Factors governing formation of todorokite at atmospheric pressure

Todorokite is a common manganese oxide in soils, sediments, and marine manganese nodules. The MnO6 octahedrons share edges within chains and share cor-ners between chains to form a 3×3 tunnel framework of todorokite. Octahedral molecular sieves with struc-ture of todorokite exhibit superior characteristics in ion exchange, specific surface area, thermal stability and molecule-sized tunnels[1]. Todorokite plays an important role in cleaning up natural water and con-trolling concentration of h…     

Synthesis of todorokite by refluxing process and its primary characteristics

Todorokite is one of the common manganese ox-ides in manganese ore deposits, weathering product of manganese-bearing rocks, soils and sediments. It is also an important component in the abundant marine manganese nodules. Since todorokite was firstly found in Japanese Todoroki mine in 1934, its properties and origination have appeared to be very interesting to many researchers[1—3]. It has a stable structure similar to porous molecular sieves, constructed of triple MnO6 octahedral chains. Th…     

Microstructure characteristics of illite from Chuanlinggou Formation of Changcheng System in Jixian County, Tianjin City

The microstructure charateristics of illite from the Chuanlinggou Formation of Changcheng System (Chch) in Jixian County, Tianjin City has been studied by means of high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), X-ray energy dispersive spectrum (EDS) and X-ray powder diffraction (XRD). The Kübler index of "illite crystallinity" is 0.505°△2θ, which indicates that the host rock is in a middle diagenetic stage. The chemical analyses of EDS for illite studied indicate a heavily absent in interlayer cation and an average chemical formula of K0.57(Al1.80Mg0.42Fe2 0.12)Σ=2.34 (Si2.92Al1.08)Σ=4O10(OH)2. It is found, from one-dimensional lattice images, that the layers of illite not only stack in a flat way but also in a curving way. A "matting fabric" illite structure results from stacking faults. Combined with SAED analysis the illite studied can be affirmed as 1M illite. The two-dimensional lattice images are obtained from [100] and [110] incidences, whose lattice images have the same d-values but different intersecting angles. The two-dimensional lattice image with [100] incidence is orthogonal to each other, whilst that with [110] incidence is oblique. This paper provides some important structure information of authigenic clay minerals for the well-known mesoproterozoic section of Jixian County.     

菱铁矿热转变过程中岩石磁学性质基本特征

利用吉林大栗子铁矿纯菱铁矿样品,系统测量了菱铁矿在空气环境下热处理产物的磁化特征．揭示出其饱和等温剩磁（ＳＩＲＭ）、剩磁矫顽力（Ｈ（ｃｒ））和居里温度（Ｔｃ）随加热温度升高而发生的系列变化,美铁矿氧化过程中准稳定态磁性矿物磁赤铁矿（ｒ－Ｆｅ２Ｏ３）是中间产物之一,并且具有较高的热稳定性．Ｘ射线衍射和穆斯堡尔（Ｍｏｓｓｂａｕｅｒ）效应等分析结果证实了岩石磁学研究所揭示的菱铁矿氧化中磁性矿物转变过程．菱铁矿氧化过程中结晶结构的转变可能会影响其氧化产物的磁性特征．     

Pathways of carbon oxidation in continental margin sediments off central Chile

Rates and oxidative pathways of organic carbon mineralization were determined in sediments at six stations on the shelf and slope off Concepcion Bay at 36.5 degrees S. The depth distribution of C oxidation rates was determined to 10 cm from accumulation of dissolved inorganic C in 1-5-d incubations. Pathways of C oxidation were inferred from the depth distributions of the potential oxidants (O2, NO3-, and oxides of Mn and Fe) and from directly determined rates of SO4(2-) reduction. The study area is characterized by intense seasonal upwelling, and during sampling in late summer the bottom water over the shelf was rich in NO3- and depleted of O2. Sediments at the four shelf stations were covered by mats of filamentous bacteria of the genera Thioploca and Beggiatoa. Carbon oxidation rates at these sites were extremely high near the sediment surface (>3 micromol cm-3 d-1) and decreased exponentially with depth. The process was entirely coupled to SO4(2-) reduction. At the two slope stations where bottom-water O2 was > 100 microM, C oxidation rates were 10-fold lower and varied less with depth; C oxidation coupled to the reduction of O2, NO3-, and Mn oxides combined to yield an estimated 15% of the total C oxidation between 0 and 10 cm. Carbon oxidation through Fe reduction contributed a further 12-29% of the depth-integrated rate, while the remainder of C oxidation was through SO4(2-) reduction. The depth distribution of Fe reduction agreed well with the distribution of poorly crystalline Fe oxides, and as this pool decreased with depth, the importance of SO4(2-) reduction increased. The results point to a general importance of Fe reduction in C oxidation in continental margin sediments. At the shelf stations, Fe reduction was mainly coupled to oxidation of reduced S. These sediments were generally H2S-free despite high SO4(2-) reduction rates, and precipitation of Fe sulfides dominated H2S scavenging during the incubations. A large NO3- pool was associated with the Thioploca, and the shelf sediments were thus enriched in NO3- relative to the bottom water, with maximum concentrations of 3 micromol cm-3. The NO3- was consumed during our sediment incubations, but no effects on either C or S cycles could be discerned.     

Dynamics and stable isotope composition of gaseous and dissolved oxygen

The vadose zone and ground water environments are a sink for atmospheric O(2). The pathways and rates of O(2) consumption are primarily related to the availability and rate of oxidation of key reductants (e.g., organics, sulfides), through a combination of biological or abiotic reactions. The range in delta(18)O of O(2) in the subsurface is large, from +20 per thousand to +39 per thousand (Vienna Standard Mean Ocean Water) in the vadose zone and from +12 per thousand to +46 per thousand in ground water. The aggregated O(2) isotope fractionation by consumption (alpha(k)) was found to range from 0.970 to 1.300 and 0.980 to 1.030 in vadose zones and aquifers, respectively. These data suggest the delta(18)O patterns in both unsaturated zones and aquifers can be attributed to microbially mediated reactions (alpha(k)= range from 0.975 to 1.000), but there are apparently other inverse isotope fractionating processes (alpha(k) > 1.000). Circumstantial evidence suggested O(2) processed during the sulfide oxidation and precipitation of Fe-oxyhydroxides process (or other unidentified processes) could be the cause of the significant (18)O depletions. Overall, delta(18)O data from vadose zones and ground water revealed that isotope fractionation by consumption of gaseous and dissolved O(2) in the subsurface and ground water environments is more complicated than what has classically been attributed solely to geomicrobial respiration. Given the questions and inexplicable data arising from this study, further detailed research on O(2) consuming processes in the Earth's subsurface and ground water is warranted.     

Mineralogical characterization of the thrusted manganese ore above the Blackridge Thrust Fault,Kalahari Manganese Field: The footprint of the Mukulu Enrichment

The thrusted manganese ore above the Blackridge Thrust Fault is a predominantly unstudied ore‐type and as such, there is an urgent need to petrographically characterize it. A total of 80 samples were collected from the thrusted lower manganese ore bed of six boreholes on Mukulu in the north of the Kalahari Manganese Field. Each sample underwent a range of optical and electron petrographic analyses in order to effectively characterize three dominant stages of alteration, namely Stages 1, 2 and 3. Similar to the hydrothermally‐altered Wessels‐type manganese ore, braunite II is the predominant mineral phase present during Stage 1 alteration, and alters to bixbyite with increasing proximity to normal faults at the onset of Stage 2 alteration. The final stage of alteration is exhibited by the development of hausmannite and jacobsite adjacent to the ferruginised zone at the normal fault plane. Apatite precipitation, in abundances previously undocumented in the Kalahari Manganese Field, is a hallmark feature of the newly identified Mukulu Enrichment. This supergene‐related enrichment process contributed to the significant abundance of arsenic‐bearing apatite in the ore, whilst residually enriching the ore‐hosted Fe and Mn oxides.     

菱铁矿热转变过程中岩石磁学性质基本特征

利用吉林大栗子铁矿纯菱铁矿样品,系统测量了菱铁矿在空气环境下热处理产物的磁化特征．揭示出其饱和等温剩磁（ＳＩＲＭ）、剩磁矫顽力（Ｈ（ｃｒ））和居里温度（Ｔｃ）随加热温度升高而发生的系列变化,美铁矿氧化过程中准稳定态磁性矿物磁赤铁矿（ｒ－Ｆｅ２Ｏ３）是中间产物之一,并且具有较高的热稳定性．Ｘ射线衍射和穆斯堡尔（Ｍｏｓｓｂａｕｅｒ）效应等分析结果证实了岩石磁学研究所揭示的菱铁矿氧化中磁性矿物转变过程．菱铁矿氧化过程中结晶结构的转变可能会影响其氧化产物的磁性特征．     

New index of ferromanganese crusts reflecting oceanic environmental oxidation

Ferromanganese crusts (hereinafter crusts) form in aerobic environment and the environmental oxida-tion degree is recorded by the redox sensitive element Co in the crusts. The ages of the layers from the surface to bottom of the crusts are determined, and main element contents at high resolution along the depth sections of three crusts from the Pacific Ocean are analyzed by an electron microprobe. Thus the variations of Co/(Fe Mn) and Co/(Ni Cu) with age/depth of the crust layers are obtained. By comparing the ratios of Co/(Fe Mn) and Co/(Ni Cu) with the δ 18O curves of the Pacific benthic foraminifera, we find that these two ratios can reflect the variation of the environmental oxidation state under which the crust layers deposit. The evolution of the oxidation degree reflected by the two indexes resembles the evo-lution of temperature since the Oligocene reflected by the δ 18O curves of the Pacific benthic foraminif-era. This suggests that the crust-forming environment after the Oligocene is controlled mainly by the oxygen-rich bottom water originated from the Antarctic bottom water (AABW). However it is not the case prior to the Oligocene. Furthermore it suggests that the environmental oxidation degree controls the formation of the crusts and the Co contents in the crusts. This explains why the Co contents in the crusts increase with time up to now.     

Elimination of Swimming Pool Water Disinfection By‐products with Advanced Oxidation Processes (AOPs)

Ozonation is a treatment step which was first applied in the 1960s in pool water treatment for disinfection as well as for oxidation of pool water contaminants. Contact time between ozone and pool water was identified to be of significance with an increased elimination efficiency regarding chloramines, trihalogenmethane formation potential and the permanganate index for longer reaction times. Oxidation via OH radicals might be the dominating pathway. In this study ozonation was compared with the ozone based advanced oxidation processes ozone/UV and ozone/hydrogen peroxide regarding the elimination efficiency of both disinfection by‐products (DBPs) and DBP precursors. It was observed that AOPs in comparison to ozonation showed an increased elimination efficiency regarding total organic carbon (TOC), the organically bound halogens adsorbable on activated carbon (AOX) and AOX formation potential. A contact time of 3 minutes between pool water and oxidant turned out to be practically sufficient. Just for the trihalomethane (THM) formation potential ozonation showed a slight advantage compared to the AOPs because ozonation is a highly selective oxidant and OH radical reactions are known to produce small reactive molecules which are easier transformed to THMs. Combination of membrane filtration and AOPs resulted in an elimination of 10 to 90 % of the DBPs and their precursors. The ozone/hydrogen peroxide process is suggested for pool water treatment because of the higher elimination rates compared to ozonation and of economic reasons compared to the ozone/UV process.     

Manganese oxidation in pH and O2 microenvironments produced by phytoplankton

Pure cultures of Chlorella sp. catalyzed the oxidation of soluble Mn(II) to particulate, extracellular, manganic oxides. Manganese oxidation was dependent on photosynthetic activity: no oxidation was observed in the dark when cells were grown heterotrophically on glucose, or in the light when photosystem II was inhibited by the addition of DCMU. Manganates were not formed when media were buffered below pH 8.0, suggesting that an important driving force for manganese oxidation was the high pH resulting from photosynthesis. Field studies with minielectrodes in Oneida Lake, New York, demonstrated steep gradients of O2 and pH and the presence of particulate manganic oxides associated with pelagic aggregates of the cyanobacterium Microcystis sp. The manganese oxidation reaction apparently occurs only when photosynthesizing algae are present as dense populations that can generate microenvironments of high (>9.0) pH, either as aggregates in the pelagic zone or concentrated cell cultures in the laboratory. A large-scale transition from soluble to particulate manganese was measured in the surface waters of Oneida Lake throughout summer 1986. Removal of Mn(II) was correlated with the presence of aggregate-forming cyanobacteria that oxidize Mn(II) by the mechanism described above.     

Majorite formation from enstatite by experimental shock-loading

Majorite has been observed for the first time after experimental shock-loading of enstatite (Bamle, Norway). The identification of this high pressure garnet has been carried out by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction experiments, majorite formation was indicated by these techniques for the pressure range between ca. 35 and 50 GPa. This also proves formation of majorite by impact metamorphosis in the Coorara meteorite as well as terrestrial formation of that phase by the same process.     

The chemistry of hydrothermal mounds near the Galapagos Rift

Samples dredged from the sediment mounds have a unique chemistry and mineralogy which reveals details of the hydrothermal processes that produce these deposits. The mounds form primarily by deposition of Fe, Mn and Si from hydrothermal fluids which circulate through the basalt crust and the overlying sediments. The Mn, Fe and Si are strongly fractionated in the process; the Fe and Si precipitate within the mounds under slightly reducing conditions as nontronite, while the Mn is deposited as Mn oxyhydroxides at the seawater-sediment interface. The nontronite is exceptionally well crystallized, and contains less than 200 ppm Al. The Mn minerals, todorokite and birnessite, also have exceptional crystallinity and the distribution of trace elements Cu, Ni, Zn, Co, Ca and Ba in these phases agrees with predictions made on the basis of models of their crystal structure. The environment of deposition which produces this suite of minerals — slow percolation of hydrothermal fluids through pelagic sediments — may not be unique to the Galapagos Rift, as the same suite of minerals has been found in similar setting in the Gulf of Aden and on the Mid-Atlantic Ridge.     

Transformation relationship among different magnetic minerals within loess-paleosol sediments of the Chinese Loess Plateau

The dominant magnetic minerals and carriers of magnetic signals within the Chinese Loess Plateau are magnetite, maghemite, hematite, and goethite. In this study, we investigated the provenance and evolution of magnetic minerals during loess pedogenesis, using X-ray diffraction (XRD) and optical and electron microscopy, including field emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM). Our results reveal that single- and multiphase mineral assemblages among magnetic minerals in the loess-paleosol sequence have been formed. Partial oxidation of coarse eolian magnetite has occurred in the desert source area and the oxidation degree is enhanced after deposition of the dust upon the Chinese Loess Plateau. This mode of origin resulted in a microtexture consisting of an inner magnetite core surrounded by a hematite rim, and strongly affected the magnetic characteristics of the loess. Goethite coexists with hematite in the loess and paleosol, and nanometer-scale hematite is formed upon goethite rims via dehydration. Our study provides direct mineralogical evidence of the magnetic record and paleoclimatic implications of the loess-paleosol sequence of the Chinese Loess Plateau. Supported by National Natural Science Foundation of China (Grant Nos. 40772032 and 40573054) and National Basic Research Program (Grant No. 2007CB815603)     

混合岩化的发生与发展

本文提出混合岩化作用是指地壳深部的深熔作用,在地壳褶皱带中引起一般岩石的深熔和分异;再由熔融物质侵入到地壳上部,与围岩发生混合和交代所成。混合岩化的全过程都按矿物组合的反应式,分为两个不同阶段表示出来。这样的混合岩化演变过程,可能在地壳褶皱带中是一般岩石变化的普遍规律。本文并证明了混合岩化作用的矿物组合变化范围和形成的温度、压力,最后讨论混合岩化的原岩问题     

Geochemical processes controlling the relationship between Co,Mn, and Fe in early diagenetic deep-sea nodules

Early diagenetic manganese nodules from the northeast Pacific nodule belt and from the southeast Pacific (Peru Basin) show primary growth features of dendritic microtextures consisting of alternating laminae of crystalline 10-Åmanganate (A1 substance) and amorphous material which is composed of an intimate mixture of ferric hydroxide, silicate, and δ-MnO₂ (A2 substance). The formation of rhythmic sequences of A1 and A2 microlayers is explained by physico-chemical changes in the peneliquid sediment layer and in the microenvironment of the accreting nodule surface: (a) upward diffusion of Mn²⁺ in the interstitial water as a result of decay of organic matter and Mn mobilization; (b) oxidation of Mn²⁺ and formation of 10-Åmanganate in the upper part of the peneliquid sediment layer, leading to pH depression in the microenvironment of the nodule surface which decreases the mobility of silicate, resulting in formation of A2 layers; (c) restoration of pH and renewed precipitation of 10-Åmanganate.Based on data of 171 bulk analyses and on electron microprobe investigations, interelement relationships between Co, Mn, and Fe are pointed out. Fe and Co show a significant positive correlation (r = 0.84), while Mn and Co are poorly negatively correlated (r = ?0.21), assuming linear regression. The enrichment of Co within the amorphous A2 phase is attributed to specific surface adsorption and subsequent oxidation of Co²⁺ to Co³⁺ in the strong electric field of Si⁴⁺. Robust complexes of Co(III) and ≡ FeH₂SiO₄^? prevent most of the Co from being available for the 10-Åmanganate precipitation. Concerning the relation between Mn and Fe and Co respectively, the highest correlation coefficients are obtained using an inverse logarithmic regression. Under early diagenetic conditions, the concentration and precipitation of Mn²⁺ in the interstitial water depends on the redox gradient which is controlled by the amount of decomposing organic matter. The Nernst equation describes the relationship as a reciprocal logarithmic function. However, the quantities of colloidal ferric hydroxide and of dissolved silicate are not affected by variations of the redox potential. These different characteristics in the precipitation of Mn and the Fe- and Si-rich colloidal phase may cause the significantly negative logarithmic correlation of Mn versus Fe and Co, respectively.     

云南抚仙湖流域废弃磷矿区水污染现状

为了探讨不同形态磷酸盐对铜绿微囊藻（Microcystis aeruginosa）和蛋白核小球藻（Chlorella pyrenoidosa）藻细胞生长的影响,采用3种不同形态的磷酸盐：磷酸氢二钾（K2HPO4）,焦磷酸钠（Na4P2O7）和一聚磷酸钠（Na5P3O10）作为BG-11培养基中的添加磷源．从两种藻的生长趋势可以看出,在K2HPO4培养基中小球藻在生长初期生长速度显著高于微囊藻,当小球藻的生长到达静止期时,微囊藻的生长速度便超过了小球藻且其藻密度也高于小球藻;而在焦磷酸钠和二三聚磷酸钠培养基中,小球藻的生长速度要显著高于微囊藻．同时微囊藻和小球藻在K2HPO4培养基中的生长速度则始终高于另两种磷酸盐培养基中的生长速度．藻细胞碱性磷酸酶活性变化曲线也显示,小球藻的磷利用能力要高于微囊藻．由此可见,小球藻对磷的吸收利用能力高于微囊藻,从而表明铜绿微囊藻成为水华优势种并不是取决于其对磷酸盐的吸收利用能力。     

Experimental studies of interaction between water and albite melts

On the basis of FTIR and Raman spectra studies on hydrous albite glasses, it is found that there exist two water solubility mechanisms in albite melts simultaneously. On the one hand, water interacts with Al -O°-Al to produce the Q3 Al-OH, leading to depolymerization, and this results in the appearance of 4500 cm(1 in FTIR spectra and 900 cm(1 in Raman spectra. On the other hand, the exchange of H+ in water with Na+ in albite melt as charge-balancing cation occurs at the same time. In the initial stage, the production of Al -OH is the dominant solubility mechanism, at the stage of higher water contents, the exchange of H+ with Na+ becomes the important dissolution mechanism. The dissolution of water into albite melt can be expressed as H2O+ 3NaAlSi3O8 = 2NaAl(OH)Si3O7.5 +HAlSi3O8 +NaOH.     

Distribution of hydrous components in jadeite of the Dabie Mountains

Two kinds of jadeite occur in the jadeite-quartzite from the Dabie Mountains, Eastern China: associated either with weak or strong deformation. The former shows a uniform composition while the latter shows both uniform and zoning composition. These jadeites were examined with infrared (IR) spectroscopy. All jadeite displays hydroxyl (OH) stretching bands, implying that hydrous components commonly exist in jadeite. The concentration of the hydrous components in the jadeite with weak deformation is homogenous, whereas the concentration of the hydrous components in strongly deformed samples is variable. The correlation between the intensity of OH-band absorbance and compositional zoning of jadeite with strong deformation indicates that Na-rich jadeite can accommodate more OH than Na-poor jadeite. Its interpretation is that there is more Na associated with greater OH availability in the initial crystallization environment. Our data of the comparatively high OH concentrations recorded in the core of the jadeite which contains relative high vacancies in M2 site imply that both OH content and the vacancies in M2 site could decrease during exhumation of the jadeite-quartzite. The decrease of OH solubility in jadeite would result in the formation of H₂O fluid during the early exhumation of UHP metamorphic rocks. The H₂O fluid transformed from OH during exhumation could trigger and enhance the early retrograde metamorphism of the host rocks and facilitate plastic deformation of jadeite grain by dislocation creep and diffusion creep.     

断层泥伊利石物理化学特征及其意义

通过X射线衍射和化学分析等方法,研究了云南水电站断层泥中伊利石物理化学特征,结果显示：①伊利石物质的X射线衍射特征为⊿[（002）-（001）] ＞8,Ir＞1,BB1 ＜4°,属I＋ISII有序混层,膨胀层小于15％,晶胞参数b0=8.991A,1M多型结构;②K2O的平均含量9.1％变化范围在8.5％-10％之间;③K2O和Fe2O3含量之间为负相关,K2O含量与⊿[（002）-（001）] 2θ值呈正相关,而K2O与Ir值呈负相关.上述特征表明该断层泥伊利石是在低温（小于200℃）低压环境下生成.它的形成与断层稳定滑动机制有关.由此推测该断层未来发生大地震的可能性较小.