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1.
Four Fe-rich deposits, two occurring at springs, one on boulders in a stream and the fourth in a stream bed on andesitic volcanoes in the North Island, New Zealand, have been investigated by mineralogical techniques. They have poorly-ordered structure with compositions intermediate between those of ferrihydrite and hisingerite. Electron microscopy revealed solid spheres of 30 Å dia which formed 0.1-0.5 μm aggregates. Surface areas, as measured by ethylene glycol monoethyl ether, were close to 600 m2/g.X-ray diffraction gave weak patterns similar to both ferrihydrite and hisingerite. Infrared absorption showed a shift in the Si-O stretching band from 965 to 1020 cm?1 with decreasing amounts of Fe and increasing amounts of Si. These frequencies imply the presence of Fe-O-Si bonds in these materials. Desilication, by treatment with KOH in the laboratory, resulted in a conversion of these intermediates towards ferrihydrite. 相似文献
2.
We studied the local coordination and structure of Fe(III)-precipitates formed in aerated Fe(II)- and As(III)-containing water (buffered to pH 7 by 8 mM bicarbonate) using synchrotron-based X-ray absorption spectroscopy (XAS) at the K-edges of Fe, P, Ca, and As. Dissolved phosphate, silicate, and Ca at different ratios relative to each other and to Fe affect the forming Fe(III)-phases in a complex manner. The high affinity of phosphate for Fe(III) results in the predominant precipitation of Fe(III)-phosphate as long as dissolved phosphate is present, with Fe(III) polymerization limited to small oligomers. In Ca-containing solution, Ca uptake by Fe(III)-Ca-phosphate involves the linkage and coagulation of negatively charged Fe(III)-phosphate oligomers via Ca-O-P bonds. In the absence of phosphate, dissolved silicate at Si/Fe ratios above ∼0.5 results in the formation of hydrous ferric oxide (HFO) with mainly edge-sharing Fe-Fe linkage. At lower Si/Fe ratios of ∼0.5-0.1, mainly 2-line ferrihydrite (2L-Fh) with both edge- and corner-sharing Fe-Fe linkage forms. Only in the absence of phosphate at low Si/Fe ratio, lepidocrocite (Lp) forms. In solutions containing sufficient Fe(II), aeration results in the sequential precipitation of Fe(III)-(Ca-)phosphate, HFO or 2L-Fh (depending on solution Si/Fe), and finally Lp. The amount and oxidation state of As co-precipitated with Fe(III) are controlled by the co-oxidation of As(III) with Fe(II), which increases with initial Fe/As ratio, and the competitive uptake of phosphate, As(V) and less strongly sorbing silicate and As(III). This study demonstrates that the diversity and sequence of short-range-ordered Fe(III)-precipitates forming by Fe(II) oxidation in near-neutral natural waters depend on water chemistry. Because differences in the colloidal stability and biogeochemical reactivity of these phases will affect the fate of associated major and trace elements, the different Fe(III)-precipitates and their specific biogeochemical properties must be taken into account when addressing nutrient and contaminant dynamics at redox boundaries in natural and engineered systems. 相似文献
3.
An attenuated total reflectance IR study of silicic acid adsorbed onto a ferric oxyhydroxide surface
Silicic acid (H4SiO4) can have significant effects on the properties of iron oxide surfaces in both natural and engineered aquatic systems. Understanding the reactions of H4SiO4 on these surfaces is therefore necessary to describe the aquatic chemistry of iron oxides and the elements that associate with them. This investigation uses attenuated total reflectance infrared spectroscopy (ATR-IR) to study silicic acid in aqueous solution and the products formed when silicic acid adsorbs onto the surface of a ferrihydrite film in 0.01 M NaCl at pH 4. A spectrum of 1.66 mM H4SiO4 at pH 4 (0.01 M NaCl) has an asymmetric Si-O stretch at 939 cm−1 and a weak Si-O-H deformation at 1090 cm−1. ATR-IR spectra were measured over time (for up to 7 days) for a ferrihydrite film (≈1 mg) approaching equilibrium with H4SiO4 at concentrations between 0.044 and 0.91 mM. Adsorbed H4SiO4 had a broad spectral feature between 750 and 1200 cm−1 but the shape of the spectra changed as the amount of H4SiO4 adsorbed on the ferrihydrite increased. When the solid phase Si/Fe mole ratio was less than ≈0.01 the ATR-IR spectra had a maximum intensity at 943 cm−1 and the spectral shape suggests that a monomeric silicate species was formed via a bidentate linkage. As the solid phase Si/Fe mole ratio increased to higher values a discrete oligomeric silicate species was formed which had maximum intensity in the ATR-IR spectra at 1001 cm−1. The spectrum of this species suggests that it is larger than a dimer and it was tentatively identified as a cyclic tetramer. A small amount of a polymeric silica phase with a broad spectral feature centered at ≈1110 cm−1 was also observed at high surface coverage. The surface composition was estimated from the relative contribution of each species to the area of the ATR-IR spectra using multivariate curve resolution with alternating least squares. For a ferrihydrite film approaching equilibrium with 0.044, 0.14, 0.40 and 0.91 mM H4SiO4 the area of the spectra accounted for by monomeric species were 92%, 49%, 23% and 6%, respectively. The remainder was oligomer apart from a small amount (<5%) of polymerized silica at the two higher H4SiO4 concentrations. The solid phase Si/Fe mole ratios for these samples were 0.020, 0.037, 0.071 and 0.138, respectively. 相似文献
4.
The effect of silica and natural organic matter on the Fe(II)-catalysed transformation and reactivity of Fe(III) minerals 总被引：3，自引：0，他引：3
The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid 55Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments. 相似文献
5.
Schwertmannite stability in acidified coastal environments 总被引：1，自引：0，他引：1
Richard N. Collins Adele M. Jones T. David Waite 《Geochimica et cosmochimica acta》2010,74(2):482-3451
A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides. 相似文献
6.
Rollog Mark Cook Nigel J. Guagliardo Paul Ehrig Kathy Gilbert Sarah E. Kilburn Matt 《Geochemical transactions》2019,20(1):1-12
Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2–0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.
相似文献7.
8.
Iron distribution in the octahedral sheet of dioctahedral smectites. An Fe K-edge X-ray absorption spectroscopy study 总被引：1，自引：1，他引：1
D. Vantelon E. Montarges-Pelletier L. J. Michot M. Pelletier F. Thomas V. Briois 《Physics and Chemistry of Minerals》2003,30(1):44-53
The distribution of iron atoms in the octahedral sheet of a series of dioctahedral smectites with varying unit-cell composition and iron content was investigated by Fe K-edge XAS spectroscopy. First-step analysis reveals that the patterns corresponding to backscattering by atoms located between 3 and 4 Å from the absorbing atom are very sensitive to the relative amount of light (Si, Al, Mg) and heavy (Fe) atoms. Detailed modelling of this domain then provides valuable information on the number of iron atoms surrounding octahedral iron. By comparing the number of iron neighbours deduced from EXAFS with that determined from unit-cell composition assuming a statistical distribution, three groups of montmorillonites can be distinguished: (1) clay samples from Wyoming display an ordered distribution of iron atoms; (2) clay samples from Georgia, Milos, China and Washington exhibit a close to random distribution of iron atoms; (3) clay samples from North Africa, Germany, Texas and Arizona display extensive iron clustering. These results complement previously obtained IR results and show that the combination of these two spectroscopic techniques could provide an additional crystal-chemistry-based framework for typological analysis of montmorillonite deposits. 相似文献
9.
铁矿石物相分析标准物质的研制 总被引：2，自引：2，他引：2
介绍了研制铁矿石物相分析标准物质的研制工艺及技术关键，列出了磁性铁中铁、碳酸铁中铁、赤（褐）铁矿中铁、硫化铁中铁、硅酸铁中铁和全铁的原始数据和定值数据。所研制的６个标准物质已于１９９５年被国家技术监督局批准为一级标准物质，编号为ＧＢＷ０７２７１～０７２７６。 相似文献
10.
Two new isostructural compounds with fresnoite, Sr2TiSi2O8 and Ba2TiGe2O8, have been synthesized and investigated by X-ray diffraction and vibrational spectroscopy. The infrared (IR) and Raman spectra of fresnoite and fresnoite-like pyrosilicates are discussed on the basis of a factor group analysis and with the help of 28–30Si and 46–50Ti isotopic shifts. The short Ti-O bond participates to the 900–800 cm?1 region of the spectrum. However, because of an important mixing with some Si-O stretching modes having the same symmetry properties, no frequency is specifically related to the stretching of this bond. An assignment is also proposed for the remaining Si-O stretching frequencies. The existence or absence of a correlation between short Ti-O distances and high vibrational frequencies is briefly discussed. 相似文献
11.
PENG Jun YI Haisheng XIA Wenjie Postdoctoral Researchers Flow Station of SW China Petroleum Institute Institute of Sedimentary Geology Chengdu University of Technology Chengdu E-mail.tjc@cdit.edu.cn Institute of Sedimentary Geology Chengdu University of Technology Chengdu 《《地质学报》英文版》2000,74(1):46-53
In the Hunan-Guizhou-Guangxi area there have developed very thick bedded siliceous rocks of the late Sinian. The rocks have a fairly pure composition, with an average content of siliceous minerals exceeding 95%. They are relatively rich in Fe and Mn, and poor in Al, Ti and Mg. The Fe/Ti, (Fe+Mn)/Ti, Al/(Al+Fe+Mn) and U/Th ratios and the Al-Fe-Mn and Fe-Mn-(Ni+Co+Cu)×10 triangle diagrams all show that they are hydrothermal sedimentary siliceous rocks. In the rocks the total amount of REEs is low, the δCe shows an obvious negative anomaly and the 8Eu a weak anomaly, and LREE>HREE, all indicating that they are products of hydrothermal processes. The δ30Si and δ18O values, as well as the formation temperature of the rocks all clearly show that the silica forming the rocks comes from hot water. Besides, analyses of the depositional environment of the rocks using the MnO/TiO2 ratio and the δCe and δ30Si values yield the same conclusion that they are formed in environments from continental marginal slope 相似文献
12.
We investigated Fe(III)-precipitates formed from Fe(II) oxidation in water at pH 7 as a function of dissolved Fe(II), As(III), phosphate, and silicate in the absence and presence of Ca. We used transmission electron microscopy (TEM), including selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX) to characterize the morphology, structure and elemental composition of the precipitates. Results from our companion X-ray absorption spectroscopy (XAS) study suggested that the oxidation of Fe(II) leads to the sequential formation of distinct polymeric units in the following order: Fe(III)-phosphate oligomers in the presence of phosphate, silicate-rich hydrous ferric oxide (HFO-Si) at high Si/Fe (>0.5) or 2-line ferrihydrite (2L-Fh) at lower Si/Fe (∼0.1-0.5), and lepidocrocite (Lp) in the absence of phosphate at low Si/Fe (<0.1). Results from this study show that the size of the polymeric units increased along the same sequence and that the aggregation of these polymeric units resulted in spherical particles with characteristic surface textures changing from smooth to coarse. The diameter of the spherical particles increased from 15 to 380 nm as the molar ratio (P + Si + As)/Fe(II) in the starting solution decreased and larger spherical particles precipitated from Ca-containing than from Ca-free solutions. These trends suggested that the size of the spherical particles was controlled by the charge of the polymeric units. Spherical particles coagulated into flocs whose size was larger in the presence than in the absence of Ca. Further observations pointed to the importance of Fe(II) oxidation and polymerization versus polymer aggregation and floc formation kinetics in controlling the spatial arrangement of the different polymeric units within Fe(III)-precipitates. The resulting structural and compositional heterogeneity of short-range-ordered Fe(III)-precipitates likely affects their colloidal stability and their chemical reactivity and needs to be considered when addressing the fate of co-transformed trace elements such as arsenic. 相似文献
13.
Magnetite is a very common mineral in various types of iron deposits and some sulfide deposits. Recent studies have focused on the use of trace elements in magnetite to discriminate ore types or trace ore-forming process. Germanium is a disperse element in the crust, but sometimes is not rare in magnetite. Germanium in magnetite can be determined by laser ablation ICP-MS due to its low detection limit (0.0X ppm). In this study, we summary the Ge data of magnetite from magmatic deposits, iron formations, skarn deposits, iron oxide copper-gold deposits, and igneous derived hydrothermal deposits. Magnetite from iron formations contains relatively high Ge (up to ~250 ppm), whereas those from all other deposits mostly contains Ge less than 10 ppm, indicating that iron formations can be discriminated from other Fe deposits by Ge contents. Germanium in magmatic/hydrothermal magnetite is controlled by a few factors. Primary magma/fluid composition may be the major control of Ge in magnetite. Higher oxygen fugacity may be beneficial to Ge partition into magnetite. Sulfur fugacity and temperature may have little effect on Ge in magnetite. The enrichment mechanism of Ge in magnetite from iron formations remains unknown due to the complex ore genesis. Germanium along with other elements (Mn, Ni, Ga) and element ratios (Ge/Ga and Ge/Si raios) can distinguish different types of deposits, indicating that Ge can be used as a discriminate factor like Ti and V. Because of the availability of in situ analytical technique like laser ablation ICP-MS, in situ Ge/Si ratio of magnetite can serve as a geochemical tracer and may provide new constraints on the genesis of banded iron formations. 相似文献
14.
Comparison of measured far-from-equilibrium dissolution rates of natural glasses and silicate minerals at 25 °C and pH 4 reveals the systematic effects of crystallinity and elemental composition on these rates. Rates for both minerals and glasses decrease with increasing Si:O ratio, but glass dissolution rates are faster than corresponding mineral rates. The difference between glass and mineral dissolution rates increases with increasing Si:O ratio; ultra-mafic glasses (Si:O ? 0.28) dissolve at similar rates as correspondingly compositioned minerals, but Si-rich glasses such as rhyolite (Si:O ∼ 0.40) dissolve ?1.6 orders of magnitude faster than corresponding minerals. This behaviour is interpreted to stem from the effect of Si-O polymerisation on silicate dissolution rates. The rate controlling step of dissolution for silicate minerals and glasses for which Si:O > 0.28 is the breaking of Si-O bonds. Owing to rapid quenching, natural glasses will exhibit less polymerisation and less ordering of Si-O bonds than minerals, making them less resistant to dissolution. Dissolution rates summarized in this study are used to determine the Ca release rates of natural rocks at far-from-equilibrium conditions, which in turn are used to estimate their CO2 consumption capacity. Results indicate that Ca release rates for glasses are faster than those of corresponding rocks. This difference is, however, significantly less than the corresponding difference between glass and mineral bulk dissolution rates. This is due to the presence of Ca in relatively reactive minerals. In both cases, Ca release rates increase by ∼two orders of magnitude from high to low Si:O ratios (e.g., from granite to gabbro or from rhyolitic to basaltic glass), illustrating the important role of Si-poor silicates in the long-term global CO2 cycle. 相似文献
15.
Carlos Alberto Spier Sonia Maria Barros de Oliveira Carlos Alberto Rosière José Domingos Ardisson 《Mineralium Deposita》2008,43(2):229-254
Several major iron deposits occur in the Quadrilátero Ferrífero (QF), southeastern region of Brazil, where metamorphosed and heterogeneously deformed banded iron formation (BIF) of the Cauê Formation, regionally called itabirite, was transformed into high- (Fe >64%) and low-grade (30%?2O3, with a higher amount of detrimental impurities, especially MnO, in the soft ore. Both hard and soft ores are depleted in trace elements. The high-grade ores at the Águas Claras Mine have at least a dual origin, involving hypogene and supergene processes. The occurrence of the hard, massive high-grade ore within “fresh” dolomitic itabirite is evidence of its hypogene origin. Despite the contention about the origin of the dolomitic itabirite (if this rock is a carbonate-rich facies of the Cauê Formation or a hematite–carbonate precursor of the soft high-grade ore), mineralogical and geochemical features of the soft high-grade ore indicate that it was formed by leaching of dolomite from the dolomitic itabirite by meteoric water. The comparison of the Águas Claras, Capão Xavier and Tamanduá orebodies shows that the original composition of the itabiritic protore plays a major role in the genesis of high- and low-grade soft ores in the QF. Under the same weathering and structural conditions, the dolomitic itabirite is the more favorable to form high-grade deposits than siliceous itabirite. Field relations at the Águas Claras and Capão Xavier deposits suggest that it is not possible to form huge soft high-grade supergene deposits from siliceous itabirite, unless another control, such as impermeable barriers, had played an important role. The occurrence in the Tamanduá Mine of a large, soft, high-grade orebody formed from siliceous itabirite and closely associated with hypogene hard ore suggests that large, soft, high-grade orebodies of the Quadrilátero Ferrífero, which occur within siliceous itabirite, have a hypogene contribution in their formation. 相似文献
16.
Macronutrients and micronutrients were measured during the phytoplankton bloom period and then seasonally monitored after
the bloom in the polluted Izmir Bay. Iron and the macronutrients (phosphate, ammonium, nitrate, nitrite, and silicate) were
abundant in the waters of the inner and middle sections of Izmir Bay. The iron concentration decreased exponentially from
the eutrophic inner bay to the oligotrophic outer bay. Suboxic–anoxic processes and the resuspension dynamics in the sediment
were the most important factor in the control of iron, ammonium, and phosphate enrichment in the bay beside the anthropogenic
activities. The biological removal of Fe in the inner and middle bay and nonbiological removal in the outer bay were effective
in controlling iron concentration in Izmir Bay. The nitrate, nitrite, and ammonium nitrogen (N) and Si decreased to critical
levels in the middle and outer bay at the end of the summer as long as the concentration of phosphate was high. The N/P ratios
in the bay suggested that N might be the controlling nutrient for phytoplankton growth particularly in the middle and outer
bay throughout summer. Furthermore, Si was also able to have controlling impact probably on diatom growth during autumn and
winter in the inner and middle bay and in the early spring in the outer bay. The N/Si/Chelex labile Fe ratios implied that
the iron could be a critical controlling nutrient for phytoplankton growth during early April in the outer bay unless the
other macronutrients were low. 相似文献
17.
Sequestration of organic carbon (OC) in environmental systems is critical to mitigating climate change. Organo-mineral associations, especially those with iron (Fe) oxides, drive the chemistry of OC sequestration and stability in soils. Short-range-ordered Fe oxides, such as ferrihydrite, demonstrate a high affinity for OC in binary systems. Calcium commonly co-associates with OC and Fe oxides in soils, though the bonding mechanism (e.g., cation bridging) and implications of the co-association for OC sequestration remain unresolved. We explored the effect of calcium (Ca2+) on the sorption of dissolved OC to 2-line ferrihydrite. Sorption experiments were conducted between leaf litter-extractable OC and ferrihydrite at pH 4 to 9 with different initial C/Fe molar ratios and Ca2+ concentrations. The extent of OC sorption to ferrihydrite in the presence of Ca2+ increased across all tested pH values, especially at pH ≥ 7. Sorbed OC concentration at pH 9 increased from 8.72 ± 0.16 to 13.3 ± 0.20 mmol OC g?1 ferrihydrite between treatments of no added Ca2+ and 30 mM Ca2+ addition. Batch experiments were paired with spectroscopic studies to probe the speciation of sorbed OC and elucidate the sorption mechanism. ATR-FTIR spectroscopy analysis revealed that carboxylic functional moieties were the primary sorbed OC species that were preferentially bound to ferrihydrite and suggested an increase in Fe-carboxylate ligand exchange in the presence of Ca at pH 9. Results from batch to spectroscopic experiments provide significant evidence for the enhancement of dissolved OC sequestration to 2-line ferrihydrite and suggest the formation of Fe–Ca-OC ternary complexes. Findings of this research will inform modeling of environmental C cycling and have the potential to influence strategies for managing land to minimize OM stabilization. 相似文献
18.
David M. Jenkins 《Physics and Chemistry of Minerals》1989,16(4):408-414
A detailed evaluation of the assignments given to the infrared (IR) vibrations in the lattice stretching region is presented here based on observations of the effects of various chemical substitutions in synthetic analogues of phlogopite, KMg3(AlSi3)O10(OH)2. As in previous studies, this study has confirmed that the 995, 960, and 460 cm?1 vibrations are influenced by Si, the 822 and 760 cm?1 vibrations by Al, the 915 and 725 cm?1 vibrations by Al and Si, and the 592 cm?1 vibration by OH. Contrary to previous studies, it is shown here that the 690, 495, and 375 cm?1 vibrations are strongly linked with Mg and not just Si. The 655 cm?1 band in phlogopite is attributed to an in-plane Al-O vibration rather than an Al-O-Si vibration. As a check on the band assignments made here, IR spectra were obtained for synthetic clintonite, CaMg2Al(Al3Si)O10(OH)2, as well as its chemical analogues and compared with the IR spectrum of phlogopite. The band intensities for the Si-O, Al-O, and Si-O-Mg vibrations changed in accord with the composition of clintonite. The most intense band in clintonite at 660 cm?1 appears to be associated only with Al and is assigned here to a tetrahedral Al-O-Al vibration which must be present, if not dominant, in this mineral. The near coincidence of an in-plane Al-O vibration at 655 cm?1 (phlogopite) and an in-plane Al-O-Al vibration at 660 cm?1 (clintonite) makes the identification of tetrahedral Al-Si order-disorder in trioctahedral layered silicates by IR spectroscopy very difficult. The ratio of the 822/995 cm?1 bands may, however, prove to be very useful for discerning the amount of tetrahedrally coordinated Al in these types of minerals. 相似文献
19.
广西南宁地区泥盆系硅质岩地球化学特征及沉积环境 总被引：2，自引：1，他引：1
泥盆纪时,广西南宁附近发育了一套从早泥盆世埃姆斯期到晚泥盆世弗拉斯期末的硅质岩建造,硅质岩多为薄层,灰黑到黑色,至弗拉斯阶上部变为灰黄色,水平纹理发育,常夹火山凝灰岩或与之互层。这套硅质岩SiO2含量高（一般>90％）,其他主量化学成分均很低（一般<5%）。TFe2O3和含量相对比较富集（平均含量3.32％）, Al2O3、TiO2、MgO和MnO相对贫乏（平均含量分别为0.71％、0.04％、0.10％和0.02％）。常量元素Fe/Ti、（Fe+Mn）/Ti和Al/（Al+Fe+Mn）比值的平均值分别为91.65,92.12和0.25,微量元素Ti/V和U/Th比值的平均值分别为4.57和4.09,其中U/Th比值在弗拉斯期早期达到最大。这些数据说明,硅质岩在形成时受到了明显的海底热液活动影响,而这种热液活动在弗拉斯期早期达到最强,后逐渐减弱,而热液活动的强度可能主要受盆地裂解（或张裂作用）的影响;因此,盆地拉张作用在弗拉斯期早期达到最强,这与硅质岩的空间分布是吻合的。 相似文献
20.
《Chemie der Erde / Geochemistry》2021,81(1):125714
The dramatic decline in aqueous Ni concentrations in the Archean oceans during the Great Oxygenation Event is evident in declining solid phase Ni concentrations in Banded Iron Formations (BIFs) at the time. Several experiments have been performed to identify the main removal mechanisms of Ni from seawater into BIFs, whereby adsorption of Ni onto ferrihydrites has shown to be an efficient process. Ni isotopic measurements have shown limited isotopic fraction during this process, however, most experiments have been conducted in simple solutions containing varying proportions of dissolved Fe and Ni as NO3 salts, as opposed to Cl salts which are dominant in seawater. Further, Archean oceans were, before the advent of siliceous eukaryotes, likely saturated with amorphous Si as seen in the interlayered chert layers within BIFs. Despite Si being shown to greatly affect the Ni elemental partitioning onto ferrihydrite solids, no studies have been made on the effects of Si on the Ni isotope fractionation. Here we report results of multiple coprecipitation experiments where ferrihydrite precipitated in mixed solutions with Ni and Si. Ni concentrations in the experiments ranged between 200 and 4000 nM for fixed concentrations of Si at either 0, 0.67 or 2.2 mM. The results show that Si at these concentrations has a limited effect on the Ni isotope fractionation during coprecipitation of ferrihydrite. At 0.67 mM, the saturation concentration of cristobalite, the isotopic fractionation factors between the precipitating solid and experimental fluid are identical to experiments not containing Si (0.34 ± 0.17‰). At 2.2 mM Si, and the saturation concentration of amorphous silica, however, the Ni isotopic composition of the ferrihydrite solids deviate to more negative values and show a larger variation than at low or no Si, and some samples show fractionation of up to 0.5‰. Despite this seemingly more unstable fractionation behaviour, the combined results indicate that even at as high concentrations of Si as 2.2 mM, the δ60Ni values of the forming ferrihydrites does not change much. The results of our study implicate that Si may not be a major factor in fractionating stable Ni isotopes, which would make it easier to interpret future BIF record and reconstruct Archean ocean chemistry. 相似文献