北太平洋铁锰结核富集区沉积物和间隙水中重金属元素地球化学

对北太平洋28个相对富集铁锰结核的沉积物和间隙水中重金属元素(Cu、Pb、Zn、Cr、Co、Ni)地球化学研究表明:沉积物中重金属元素明显的比陆地土壤、河口、陆架及贫结核洋区的沉积物富集,并与沉积物类型密切有关;沉积物中元素的赋存状态不同,进入间隙水的途径不同;由于Cu、Co的生物作用大于Zn、Ni,使沉积物中 Cu/Zn、Co/Ni比值由钙质软泥—钙、硅软泥—硅质软泥—褐色粘土升高。     

东太平洋海盆沉积物间隙水地球化学研究

研究了东太平洋海盆沉积物间隙水中元素的变化趋势及组合特征。结果表明，经过成岩改造的间隙水化学组成相对于海水发生了较大的变化。其中K、Sr、B趋于亏损，Ca、Mg、Li则表现出亏损和富集两种不同的变化趋势：Si、Ba、Rb富集，Mn、Fe、Zn、Pb、Cu、Ni、Co则高度富集。R型聚类分析结果表明，间隙水中金属元素可分成K、Sr、Mg、Li、Ca和Mn、Fe、Rb、Co，Zn、Cu、Ni、Pb两组。影响间隙水元素组成变化的主要因素有火山物质的海解作用，硅质生物组分和岩成碎屑组分的成岩作用及有机物的分解作用等。     

夏威夷群岛东南海域多金属结核的物源特征及其对古海水、亚洲季风信息的记录

为深入探讨夏威夷群岛东南海域结核的物源特征及其所记录的古海水、亚洲季风信息,采用电感耦合等离子体质谱(ICP-MS)、X射线荧光光谱仪(XRF)、电子探针(EPMA)方法,对来源于原地质矿产部和国家海洋局"海洋四号"科考船DY85-1航次采集的研究区的4块多金属结核样品进行了详细的元素地球化学分析测试,并对分析结果进行了Fe-Mn-[(Cu+Ni)×10]、Fe-Mn-[(Cu+Co+Ni)×10]图解与元素间相关性分析。结果表明,结核中的成矿元素直接来源于海水;应用Co含量经验公式、结合Mn/Fe值计算方法对其生长速率进行验证,得到结核的Fe/Mn、Al/(Fe+Mn)值变化曲线与太平洋底栖有孔虫的δ18O曲线、亚洲内陆粉尘通量曲线呈现出相似的变化趋势,表明多金属结核可作为古海水氧化程度及亚洲季风演化研究的新载体。     

中国多金属结核开辟区沉积物中微量元素地球化学特征

分析了中国多金属结核开辟区沉积物中Ba、Ce、Co、Cr、Cu、Mo、Ni、Sr、V、Y和Zn等11个微量元素的含量。研究表明，开辟区沉积物中微量元素在不同沉积单元中的分布特征存在明显差异，反映了地质历史上沉积环境的不同。沉积物中的Zn、Ni和Mn具有共同来源，反映铁锰氧化物、氢氧化物对这些元素的吸附控制作用；Sr、Ba以及Ce和Y等元素在东区主要与岩源碎屑有关，而西区则主要来自生物碎屑；Cu具有多种来源，东区主要与生物组分和岩源碎屑有关，西区则主要与自生铁锰氧化物的吸附有关。而通常认为与有机物有关的Cr、V等元素在研究区内则主要来自岩源碎屑。     

成矿元素Mn、Co和Ni在富钴结壳生长界面的热力学行为

富钴结壳是广泛分布在海底正地形上的一种铁锰氧化物,由于富钴结壳富含Co等战略金属元素,使其成为潜在的待开发海底资源。它包括结核型和层状型两种类型,受地形控制,使得坡度比较陡峭的地形上板状结壳分布广泛,结核型的则少见。富钴结壳分布水深介于400～4000m之间,其主要成矿元素Mn、Fe、Co和Ni等不     

大洋多金属结核成因的地球化学标志

本文通过对取自太平洋不同地区的近百个多金属结核样品研究表明,不同成矿介质中形成的结核,地球化学特征明显不同,水成型结核矿物成分上富含σ—MnO_2,化学成分上富含Fe、Co、Pb,而贫Mn、Cu、Ni、Zn,TiO_2>1%,ΣREE>1000ppm,σCe>1.5;早期成岩型结核矿物成分上相对富含钡镁锰矿,化学成分上富含Mn、Cu、Ni、Zn,而贫Fe、Co、Pb,TiO_2<1%,ΣREE<1000ppm,σCe≤1.在此基础上通过对Bonatti图解的实际应用和理论分析,证明Mn-Fe-(Cu+Co+Ni)x10图解不具判别意义,并提出Mn/Fe-TiO_2,Mn-Fe-TiO_2×10,Mn-Fe-ΣREE×100和Mn-Fe-σCe×10成因判别图解.     

索马里海盆多金属结核中关键金属富集机制及古环境记录

多金属结核富含Mn、Fe、Ni、Cu等元素以及Co和REY(稀土元素和钇)等关键金属, 是重要的大洋矿产资源。为了探究西北印度洋索马里海盆结核中关键金属的富集机制及古环境记录, 本文使用X射线衍射仪(XRD)分析了一个结核的矿物成分, 并通过激光剥蚀电感耦合等离子体质谱仪(LA-ICPMS)和电子探针(EPMA)原位分析了该结核的微区元素组成。结果表明, 研究区结核内层为柱状结构, 中间为掌状, 外层又变为柱状。结核主要由水成型富铁层构成, 但外层中还存在薄的(100~200μm)成岩-混合型富锰层。富铁层MnO平均含量为25.1%, FeO为30.4%, Co为0.26%, Ni为0.24%, Cu为0.09%, ΣREY为1981×10^-6。富锰层MnO平均含量为52.0%, FeO为7.40%, Co为0.09%, Ni为2.45%, Cu为0.53%, ΣREY为719×10^-6。富铁层主要由含铁水羟锰矿构成, 而富锰层主要由Ⅰ型布赛尔矿构成。Ni和Cu主要赋存于Ⅰ型布赛尔矿, Co和REY则主要赋存于含铁水羟锰矿中, 并且Co存在一个“拐点”。富锰矿物(Ⅰ型布赛尔矿)相对更富集HREE, 而含铁水羟锰矿中更富集LREE。从内到外, 结核中ΣREY呈下降趋势, REY的变化主要受Ce影响。结核Mn/Fe比值与δCe不相关, 但生长速率与δCe显著负相关, 表明生长速率可能是控制Ce异常的主要因素, 仅凭Ce异常不能区分结核微区的成因及氧化还原环境。根据Co经验公式估算, 索马里海盆结核形成年龄为~1.46Ma。柱状结构的开始形成可能与早更新世晚期的古海洋环境转型有关。而掌状结构开始生长于~0.6Ma, 中更新世气候转型之后风尘增加使得结核中Si和Al增加, 并稀释了其他成矿元素。结核富锰层可能生长于末次间冰期的亚氧化底层水环境, 且具有一定对称性和渐变性, 指示了氧化还原环境的逐渐改变和恢复。

     

深海多金属结核分布与有价元素提取工艺进展

深海多金属结核主要分布在CP区和CC区等不同海域,表层沉积物均以硅质粘土为主,CP区多金属结核丰度一般大于15 kg/m~2,Cu+Co+Ni品位较低,一般小于1.8%;CC区区内丰度大于5 kg/m~2的占45%,主要集中在本区的中部和南部,其对应的品位高于2.5%,基本呈纬向带状分布。外部结核层、内部结核层与核心层w(Fe_2O_3)、w(MnO)分别为9.4%～12.8%、39.7%～46.5%,不同结核层中钠水锰矿、钡镁锰矿、δ-Mn_2等主要矿物的XRD衍射峰强度呈现一定差异。外部结核层较薄,内部结核层较厚表面布满规则裂纹,核心层至少具有一个形核核心。多金属结核中所含金属元素种类丰富、多矿物紧密混杂,难以提取其中的Mn、Fe、Cu、Co和Ni等有价金属元素。火法冶炼有熔炼法与直接还原法,其产品一般为富锰渣与合金,酸/碱法浸出可得到Mn、Fe、Cu、Co和Ni等的金属,其浸出率基本能达到85%以上,甚至可以达到95%以上。生物法可通过微生物浸出多金属结核的Mn、Fe、Cu、Co和Ni等元素。此外,熔炼-锈蚀法、电解法等处理多金属结核同样效果显著。     

雅鲁藏布江表层沉积物地球化学元素研究

雅鲁藏布江流域还没有大的工业污染源,仍然属于自然河流.对雅鲁藏布江16个表层沉积样品的全样、小于20μm 和小于63μm 粒级的32种元素含量进行了测定,并分析了与人类活动密切相关的元素 Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Cd 和 Pb 的含量分布特征,以及这些元素含量与粒径之间的关系.结果表明,多数元素(Cs 除外)与西藏土壤元素背景值相差不大, B、Cr、Ni、As 和 Cs 含量高于中国陆壳元素丰度值,但这些元素主要来源于该流域富含这些元素的页岩、片岩和千枚岩等母岩.由于相似的地球化学行为,沉积物中 Cr、Mn、Fe、Co、Ni、Cu、Zn 之间显著正相关;除 Pb、As 外,一些元素(如 Zn、Ni)与沉积物的粒径显著负相关     

太平洋北部铁锰结核富集区沉积物的元素地球化学特征

本文对太平洋北部铁锰结核富集区沉积物的元素地球化学作了较为详细的研究。因子分析提供的信息表明,元素的分布主要受三个因子控制:（1）粘土及Fe、Mn氧化物水化物胶体的吸附作用;（2）生物化学作用过程有关的自生沉积作用;（3）海底页岩风化及附近海区的火山喷发作用。元素的来源:（1）Fe、Mn、Cu、Co、Ni、Zn、Cr、Cr、Mg、Al、Ti、K共生,主要来自粘土吸附;（2）C_有机、N、Sr、Na及Si、Ca、Sr主要来自生物化学过程沉积;（3）Pb主要来源于岩石碎屑（火山喷发碎屑）。     

Assessment of trace metal contents in water and bottom sediments from Eğirdir Lake,Turkey

The concentration of metals (Pb, As, Co, Cu, Ni, Zn, Fe and Mn) was investigated in water and sediment samples of E?irdir Lake. The Lake is the second largest fresh water lake of Turkey and it is used as drinking water in the region. The anthropogenic pollutants are primary sources of trace metals which are negatively affected lake water quality. These negative effects were observed in both lake water and bottom sediments. According to obtained data, Pb, Cu, Ni, Fe and Zn have significant enrichment in sediments samples. In addition, the hydrodynamic model of the lake was determined as effectively for Pb, Co, Cu, Ni, Zn, Fe and Mn accumulations. Also, the effect of anthropogenic pollutants was found to be more dominant than geogenic effect in metal accumulation of the lake bottom sediments. Therefore, anthropogenic pollutants within the lake basin should be consistently controlled for the sustainable usage of the lake.     

Surface metal enrichment and partitioning of metals in a dated sediment core from a Norwegian fjord

A 24-cm long sediment core from an oxic fjord basin in Ranafjord, Northern Norway, was sliced in 2 cm sections and analysed for As, Co, Cu, Ni, Hg, Pb, Zn, Mn, Fe, ignition loss and Pb-210. Partitioning of metals between silicate, non-silicate and non-detrital phases was assessed by leaching experiments, in an attempt to understand the mechanisms of surface metal enrichment in sediments. Relative to metal concentrations in sediments deposited in the 19th century, metals in near surface sediments were enriched in the following order: Pb > Mn > Hg > Zn > Cu > As > Fe. Cobalt and Ni showed no enrichment. The non-detrital fraction of Cu, Pb, Mn and Zn was significantly higher in the upper 10 cm than at greater depth in the core. This corresponds to sediments deposited since 1900, when mining activities started in the area. The enrichment of Cu, Pb and Zn is assumed to be mainly a result of mining, while Mn is apparently enriched in the surface due to migration of dissolved Mn and precipitation in the oxic surface layer. Elevated concentrations of As and Fe in the upper 4 cm are presumably due to discharges from a coke plant and an iron works respectively. The excess Hg present in the near surface sediments is tightly bound, either in coal particles or ore dust introduced by local industry, or via long distance transport of atmospheric particles. Calculations of metal flux to the sediments indicate an anthropogenic flux of Zn equal to its natural flux, while the flux of Pb shows a threefold increase above natural input.     

Heavy metal distribution in the surface layer of bottom sediments of the Kara Sea

This paper addresses the distribution of heavy metals (Co, Ni, Cu, Zn, Cd, Sn, Sb, Pb, and Bi) as well as Si, Al, Fe, and Mn in the surface (0–2 cm) layer of bottom sediments of the Kara Sea. The contents of these elements are determined in each of the previously distinguished facies-genetic types of terrigenous sediments: fluvial, glacial, estuarine, shallow water–marine, “background” marine, and relict sediments. It is shown that these types reflect the modern conditions of accumulation of river discharge material, which forms fans of two greatest Siberian rivers, Ob and Yenisei. The main stages are distinguished in heavy metal accumulation. The first stage is related to the avalanche sedimentation of terrigenous sediments in the estuary and characterized by the elevated contents of Co, Ni, Cu, Zn, Cd, Sb, and Bi. The second stage reflects the mechanical differentiation of sedimentary material by waves and bottom currents in a shallow-water sea part adjacent to the estuarine zone, with accumulation of Pb- and Sn-bearing “heavy” ore minerals. The deepwater background terrigenous–marine sediments accumulate mainly Ni, Zn, and Cd, as well as Mn. The relict sediments differ in the high contents of Si, Mn, and Sn.     

Ferromanganese oxide deposits from the Central Pacific Ocean,II. Nodules and associated sediments

Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO₂-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO₂ nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.     

Managanese and iron in the White Sea: Sedimentation and diagenesis

Iron and manganese in bottom sediments studied along the sublatitudinal transect from Kandalaksha to Arkhangelsk are characterized by various contents and forms depending on sedimentation environments, grain size of sediments, and diagenetic processes. The latter include redistribution of reactive forms leading to enrichment in Fe and Mn of the surface sediments, formation of films, incrustations, and ferromanganese nodules. Variations in the total Fe content (2–8%) are accompanied by changes in the concentration of its reactive forms (acid extraction) and the concentration of dissolved Fe in the interstitial water (1–14 μM). Variations in the Mn content in sediments (0.03–3.7%) and the interstitial water (up to 500 μM) correspond to a high diagenetic mobility of this element. Changes in the valence of chemical elements results in the redox stratification of sediment strata with maximum concentrations of Fe, Mn, and sulfides. Organic matter of sediments with a considerable terrestrial constituent is oxidized by bottom water oxygen mainly at the sediment surface or in anaerobic conditions within the sediment strata. The role of inorganic components in organic matter oxidation changes from surface sediments, where manganese oxyhydroxide dominates among oxidants, to deeper layers, where sulfate of interstitial water serves as the main oxidant. Differences in river runoff and hydrodynamics are responsible for geochemical asymmetry of the transect. The deep Kandalaksha Bay serves as a sediment trap for manganese (Mn content in sediments varies within 0.5–0.7%), whereas the sedimentary environment in the Dvina Bay promotes its removal from sediments (Mn 0.05%).     

The Heavy Metals Speciations in Bottom Sediments of Vyshny Volochek Reservoir

The water ecosystem of the Vyshny Volochek Reservoir is characterized based on the study of the distribution of heavy metals speciations in the solid phase and pore waters of bottom sediments. Using the sequential extraction procedure, it is shown that Mn is mainly present in exchangeable and carbonate-bound forms; significant roles for Fe, Zn, Pb, and Co are played by forms that are bound to iron and manganese hydroxides and Cu and Ni are mainly bound to organic matter. Thermodynamic calculations have established the prevailing share of the following forms in pore waters: free ions for Zn, Ni, Co, and Cd, carbonate complexes for Pb, and fulvic complexes for Cu. It has been revealed that the speciation forms of heavy metals in bottom sediments depend on the lithological features and content of organic matter in sediments.     

Nodules in sediments of an artificial reservoir in the Altai Territory

Nodules of various compositions, including ferromanganese nodules, have been found in bottom sediments of an artificial reservoir in the central Altai Territory. The nodules were formed in the alkaline environment against the background of a high carbonate content and saturation with oxygen. The rate of nodule growth is no less than 1.7–1.8 mm/yr and the pH value of water varies from 8.0 to 9.7. Fe and Mn contents in soil and loam of the drainage area are lower than the global clarke value, whereas Ca, K, and Na contents are much higher. The main mass of bottom sediments in the reservoir is markedly enriched in Cd, Mg, Mn, Sr, Ni, Cr, Sb, V, and Pb, but they are depleted in Cu, Mo, Zn, and Li, relative to the soil and loam. Elements in ferromanganese nodules are arranged in the following way in terms of the decreasing concentration coefficient: Mn (27) > Ba (13.4) > Co (10.7) > Mo (9.2) > Cd (5.35) > Ni (3.88) > V (3.52) > Cu (3.3) > Fe (3.2) > Sb (2.17) > Sr (2.04) > Pb (1.5) > Zn (1.43) > Cr (1.1) > Li (0.78) > Mg (0.75) > Na (0.69) > K (0.67) > Ca (0.51). The microelemental composition of nodules in the reservoir qualitatively fits the composition of ferromanganese nodules in seas and oceans. However, the contents of major ore elements (Ni, Cu, Co, Zn, Pb, Mo, and V) in ferromanganese nodules from the World Ocean are much higher than in nodules from the examined reservoir.     

Sedimentary Trace Elements as Proxies to Depositional Changes Induced by a Holocene Fresh-Brackish Water Transition

A halocline developed in the GotlandDeep, Baltic Sea, at c. 8.0 ¹⁴C ky BP, as theresult of a transition from fresh to brackish water.The sediment-water interface changed from oxic topredominantly anoxic, depositional conditions wereperiodically euxinic and pyrite formation wasextensive. This environmental change led topyritization of the upper part of earlier depositedsediments. This study discusses how the distributionof trace elements (As, Ba, Cd, Cu, Co, Mo, Mn, Ni, Pb,U, Zn and V) were affected by the changing redoxconditions, productivity and salinity. The reducingconditions led to pyritization of Cu, Co, Ni, Cd, Mo,Mn and As. Lead and Zn concentrations are very low inpyrite, in agreement with their coordination tosulfide being tetrahedral. Certain elements areenriched in those sediments deposited under euxinicconditions. This enrichment was caused by scavengingof elements dissolved in the water column and isrestricted to elements that have a comparably longresidence time in the Baltic Sea. Molybdenum appearsto be the most unambigious proxy for euxinicconditions, whereas enrichment of U also requiresbrackish water in the productive zone. In the brackishenvironment, enrichment of Ba and V are linked to thecycling of organic carbon. Manganese and As are theonly elements that have been significantly remobiliseddue to the downward moving pyritization front.     

太平洋调查区多金属结核的地球化学特征和成因

东太结核主要为半埋藏和埋藏型,发育于以黏土和硅质组分为主的沉积环境.东太结核的锰相矿物主要有水羟锰矿和钡镁锰矿,具有较高的REY、Cu、Ni含量和Mn/Fe比值,显示遭受间隙水的影响,落入水成成因和成岩成因两个区间范围.西太结核主体暴露在海水中,周围沉积物主要由深海黏土组成.西太结核的锰相矿物几乎只有水羟锰矿,具有较高...