using high pressure cold-seal apparatus and solid oxygen buffering techniques at temperatures between 250°C and 550°C and 2.0–9.1 kbar Pfluid. Fe-pumpellyites were synthesized from partially crystalline gel mixtures of compositions: 4CaO - 2.1Al2O3_1.5FeO - 0.3MgO - 6SiO2 (II) and 3CaO - 1.5 Al2O3 - 2.7FeO - 0.3MgO - 6SiO2 (III) in the presence of excess H2O at Pfluid of 5–9.1 Kbar, temperatures between 275°C and 325°C, and fO2 defined by the QFM and HM buffers; for both of these compositions (II and III), the condensed synthetic run products included minor 7Å chlorite ± garnet ± Fe-oxide. The cell dimensions and aggregate refractive index (a= 19.13(2)Å, b= 5.940(4)Å, c= 8.847(5)Å, ±= 97.37(6)±, and n= 1.702(2)) of the pum-pellyite synthesized from the bulk composition II mix are compatible with those of natural pumpellyites containing similar total Fe contents. Attempts at synthesizing Fe-pumpellyites from a Mg-free bulk composition were not successful; these results are consistent with the total absence of natural Mg-free pumpellyites. The higher temperature, higher oxygen fugacity assemblages of the equivalent bulk compositions (II and III) consist of epidote ± minor amounts of chlorite, garnet, quartz, hematite, and magnetite. The results of these synthesis experiments accord with the mineral parageneses observed in low-grade metabasites which imply that Fe-pumpellyites are replaced by epidote with increasing temperature and/or fO2 and that Fe3+ is preferentially partitioned into epidote with respect to coexisting pum-pellyite. In addition, these synthesis experiments indicate that Fe-bearing pumpellyites crystallize at and are stable to lower temperatures than more aluminous pumpellyites—a result also consistent with natural systems.  相似文献   

8.
The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al2O3–SiO2 (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe2O3, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al2O3–SiO2–O (FMASO) and FeO–MgO–Al2O3–SiO2– TiO2–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe2O3 and TiO2 on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.  相似文献   

9.
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10.
FeO*‐Al2O3‐TiO2‐rich rocks are found associated with transitional tholeiitic lava flows in the Tertiary Bana plutono‐volcanic complex in the continental sector of the Cameroon Line. These peculiar rocks consist principally of iron‐titanium oxides, aluminosilicates and phosphates, and occur as layers 1–3 m thick occupying the upper part of lava flows on the southwest (site 1) and northwest (site 2) sites of the complex. Mineral constituents of the rocks include magnetite, ilmenite, hematite, rutile, corundum, andalusite, sillimanite, cordierite, quartz, plagioclase, alkali feldspar, apatite, Fe‐Mn phosphate, Al phosphate, micas and fine mixtures of sericite and silica. Texturally and compositionally, the rocks can be subdivided into globular type, banded type, and Al‐rich fine‐gained massive type. The first two types consist of dark globule or band enriched in Fe‐Ti oxides and apatite and lighter colored groundmass or bands enriched in aluminosilicates and quartz, respectively. The occurrence of andalusite and sillimanite and the compositional relations of magnetite and ilmenite in the FeO*‐Al2O3‐TiO2‐rich rocks suggest temperatures of crystallization in a range of 690–830°C at low pressures. The Bana FeO*‐Al2O3‐TiO2‐rich rocks are characterized by low concentrations of SiO2 (25–54.2 wt%), Na2O + K2O (0–1%), CaO (0–2%) and MgO (0–0.5%), and high concentrations of FeO* (total iron as FeO, 20–42%), Al2O3 (20–42%), TiO2 (3–9.2%), and P2O5 (0.26–1.30%). TiO2 is positively correlated with Al2O3 and inversely correlated with FeO*. The bulk rock compositions cannot be derived from the associated basaltic magma by crystal fractionation or by partial melting of the mantle or lower crustal materials. In ternary diagrams of (Al2O3)?(CaO + Na2O + K2O)?(FeO*+ MnO + MgO) and (SiO2)?(FeO*)?(Al2O3), the compositional field of the rocks is close to that of laterite and is distinct from the common volcanic rocks, suggesting that the rocks are derived from lateritic materials by recrystallization when the materials are heated by the basaltic magmas. A hydrothermal origin is discounted because the rocks contain high‐temperature mineral assemblages and lack sulfide minerals. It is proposed that the FeO*‐Al2O3‐TiO2‐rich rocks of the Bana complex were formed by pyrometamorphism of laterite by the heat of basaltic magmas.  相似文献   

11.
The mercury content of 116 reference materials (RMs) from ten international organisations was determined in this study, which focused on variability within and between batches of RMs. Direct mercury analysis (DMA) was applied to RMs having Hg contents between 1 and 6300 ng g?1 and provided good precision and accuracy. Accuracy was demonstrated by the agreement of our results with certified values, while replicates were made to establish the precision. Low within‐batch variability was noted, with precision from 0.1 to 23% (n = 3–5) apparently depending on Hg content and homogeneity, whereas systematic offsets were detected among several batches. Thanks to the analysis of different batches; the homogeneity or heterogeneity of several RMs was shown, and thus, suitable RMs for quality control for Hg determinations could be recommended.  相似文献   

12.
Natural attenuation of arsenic by simple adsorption on oxyhydroxides may be limited due to competing oxyanions, but uptake by coprecipitation may locally sequester arsenic. We have systematically investigated the mechanism and mode (adsorption versus coprecipitation) of arsenic uptake in the presence of carbonate and phosphate, from solutions of inorganic composition similar to many groundwaters. Efficient arsenic removal, >95% As(V) and ∼55% in initial As(III) systems, occurred over 24 h at pHs 5.5-6.5 when Fe(II) and hydroxylapatite (Ca5(PO4)3OH, HAP) “seed” crystals were added to solutions that had been previously reacted with HAP, atmospheric CO2(g) and O2(g). Arsenic adsorption was insignificant (<10%) on HAP without Fe(II). Greater uptake in the As(III) system in the presence of Fe(II) was interpreted as due to faster As(III) to As(V) oxidation by molecular oxygen in a putative pathway involving Fe(IV) and As(IV) intermediate species. HAP acts as a pH buffer that allows faster Fe(II) oxidation. Solution analyses coupled with high-resolution transmission electron microscopy (HRTEM), X-ray Energy-Dispersive Spectroscopy (EDS), and X-Ray Absorption Spectroscopy (XAS) indicated the precipitation of sub-spherical particles of an amorphous, chemically-mixed, nanophase, FeIII[(OH)3(PO4)(AsVO4)]·nH2O or FeIII[(OH)3( PO4)(AsVO4)(AsIIIO3)minor]·nH2O, where AsIIIO3 is a minor component.The mode of As uptake was further investigated in binary coprecipitation (Fe(II) + As(III) or P), and ternary coprecipitation and adsorption experiments (Fe(II) + As(III) + P) at variable As/Fe, P/Fe and As/P/Fe ratios. Foil-like, poorly crystalline, nanoparticles of FeIII(OH)3 and sub-spherical, amorphous, chemically-mixed, metastable nanoparticles of FeIII[(OH)3, PO4]·nH2O coexisted at lower P/Fe ratios than predicted by bulk solubilities of strengite (FePO4·2H2O) and goethite (FeOOH). Uptake of As and P in these systems decreased as binary coprecipitation > ternary coprecipitation > ternary adsorption.Significantly, the chemically-mixed, ferric oxyhydroxide-phosphate-arsenate nanophases found here are very similar to those found in the natural environment at slightly acidic to circum-neutral pHs in sub-oxic to oxic systems, such phases may naturally attenuate As mobility in the environment, but it is important to recognize that our system and the natural environment are kinetically evolving, and the ultimate environmental fate of As will depend on the long-term stability and potential phase transformations of these mixed nanophases. Our results also underscore the importance of using sufficiently complex, yet systematically designed, model systems to accurately represent the natural environment.  相似文献   

13.
王海芝  程捷 《第四纪研究》2008,28(6):1090-1097
周口店地区的古环境变化研究多数研究集中在中更新世时期,而缺乏对早更新世时期环境变化的研究。这主要是由于缺少保存完好的早更新世沉积记录造成的。随着对20世纪80年代在周口地区发现的东洞剖面,发现这是一个保存完好的早更新世剖面,为研究早更新世时期的古环境变化特征提供了良好的研究材料。为了重建早更新世时期的古环境变化特征,利用XRF对东洞洞穴沉积物的主要元素（SiO2,Al2O3,Fe2O3和CaO）的化学组成进行了高分辨率分析,同时对沉积物中的FeO含量进行了测试。结果显示东洞剖面沉积物的主要化学组成为SiO2,占41.6%～58.9%,其次是Al2O3和Fe2O3,其含量的变化范围分别为13.69%～29.63%和5.00%～9.81%。Al2O3和Fe2O3在剖面上与SiO2含量成明显的镜像变化关系,显示出Al2O3和Fe2O3对沉积物中SiO2含量的稀释作用。另外,Fe2O3与Al2O3在剖面上具有很好的相关性,表明Fe2O3主要富集在富铝的矿物中。从元素含量在剖面的上分布看,东洞剖面的化学组成发生3次大的波动,主要表现为SiO2和FeO含量增高,而Fe2O3与Al2O3含量的减少。这3次波动分别出现在剖面的15.3～14.6m,11.0～9.9m和8.40～7.84m深度处。在3次化学组成的波动出现的同时,指示沉积物风化程度和温度变化的Si/Al（SiO2/Al2O3）和FeO/Fe2O3比值也发生了明显变化,比值增高,指示了3次大的干冷事件。另外,在剖面上部（10.00～7.84m,即第2次事件以后）SiO2/Al2O3和FeO/Fe2O3比值变高且波动频繁,表明自第2次干冷事件后沉积区的环境变得不稳定,逐渐向冷干气候转变。东洞剖面的地球化学记录（SiO2/Al2O3和FeO/Fe2O3）与泾川黄土剖面的粒度曲线具有较好的对比性,支持了东洞剖面记录的环境信息与黄土沉积记录的环境变化具有一致性。通过与泾川粒度曲线的对比发现,东洞剖面记录的3次干冷事件在时段上分别对应于黄土-古土壤序列中的L26,L15和L13。  相似文献   

14.
《地学前缘(英文版)》2018,9(6):1711-1724
The Helanshan tectonic belt(HTB) is a major tectonic divide between the Alxa and Ordos blocks in the North China Craton. The geochronology and petrogenesis of the mafic dykes in the northern HTB are keys to understanding the tectonic evolution of this belt. The mafic dykes, intruded into the Neoarchean-Paleoproterozoic metamorphic basement, are mainly composed of diabase with a mineral assemblage of plagioclase(45%-60%), pyroxene(25%-35%), minor quartz and Fe-Ti oxides. The LA-ICPMS U-Pb analysis of zircon grains from representative dykes yield a weighted mean age of 206 ± 1.9 Ma, which represents the crystallization age of the dyke. The diabases show high contents of Fe_2 O_3~T(11.88-17.55 wt.%), low contents of SiO_2(45.65-50.95 wt.%) and MgO(3.31-5.50 wt.%) with low Mg#(=100×MgO/(MgO + FeO) atomic ration) of 33-44. They are characterized by enrichment of light rare earth elements(LREEs) and large ion lithophile elements(LILEs)(e.g., Rb, Ba and Pb), and slight depletion of high field strength elements(HFSEs). These features suggest that the magma has undergone extensive fractionation of olivine and pyroxene but only minor crustal contamination during its evolution. Their high Sm contents and La/Sm ratios, and low Sm/Yb ratios indicate that magma from which the dykes formed was derived from low degree(about 5%) partial melting of an enriched garnet + spinel lherzolite mantle source. Together with regional geology, these geochemical and geochronological data suggest that the mafic dykes in the HTB were formed in an intracontinental extensional setting during the late Triassic.  相似文献   

15.
Data reported by laboratories contributing to the GeoPT proficiency testing programme for geochemical laboratories over the period from 2001 to 2011 have been assessed to identify the elements and concentration ranges over which analytical performance can be considered satisfactory. Criteria developed in the paper indicated that performance in the content determination of the elements/constituents SiO2, Al2O3, MnO, Cs, Dy, Er, Eu, Ga, Hf, Ho, Lu, Nd, Pr, Sm, Sr, Tb, Tl, Tm, U, Y, Yb and Zn was satisfactory over the full concentration range assessed. The elements/constituents TiO2, Fe2O3(T), MgO, CaO, Na2O, K2O, P2O5, Ba, Be, Cd, Ce, Co, Gd, La, Li, Nb, Rb, Sb, Sc, Sn, Ta, Th, V and Zr showed some degradation in performance at lower concentration levels (approaching the detection limit of some techniques). Performance in determining LOI, As, Bi, Cr, Cu, Ge, Mo, Ni, Pb and W was in general unsatisfactory over the full concentration range assessed. Other elements (especially Fe(II)O, H2O+, CO2, Ag, Au, B, Br, Cl, F, Hg, I, In, Ir, N, Os, Pd, Pt, Re, Rh, S, Se, Te) could not be evaluated as they were not routinely reported by laboratories participating in the GeoPT programme, often because they are present in silicate rocks at sufficiently low concentrations to require a pre‐concentration stage. Some suggestions are made for the causes of unsatisfactory performance, but further progress will require a detailed assessment of the methods used by participating laboratories, which will form the subject of a further paper.  相似文献   

16.
Cordierite–orthoamphibole gneisses and rocks of similar composition commonly contain low‐variance mineral assemblages that can provide useful information about the metamorphic evolution of a terrane. New calculated petrogenetic grids and pseudosections are presented in the FeO–MgO–Al2O3–SiO2–H2O (FMASH), Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH) and Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3 (NCKFMASHTO) chemical systems to investigate quantitatively the phase relations in these rocks. Although the bulk compositions of cordierite–orthoamphibole gneisses are close to FMASH, calculations in this system do not adequately account for the observed range of mineral assemblages. Calculations in NCKFMASH and NCKFMASHTO highlight the role of minor constituents such as Ca, Na and Fe3+ in the mineral assemblage evolution of such rocks and these systems are more appropriate for interpreting the evolution of natural examples.  相似文献   

17.
The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al2O3–SiO2 (FMAS) system. However, the potential for sapphirine to contain significant Fe3+ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O (FMASTO), expansion into K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H2O and O contents to use in the modelled compositions are investigated using T–MH2O and T–MO pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.  相似文献   

18.
This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe2+ substitution on SIMS δ18O bias measured from the dolomite–ankerite solid solution series [CaMg(CO3)2–CaFe(CO3)2], whereas this complementary work explores the compositional dependence of SIMS δ13C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ13C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).  相似文献   

19.
Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5–Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least ~?1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+?+?[6]Mg2+?=?2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298?=???1981.5 kJ mol??1. Solid solution is complete across the Fe4O5–Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg–Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.  相似文献   

20.
《Geochimica et cosmochimica acta》1999,63(19-20):3171-3182
The oxidation rate of pyrite at pH 7, 25°C and at constant partial pressure of oxygen (0.21 and 0.177 atm) was measured in the presence of the Fe(III)-chelators NTA, oxalate, leucine, EDTA, citrate, IDA and the Fe(III)-reductant ascorbic acid. With the exception of leucine and EDTA, non-reducing Fe(III)-chelators increased the oxidation rate relative to the reference state of formation of the Fe(OH)2+ complex at pH 7. The rate increase was proportional to the logarithm of the conditional stability constant of the ligands for the complexation of Fe3+. No effect on the oxidation rate was observed in the presence of EDTA, which shifted the redox potential of the redox couple Fe2+/Fe3+ to a value below that in the absence of any ligand at pH 7. Ascorbic acid decreased the pyrite oxidation rate by a factor of 5 at ascorbic acid concentrations between 10−4 and 10−2 mol L−1. Comparison of the rate constants for the oxidation of ascorbic acid by surface bound Fe(III) in the absence and presence of pyrite shows that the pyrite surface accelerates this reaction by a factor of 10. The oxidation of both pyrite and ascorbic acid is of fractional order with respect to ascorbic acid (HAsc): rpy=0.55 c(HAsc)−0.35 rHAsc=3.6 c(HAsc)0.59. Both the results from experiments with Fe(III)-chelating ligands and the Fe(III)-reductant, suggest a very efficient interference in the electron cycling between Fe(II) and Fe(III) at the pyrite surface. The interference seems to be mainly related to the reductive side of the iron cycling. It is therefore concluded that the electron transfer between ferric iron and pyritic sulfur limits the pyrite oxidation rate at pH 7.  相似文献   

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