Parameterization of iron and manganese cycling in the Black Sea suboxic and anoxic environment

New and published data on the distribution and speciation of manganese and iron in seawater are analyzed to identify and parameterize major biogeochemical processes of their cycling within the suboxic (15.6σ_t16.2) and anoxic layers (σ_t16.2) of the Black Sea. A steady-state transport-reaction model is applied to reveal layering and parameterize kinetics of redox and dissolution/precipitation processes. Previously published data on speciation of these elements in seawater are used to specify the nature of the transformations. Two particulate species of iron (Fe(III) hydroxide and Fe(II) sulfide) are necessary to adequately parameterize the vertical profile of suspended iron, while three particulate species (hydrous Mn(IV) oxide, Mn(II) sulfide, and Mn(II) carbonate) are necessary to describe the profile of suspended manganese. In addition to such processes as mixing and advection, precipitation, sinking, and dissolution of manganese carbonate are found to be essential in maintaining the observed vertical distribution of dissolved Mn(II). These results are used to interpret the observed difference in the form of vertical distribution for dissolved Mn(II) and Fe(II). Redox transformations of iron and manganese are coupled via oxidation of dissolved iron by sinking suspended manganese at σ_t16.2±0.2 kg m⁻³. The particulate manganese, necessary for this reaction, is supplied through oxidation of dissolved Mn(II). The best agreement with observations is achieved when nitrate, rather than oxygen, is set to oxidize dissolved Mn(II) in the lower part of the suboxic layer (15.90σ_t16.2). The results support the idea that, after sulfides of these metals are formed, they sink with particulate organic matter. The sinking rates of the particles and specific rates of individual redox and dissolved-particulate transformations have been estimated by fitting the vertical profile of the net rate.     

Mesozooplankton responses to iron-fertilization in the western subarctic Pacific (SEEDS2001)

A mesoscale iron-fertilization experiment was carried out in the western subarctic Pacific during summer 2001. The iron-patch was traced for 14 days after the fertilization, and the abundance and behavior of mesozooplankton were compared with those outside of the patch. The phytoplankton biomass in the patch rapidly increased to over 15 times the initial level by the later half of the observation period, and was composed of large-sized (>10 mm), centric diatoms. Dominant zooplankton species in the upper 200-m depth were large copepods: Neocalanus plumchrus, Neocalanus cristatus, Eucalanus bungii and Metridia pacifica. Mesozoplankton biomass as well as species composition did not change significantly in the patch over the observation period. Furthermore, no changes of vertical distribution or diel vertical migration were observed for any species or stages of mesozooplankton throughout the observation period. However, the abundance of the first copepodite stages of N. plumchrus and E. bungii increased several fold in the patch after the diatom bloom formation compared to the densities outside the patch. The increases of both species are considered to be due to lowered mortality during the egg and nauplius stages. Spawning of N. plumchrus takes place at depth using lipid storage, while spawning of E. bungii takes place in the surface layer supported by grazing. These facts suggest that the relative importance of nauplii in the diets of the large copepods was decreased in the patch by the diatom bloom. Gut-pigment contents of dominant copepods in the patch increased 4–18 times, and the maximum values were observed during the bloom peak. However, the grazing impact on phytoplankton was low throughout the experiment, especially during the bloom period (<6% of the primary production).     

Zircon and titanite U-Pb dating of the Zhangjiawa iron skarn deposit,Luxi district,North China Craton: Implications for a craton-wide iron skarn mineralization

The North China craton hosts numerous iron skarn deposits containing more than 2600 Mt of iron ores, mostly with an average grade of >45 wt% Fe, which have been among the most important source of high-grade iron ores for the last three decades in China. These deposits typically form clusters and can be roughly divided into the western and eastern belts, which are located in the middle of Trans-North China orogen and to the west of the Tan-Lu fault zone in the eastern part of North China craton, respectively. The western belt mainly consists of the southern Taihang district, as well as the Linfen and Taiyuan ore fields, whereas the eastern belt comprises the Luxi and Xu-Huai districts. The Zhangjiawa deposit in the Luxi district has proven reserves of 290 Mt at an average of 46% Fe (up to >65%). The iron mineralization occurs mainly along contact zones between the Kuangshan dioritic intrusion and middle Ordovician marine carbonate rocks that host numerous evaporite intercalations. Titanite grains from the mineralized skarn are closely intergrown with magnetite and retrograde skarn minerals including chlorite, phlogopite and minor epidote, indicating a hydrothermal origin. The titanite grains have extremely low REE contents and low Th/U ratios, consistent with their precipitation directly from hydrothermal fluids responsible for the iron mineralization. Ten hydrothermal titanite grains yield a weighted mean ²⁰⁶Pb/²³⁸U age of 131.0 ± 3.9 Ma (MSWD = 0.1, 1σ), which is in excellent agreement with a zircon U-Pb age (130 ± 1 Ma) of the ore-related diorite. This age consistency confirms that the iron skarn mineralization is temporally and likely genetically related to the Kuangshan intrusion. Results from this study, when combined with existing isotopic age data, suggest that iron skarn mineralization and associated magmatism throughout both the eastern and western belts took place coevally between 135 and 125 Ma, with a peak at ca. 130 Ma. As such, those deposits may represent the world's only major Phanerozoic iron skarn concentration hosted in Precambrian cratons. The magmatism and associated iron skarn mineralization coincide temporally with the culmination of lithospheric thinning and destruction of the North China craton, implying a causal link between the two.     

新疆蒙库铁矿床稀土元素地球化学及对铁成矿作用的指示

新疆富蕴县蒙库大型铁矿呈层状、似层状、透镜状赋存于下泥盆统康布铁堡组变质火山-沉积岩系中.矿体中发育矽卡岩,但矽卡岩并不产在侵入岩接触带上.绿帘石、石榴石和矿石的稀土配分模式具有相似性,均为轻稀土富集,正铕异常,基本上无铈异常,暗示它们之间存在成因联系.石榴石稀土配分模式呈折线型,具有明显的正铕异常,石榴石流体包裹体中熔融包裹体、熔流包裹体和气液包裹体共存,表明石榴石矽卡岩具有岩浆成因和热液成因的特征,形成于晶体 熔体 流体三相共存的岩浆-热液过渡阶段.矿床地质特征、矽卡岩矿物和矿石稀土特征表明蒙库铁矿为矽卡岩型矿床.     

河南省舞阳冷岗铁矿床地质特征及控矿因素

通过对冷岗铁矿地质特征、控矿因素的分析，认为该矿床是在火山—沉积作用形成的含铁建造基础上，经区域变质作用，再次交代富集而形成的铁矿床，该矿床受地层、变质作用、构造等多重因素影响和控制。     

青海喀雅克登铁多金属矿床 地质特征及找矿标志

[摘　要]青海省格尔木市喀雅克登铁多金属矿区位于柴达木盆地西南缘,喀雅克登铁多金属矿是近几年在东昆仑祁漫塔格地区发现的小型矿床,成矿时代为晚三叠世。矿区共圈出铁锌多金属矿体39条,其中矿体规模相对较大的有8条,矿体长度在50-620m,厚度在4.45-16.95m,Zｎ的平均品位在2-3%,WO3的平均品位在0.097-0.16%,估算锌资源量为5.11万吨,矿区具有典型的矽卡岩型成矿特征,并具有热液成矿的特点,深部具有热液型钨钼找矿前景,热液成矿事实为东昆仑找矿拓宽了思路     

雷州半岛玄武岩残积土的物质成分与结构特征

雷州半岛玄武岩残积土属于区域性特殊土,具有高液限、大孔隙比的较差的物理特性和高强度的较优的力学特性的异常组合,同时具有强收缩性、遇水湿化、易崩解的特殊性质。为探寻玄武岩残积土特殊的工程地质特性的机理,对其矿物成分、化学成分、结构形态、孔隙分布进行研究。结果表明,雷州半岛玄武岩残积土发育过程经历明显的富铝化、铁富集和盐淋失过程,黏土矿物以高岭石、三水铝石和伊利石为主,富含游离氧化铁、铝成分; 微观结构类型为凝块结构和絮凝结构,游离氧化铁作为胶结物质以包膜形式包裹颗粒形成团聚体,增强了土的结构强度; 孔隙以溶蚀孔隙以及团粒和絮凝体内微孔为主,微孔具有较大的比表面积和吸附能,吸水会产生较大的表面张力,引发软化、崩解现象。由于雷州半岛玄武岩残积土具有对水敏感,抗水性差特点,施工中应重点关注降雨引发的工程灾害。     

Geology and geochemistry of the Águas Claras and Pico Iron Mines, Quadrilátero Ferrífero, Minas Gerais, Brazil

The Águas Claras and Pico Mines are two world-class iron-ore mines hosted within the Lower- Proterozoic banded iron-formations (locally known as itabirites) of the Minas Supergroup located in the Quadrilátero Ferrífero district, Minas Gerais, Brazil. The Águas Claras orebody consists of a 2,500-m-long roughly tabular-shaped lens hosted within the dolomitic itabirite of the Cauê Formation. Dolomitic itabirite is the protore of the soft high-grade iron ore, which is the main ore type of the Águas Claras orebody, representing about 85% of the 284 Mt mined since 1973, with the remaining 15% comprising hard high-grade ore. Hematite is the main constituent of the iron ores. It occurs as martite, granular hematite and locally as specularite. Magnetite appears subordinately as relicts within martite and hematite crystals. Gangue minerals are very rare. These consist of dolomite, chlorite, talc, and apatite, and are especially common in contact with the protore. This virtual absence of gangue minerals is reflected in the chemistry of ores that are characterized by very high Fe contents (an average of 68.2% Fe).The Pico orebody is a continuous ~3,000-m-long body of a lenticular shape hosted within siliceous itabirite, which is the protore of the soft high- and low-grade ores at the Pico Mine. The soft high-grade ores, together with the low-grade ores, called iron-rich itabirite, are the main types of ore, and respectively represent approximately 51 and 29% of the reserves. The remaining 20% consists of hard high-grade ore. The iron oxide mineralogy is the same as that of the Águas Claras Mine, but in different proportions. Gangue minerals are very rare in the high-grade ores, but are slightly more common in the iron-rich itabirite. Quartz is the dominant gangue mineral, and is found with minor quantities of chlorite. The chemistry of the high-grade ores is characterized by high Fe contents (an average of 67.0%) and low P, Al₂O₃, and SiO₂, which are concentrated in the fines. Iron-rich itabirites average 58.6% Fe and 13.5% SiO₂.The genesis of the soft high-grade ores and iron-rich itabirites is related to supergene processes. Leaching of the gangue minerals by groundwater promoted the residual iron enrichment of the itabirites. This process was favored by the tropical climate and topographic situation. The original composition of the itabirites and the presence of structures controlling the circulation of the groundwater have influenced the degree of iron enrichment. The hard high-grade ores are of a hypogene origin. Their genesis is attributed to hydrothermal solutions that leached the gangue minerals and filled the spaces with hematite. This process remains a source of debate and is not yet fully understood.Editorial handling: S.G. Hagemann     

Chemical and structural characterization of As immobilization by nanoparticles of mackinawite (FeSm)

The mobility and availability of arsenite, As(III), in anoxic environments is largely controlled by adsorption onto iron sulfides and/or precipitation of arsenic in solid phases. The interaction of As(III) with synthetic mackinawite (FeS_m) in pH 5 and 9 suspensions was investigated using high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM), STEM elemental mapping, high resolution TEM, and X-ray photoelectron spectroscopy (XPS). At pH 5, arsenic sulfide phases precipitate among the FeS_m particles as discrete particles that are an amorphous hydrous phase of arsenic sulfide. The oxidation state of As in the surface layers of the arsenic sulfide precipitates is ‘realgar-like’ based on XPS results showing that > 75% of the As 3d peak area is due to As with oxidation states between 0 and 2+. Discrete, arsenic sulfide precipitates are absent at pH 9, but elemental mapping in STEM-EDX mode shows that arsenic is uniformly distributed on the FeS_m, suggesting that uptake is caused by the sorption of As(III) oxyanions and/or the precipitation of highly dispersed arsenic sulfides on FeS_m. XPS also revealed that the FeS_m that equilibrated without As(III) has a more oxidized surface composition than the sample at pH 9, as indicated by the higher concentration of O ( three times greater than that at pH 9) and the larger fraction of Fe(III) species making up the total Fe (2p_3/2) peak. These findings provide a better understanding of redox processes and phase transitions upon As(III) adsorption on iron sulfide substrates.     

谷氨酸插层镁铝水滑石微观结构与性能:实验与理论研究

采用共沉淀法合成了谷氨酸插层镁铝水滑石(LDHs-Glu),并使用XRD表征技术以及分子动力学模拟方法对其微观结构与性能进行了研究。结果表明随着LDHs-Glu中水分子数量增加,层间距d003逐渐增大。XRD表征得到其层间距为1.328 nm,与理论模拟得到的当水分子数Nw=7时的水滑石层间距d003=1.323 nm相近。随着层间水分子数量增加,水合能逐渐增大,最终趋于流体水的特征值(-41.8 kJ/mol)。水合过程中,水滑石层板与阴离子间的氢键逐渐减少,而层板与水分子间的氢键逐渐增多,说明水分子与层板间的亲和力更强。实验表征与理论模拟相结合的研究方法,有望成为插层复合材料微观结构研究的重要手段。