纳米镍/铁去除氯代烃影响因素的探讨

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法去除率很低。近年来随着铁还原技术的发展,纳米铁和纳米双金属也成为一个活跃的研究领域。利用批实验的研究方法以四氯乙烯(PCE)和四氯化碳(CT)为目标污染物,研究纳米镍/铁在去除PCE过程中的影响因素。实验结果表明,在碱性条件下,纳米Ni/Fe对PCE脱氯速率比在酸性和中性条件下脱氯速率更快;纳米Ni/Fe对初始浓度为6·51mg/L的PCE溶液脱氯速率是对初始浓度为20·56mg/L的PCE溶液脱氯速率的1·8倍;对于氯代程度相同的CT和PCE,对CT的脱氯速率明显快于对PCE。     

壳聚糖包覆纳米铁镍双金属的迁移性能及其降解地下水中三氯乙烯的研究

地下水中三氯乙烯(TCE)严重威胁公众健康和环境安全,纳米零价铁原位注射技术可以还原降解TCE,但是应用中,纳米零价铁存在易氧化团聚而失活、迁移性差等问题。为此,利用天然高分子壳聚糖作包覆剂增强分散性和稳定性,镍作催化剂增强反应活性,成功制备获得壳聚糖包覆纳米铁镍双金属颗粒(CS Fe Ni)。沉降光谱实验表明包覆壳聚糖后纳米铁的分散稳定性得到增强,Zeta电位测试进一步证实颗粒表面负电荷增加,提高了静电排斥力,使得CS Fe Ni分散稳定性明显改善。柱迁移实验表明改性后的CS Fe Ni迁移能力得到提高。批实验表明CS Fe Ni能够高效降解TCE并能完全脱氯,研究结果为纳米铁原位注射技术的实际应用提供了理论基础和实验参考。     

The supergene origin of ruthenian hexaferrum in Ni‐laterites

For two decades, the nature of Fe‐rich, oxygen‐bearing, Ru–Os compounds found in the supergene environment has been debated. Ru–Os–Fe‐oxides and nano‐intergrowths of ruthenium with magnetite have been proposed. We applied FE‐SEM, EMPA, μ‐Raman spectroscopy and synchrotron tts‐μXRD to Ru–Os–Fe compounds recovered from Ni‐laterites from the Dominican Republic. The results demonstrate that a significant portion of Fe exists in a common structure with the Ru–Os alloy, that is, ruthenian hexaferrum. This mineral occurs both as nanoparticles and as micrometric patches within a matrix of Fe‐oxide(s). Our data suggest that supergene ruthenian hexaferrum with a (Ru_0.4(Os,Ir)_0.1Fe_0.5)_?1.0 stoichiometry represents the most advanced weathering product of primary laurite within Ni‐laterites from the Dominican Republic.     

天然有机质对纳米零价铁去除水中六价铬的影响

应用纳米零价铁进行地下水污染治理是近年迅速发展的环境修复新技术,但在实际应用中,纳米零价铁的反应活性受到环境条件的影响,其中自然界中广泛存在的天然有机质就是重要影响因素。通过批实验研究腐殖酸(天然有机质代表物)对纳米零价铁去除水中六价铬的影响,结果表明,腐殖酸的存在能够极大地抑制纳米铁去除六价铬的反应速度和去除效率,原因在于纳米铁对腐殖酸具有一定的吸附作用,从而减少了纳米铁表面的有效活性位点,降低了对六价铬的作用。此外发现,水体中溶解氧的存在有利于纳米铁对六价铬的去除。关于腐殖酸-纳米零价铁-六价铬的相互作用研究,对于进一步揭示修复体系作用机制具有重要的理论和应用价值。     

Diffusion of trace elements in FeNi metal: Application to zoned metal grains in chondrites

We have measured diffusion coefficients for P, Cr, Co, Ni, Cu, Ga, Ge, Ru, Pd, Ir, and Au in Fe metal from 1150 to 1400°C and at 1 bar and 10 kbar. Diffusion couples were prepared from high-purity Fe metal and metal from the IIA iron meteorite Coahuila (single crystal kamacite) or the pallasite Springwater (polycrystalline kamacite) and held at run conditions for 3.5 to 123 h. Diffusion profiles were measured using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) or the electron microprobe. Many elements were measured from the same experimental runs so interelemental comparisons are improved over other data sets in which data for different elements come from different experiments. Some literature diffusion coefficients (D) for Ni and Co in taenite can be up to a factor of 3 higher for Ni than Co, yet our results show no difference (e.g., D_Ni and D_Co ∼ 2.2 × 10^-15 m²/s at 1150°C). Thus, diffusion of Ni and Co in single crystal taenite will not measurably fractionate the Ni/Co ratio. On the other hand, the large difference in D_Ni and D_Ir (D_Ir is ∼5 times lower) and the similarity of D_Ni and D_Ru at all temperatures investigated indicates that Ni/Ir and Ni/Ru ratios in zoned metal grains will be useful discriminators of processes controlled by diffusion vs. volatility. In zoned metal grains in primitive chondrites, deviations of the Ni/Ru and Ni/Ir ratios from a condensation curve are opposite to a diffusion-controlled process, but consistent with a volatility-controlled process. The new multielement diffusion coefficients will also be useful in evaluating a variety of other processes in planetary science.     

Yarlongite: A New Metallic Carbide Mineral

Yarlongite occurs in ophiolitic chromitite at the Luobusha mine (29°5′N 92°5′E, about 200 km ESE of Lhasa), Qusum County, Shannan Prefecture, Tibet Autonomous Region, People’s Republic of China. Associated minerals are: diamond, moissanite, wüstite, iridium (“osmiridium”), osmium (“iridosmine”), periclase, chromite, native iron, native nickel, native chromium, forsterite, Cr-rich diopside, intermetallic compounds Ni-Fe-Cr, Ni-Cr, Cr-C, etc. Yarlongite and its associated minerals were handpicked from a large heavy mineral sample of chromitite. The metallic carbides associated with yarlongite are cohenite, tongbaite, khamrabaevite and qusongite (IMA2007-034). Yarlongite occurs as irregular grains, with a size between 0.02 and 0.06 mm, steel-grey colour, H Mohs: 5?-6. Tenacity: brittle. Cleavage: {0 0 1} perfect. Fracture: conchoidal. Chemical formula: (Cr4Fe4Ni)Σ9C4, or (Cr,Fe,Ni)Σ9C4, Crystal system: Hexagonal, Space Group: P63/mc, a = 18.839(2) ?, c = 4.4960 (9) ?, V = 745.7(2) ?3, Z = 6, Density (calc.) = 7.19 g/cm3 (with simplified formula). Yarlongite has been approved as a new mineral by the CNMNC (IMA2007-035). Holotype material is deposited at the Geological Museum of China (No. M11650).     

Geochemical Constraints on the Origin of Banded Iron Formation‐Hosted Iron Ore from the Archaean Ntem Complex (Congo Craton) in the Meyomessi Area,Southern Cameroon

Banded iron formations (BIFs) are the most significant source of iron in the world. In this study, we report petrographic and geochemical data of the BIF from the Meyomessi area in the Ntem Complex, southern Cameroon, and discuss their genesis and the iron enrichment process. Field investigations and petrography have revealed that the studied BIF samples are hard; compact; weakly weathered; and composed of magnetite, subordinate quartz, and geothite. The geochemical composition of the whole rock reveals that iron and silica represent more than 98 wt% of the average composition, whereas Al₂O₃, TiO₂, and high‐field strength elements (HFSE) contents are very low, similar to detritus‐free marine chemical precipitates. The total iron (TFe) contents range from 48.71 to 65.32 wt % (average of 53.29 wt %) and, together with the low concentrations of deleterious elements (0.19 wt % P on average), are consistent with medium‐grade iron ores by global standards. This interpretation is confirmed by the SiO₂/Fe₂O_3total versus (MgO + CaO + MnO)/Fe₂O_3total discrimination plot in which most of the Meyomessi BIF samples fall in the field of medium‐grade siliceous ore. Only one sample (MGT94) plots in the high‐grade magnetite–geothite ore domain. The high Fe/Ti (376.36), Fe/Al (99.90), and Si/Al (29.26) ratios of the sample are consistent with significant hydrothermal components. The rare earth elements (REE) contents of the studied BIF samples are very low (∑REE: 0.81–1.47 ppm), and the Post‐Archaean Australian Shale (PAAS)‐normalized patterns display weak positive Eu anomalies (Eu/Eu*: 1.15–1.33), suggesting a syngenetic low‐temperature hydrothermal solutions, similar to other BIF worldwide. However, the Meyomessi BIFs show high Fe contents when compared to the other BIFs. This indicates an epigenetic mineralization process affected the Meyomessi BIF. From the above results and based on the field and analytical data, we propose that the genetic model of iron ores at the Meyomessi area involves two stages of the enrichment process, hypogene enrichment of BIF protore by metamorphic and magmatic fluids followed by supergene alteration as indicated by the presence of goethite in the rocks.     

利用铁屑腐蚀电池原位修复被氯代烃污染地下水的研究进展

简述了氯代烃的主要物理性质和用途，认为铁屑腐蚀电池处理氯代烃污水是基于氧化还原反应、铁屑中活性炭微粒对氯代烃的吸附与对反应的催化、氯离子对氧化膜的破坏和微电池的电场效应等原理；简要总结了迄今利用铁屑去除氯代烃的室内实验和利用原位铁屑反应墙处理地下水中的氯代烃污染研究所取得的成果，认为这种反应墙是一种效果好，成本低，维护方便，有望投入商业运行的最佳方法，并指出了其存在的问题。     

Cation distribution in pentlandites (Fe,Ni)9S8: Dependence on pressure and temperature and kinetics of the cation exchange reaction

This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)₉S₈. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol^–1, 20.52 J K^–1 mol^–1, and 6.99 × 10^–6 m³ mol^–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 10² T ^–1+8.41 x 10^–7 T ^–1 P, where K = (Fe/Ni)_octahedral /(Fe/Ni)_tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol^–1.     

Chemical Analysis of Iron Meteorites Using a Hand‐Held X‐Ray Fluorescence Spectrometer

We evaluate the performance of a hand‐held XRF (HHXRF) spectrometer for the bulk analysis of iron meteorites. Analytical precision and accuracy were tested on metal alloy certified reference materials and iron meteorites of known chemical composition. With minimal sample preparation (i.e., flat or roughly polished surfaces) HHXRF allowed the precise and accurate determination of most elements heavier than Mg, with concentrations > 0.01% m/m in metal alloy CRMs, and of major elements Fe and Ni and minor elements Co, P and S (generally ranging from 0.1 to 1% m/m) in iron meteorites. In addition, multiple HHXRF spot analyses could be used to determine the bulk chemical composition of iron meteorites, which are often characterised by sulfide and phosphide accessory minerals. In particular, it was possible to estimate the P and S bulk contents, which are of critical importance for the petrogenesis and evolution of Fe‐Ni‐rich liquids and iron meteorites. This study thus validates HHXRF as a valuable tool for use in meteoritics, allowing the rapid, non‐destructive (a) identification of the extraterrestrial origin of metallic objects (i.e., archaeological artefacts); (b) preliminary chemical classification of iron meteorites; (c) identification of mislabelled/unlabelled specimens in museums and private collections and (d) bulk analysis of iron meteorites.     

Experimental Study on the Electrical Conductivity of Orthopyroxene atHigh Temperature and High Pressure under Different Oxygen Fugacities

1 Introduction recognized and accepted by more and more experts engaged in experimental research at high temperature and In-situ laboratory measurement of the electricity of high pressure. This method has been regardedgeological materials at high temperature and high pressure internationally as the most advanced one for the in-situis an important approach to revealing the composition, laboratory measurement of the electric properties ofstructure and properties of materials in the deep interior…     

Experimental study of chloritoid stability at high pressure and various fO2 conditions

The reaction chloritoid (ctd)=almandine (alm)+diaspore+H₂O (CAD) has been reversed using Fe³⁺-free synthetic chloritoid and almandine, under fO₂ conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO₂ conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO₂ conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH₂O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H₂O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H₂O bracketed on the Fe/FeO buffer and under unbuffered fO₂ conditions. For fO₂ buffered by the assemblage Fe/FeO, aH₂O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO₂ buffered by the assemblage Ni/NiO, aH₂O=1. The aH₂O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H₂O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H ^o f,ctd and S ^octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and K_D=(Fe³⁺/Al)ctd/(Fe³⁺/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe³⁺ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl₂SiO₅(OH)₂ formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe³⁺ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H₂O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for K_D=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the K_D values reported from chloritoid+garnet+quartz+kyanite natural assemblages.     

The chemical composition of metallic spheroids and metallic particles within impactite from Barringer Meteorite Crater,Arizona

Atomic absorption analyses of 25 metallic spheroids from Barringer Meteorite Crater have been carried out for Fe, Ni, Co and Cu. In addition, electron microprobe analyses of 58 impactite metallic particles have been carried out for Fe, Ni and Co from four different impactite samples. The normalized Ni, Co and Cu contents of the spheroids were from 13–22 per cent, 0.8–1.3 per cent and 260–430 μg/g, respectively. These figures represent enrichment factors of 2–3 in the spheroids compared to analyses of the bulk meteorite. The Co/Ni and Cu/Ni ratios in the spheroids are close to the respective ratios in the bulk meteorite. This suggests that the spheroids were formed by preferential removal of iron by oxidation from a chemically homogeneous liquid.The impactite metallic particles had Ni contents from 10 to 95 per cent and Co contents from 0·3 to 4 per cent. The Co contents of these particles showed a positive correlation with Ni up to 60 per cent Ni and a negative correlation beyond 60 per cent Ni. Reaction of the impactite metallic particles with SiO₂ of the target can explain these variations. Our findings show that extensive chemical reaction between projectile and target occurs at impact.     

Characterization of accumulated precipitates during subsurface iron removal

The principle of subsurface iron removal for drinking water supply is that aerated water is periodically injected into the aquifer through a tube well. On its way into the aquifer, the injected O₂-rich water oxidizes adsorbed Fe²⁺, creating a subsurface oxidation zone. When groundwater abstraction is resumed, the soluble Fe²⁺ is adsorbed and water with reduced Fe concentrations is abstracted for multiple volumes of the injection water. In this article, Fe accumulation deposits in the aquifer near subsurface treatment wells were identified and characterized to assess the sustainability of subsurface iron removal regarding clogging of the aquifer and the potential co-accumulation of other groundwater constituents, such as As. Chemical extraction of soil samples, with Acid-Oxalate and HNO₃, showed that Fe had accumulated at specific depths near subsurface iron removal wells after 12 years of operation. Whether it was due to preferred flow paths or geochemical mineralogy conditions; subsurface iron removal clearly favoured certain soil layers. The total Fe content increased between 11.5 and 390.8 mmol/kg ds in the affected soil layers, and the accumulated Fe was found to be 56-100% crystalline. These results suggest that precipitated amorphous Fe hydroxides have transformed to Fe hydroxides of higher crystallinity. These crystalline, compact Fe hydroxides have not noticeably clogged the investigated well and/or aquifer between 1996 and 2008. The subsurface iron removal wells even need less frequent rehabilitation, as drawdown increases more slowly than in normal production wells. Other groundwater constituents, such as Mn, As and Sr were found to co-accumulate with Fe. Acid extraction and ESEM-EDX showed that Ca occurred together with Fe and by X-ray Powder Diffraction it was identified as calcite.     

负载型纳米Pd/Fe对挥发性氯代烃的去除

氯代烃的污染治理已成为当今世界最热门的研究领域之一。以水体中最常见的氯代烃污染物1,1-二氯乙烯（1,1-DCE）、林丹（γ-HCH）为主要目标污染物,探讨了不同条件下负载型纳米Pd/Fe对氯代烃的去除效果。负载型纳米Pd/Fe采用浸渍→液相还原→还原沉淀的方法制备,透射电镜显示采用该方法制备的负载型金属钯和铁的平均粒径均在纳米级范围内。负载型纳米Pd/Fe具有较高的表面反应活性,当负载型纳米Pd/Fe 用量为40 g/L、反应时间达2 h时,1.1-二氯乙烯和林丹的去除率分别达到85%和100%。脱氯率与Pd/Fe投加量、钯含量、初始pH值、反应温度等因素有关,与溶液的初始浓度关系不大。负载型纳米Pd/Fe对11-DCE和γ-HCH去除均符合一级反应动力学方程,速率常数分别为0-528 3 h^-1及2-012 9 h^-1,反应的半衰期t1/2分别为1.31 h和0.34 h。推断在反应过程中,Fe腐蚀产生的H2为主要还原剂,Pd是良好的加氢催化剂,在金属颗粒表面形成高浓度反应相,使反应短时间内完成。     

The structure of a small complexly‐deformed area within Ordovician rocks near Mansfield,Victoria

Two distinct groups of granitoids occur on the eastern side of the Kosciusko Batholith. Those considered to be derivatives of sedimentary source rocks (S‐types) are usually foliated and either contain cordierite or white‐mica secondary after cordierite. The granitoids produced from igneous source material (I‐types) are generally massive and frequently contain hornblende. Geochemical parameters provide the best discriminant between the two groups, I‐types have higher Ca, Al, Na₂O/K₂O, and Fe₂O₃/FeO, and lower Fe, Mg, Sc, V, Cr, Co, Ni, Cu, Zn, Ba, Rb, Th, La, Ce, and Y than S‐types of comparable SiO₂ values.

The differences between the two groups are not the result of differences in the melt‐forming process but reflect differences in the nature of the source material. Thus the geochemical features of the S‐type granitoids are indicative of their source rocks having been through a process of chemical weathering in a sedimentary cycle. Conversely, the I‐type granitoids were derived from fractionated rocks that had not been involved in weathering processes.     

Adsorption kinetics and thermodynamics of organophosphorus profenofos pesticide onto Fe/Ni bimetallic nanoparticles

Bimetallic Fe/Ni nanoparticles were synthesized and used for the removal of profenofos organophosphorus pesticide from aqueous solution. These novel bimetallic nanoparticles (Fe/Ni) were characterized by scanning electron microscopy, energy-dispersive X-ray analysis spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The effect of the parameters of initial pesticide concentration, pH of the solution, adsorbent dosage, temperature, and contact time on adsorption was investigated. The adsorbent exhibited high efficiency for profenofos adsorption, and equilibrium was achieved in 8 min. The Langmuir, Freundlich, and Temkin isotherm models were used to determine equilibrium. The Langmuir model showed the best fit with the experimental data (R ² = 0.9988). Pseudo-first-order, pseudo-second-order, and intra-particle diffusion models were tested to determine absorption kinetics. The pseudo-second-order model provided the best correlation with the results (R ² = 0.99936). The changes in the thermodynamic parameters of Gibb’s free energy, enthalpy, and entropy of the adsorption process were also evaluated. Thermodynamic parameters indicate that profenofos adsorption using Fe/Ni nanoparticles is a spontaneous and endothermic process. The value of the activation energy (E _a = 109.57 kJ/mol) confirms the nature of the chemisorption of profenofos onto Fe/Ni adsorbent.     

利用扫描电镜技术研究纳米Ni-Fe颗粒对四氯化碳快速脱氯的机理

纳米铁具有高的比表面积和高反应活性,能快速将氯代烯烃还原成无毒氯离子、乙烯和乙烷,但对于氯代烷烃的脱氯仍能产生大量的氯代中间或最终产物,可以通过合成制得纳米双金属提高脱氯速率和减少氯代中间产物。本文利用扫描电镜测得实验室制备的纳米Ni-Fe(2%,质量分数)颗粒直径为20~60 nm,通过批实验方式对纳米Ni-Fe降解四氯化碳的反应动力学性质、产物、持久性能和反应机理进行了探讨。结果表明,纳米Ni-Fe体系主要最终产物为42%CH4和17%CH2Cl2。与铸铁屑和纳米铁相比,纳米Ni-Fe由于催化脱氯加氢,显著提高了氯代烃脱氯速率,同时降低了有毒氯代产物的产量,且Ni作为催化剂不会进入水体引起二次污染。纳米Ni-Fe颗粒在空气中具有很好的稳定性,虽然降解四氯化碳的最终产物CH4与纳米Pd-Fe相比少13%,但由于价格便宜,有望在工程上应用于氯代有机化合物水土污染治理。     

High Pressure Response of Rutile Polymorphs and Its Significance for Indicating the Subduction Depth of Continental Crust

α-PbO2-type TiO2 （TiO2-Ⅱ） is an important index mineral for ultrahigh-pressure metamorphism. After the discovery of a natural high-pressure phase of titanium oxide with α-PbO2- structure in omphacite from coesite-bearing eclogite at Shima in the Dabie Mountains, China, a nanoscale （〈2 nm） α-PbO2-type TiO2 has been identified through electron diffraction and high-resolution transmission electron microscopy in coesite-bearing jadeite quartzite at Shuanghe in the Dabie Mountains. The crystal structure is orthorhombic with lattice parameters a = 4.58×10-1 nm, b = 5.42×10-1 nm, c = 4.96×10-1 nm and space group Pbcn. The analysis results reveal that ruffle {011}R twin interface is a basic structural unit of α-PbO2-type TiO2. Nucleation of α-PbO2-type TiO2 lamellae is caused by the displacement of one half of the titanium cations within the {011}R twin slab. This displacement reduces the Ti-O-Ti distance and is favored by high pressure. The identification of α- PbO2-type TiO2 in coesite-bearing jadeite quartzite from Shuanghe, Dabie Mountains, provides a new and powerful evidence of ultrahigh-pressure metamorphism at 4--7 GPa, 850℃-900℃, and implies a burial of continental crustal rocks to 130-200 kilometers depth or deeper. The α-PbO2-type TiO2 may be a useful indicator of the pressure and temperature in the diamond stability field.     

Geochemical Characteristics of Wuyang Siliceous Rocks in the Southern Margin of North China Craton and its Constraint on the Formation Environment of BIF of Tieshanmiao Formation

Precambrian banded iron formation(BIF) is one of the most important mineral resources in China, mostly abundant in the North China Craton(NCC) with relatively less common in South China. Since the BIF and siliceous rocks both originated from chemical deposition, the syngenetic BIF and Siliceous rocks can help evaluate their environment of formation. We examine here the mineralogy and geochemistry of siliceous rocks associated with the Tieshanmiao Formation BIF, aiming to decipher the conditions of formation of both BIF and Siliceous rocks in the Wuyang area in the NCC. Analysis of the geochemical characteristics of whole rock shows that the Si O2 content of the siliceous rock ranges from 90.11% to 94.85% and is relatively high overall. Trace element contents of Ba and U are also high, the Ba/Sr ratio ranges from 3.89 to 25.28 and the U/Th ratio ranges from 0.09 to 0.20. Finally, the ΣREE value of rare earth elements ranges from 57.03 ppm to 152.59 ppm, and these indexes all indicate that siliceous rock resulted from hydrothermal deposition. Plots of Al2 O3-Si O2, Si O2/(K2 O+Na2 O)-Mn O2/Ti O2 and Mn-10×(Cu+Co+Ni)-Fe in discrimination diagrams also verify this interpretation. However, both the Mg O content, ranging from 0.16 to 0.32, and the Fe/Ti ratio, ranging from 2.50 to 9.72, suggest that terrigenous material was added during the depositional process. Major and trace element parameters of siliceous rock, such as the Al/(A1+Fe+Mn) ratio(from 0.81 to 0.93), Mn O/Ti O2(from 0.00 to 0.17), Al/(Al+Fe)(from 0.82 to 0.93), Sc/Th ratio(from 0.21 to 0.50), U/Th(from 0.09 to 0.20),(La/Yb)N(from 0.83 to 3.04), and the(La/Ce)N(from 0.01 to 0.02) all imply that the siliceous rock formed in a continental margin. In addition, the Sr/Ba ratio from 0.08 to 0.26, the δCe value from 0.31 to 0.90, and the δEu value from 0.14 to 0.58, all indicate that the siliceous rock was formed at a relatively deeper water depth and under weak hydrodynamic conditions. Siliceous rock and BIF formed in the same geological setting, with the Si O2/(K2 O+Na2 O) ratio of siliceous rock ranging from 28.61 to 47.43, the Si O2/Al2 O3 ratio from 16.53 to 32.37, and the Si O2/Mg O ratio from 287.28 to 592.81, which are all in agreement with chemical deposition associated with volcanic eruptions. The Al2 O3/Ti O2 ratio from 37.82 to 50.30 indicates that the magma source of siliceous rock was of slightly intermediate composition. During the Late Archean in the Wuyang area, the high concentration and high purity Si O2 quickly precipitated from hydrothermal fluids to finally result in the accumulation of siliceous rock in a marginal sea, while the input corresponding to iron formation components was deposited to form iron formation layers, and limestone was only the product formed during the deposition intervals of siliceous rock and iron formations. In this study, the synsedimentary siliceous rocks of BIF act as a new way to provide direct evidence to understand the formation environment of BIF due to its high geochemical stability.