Temporal and spatial variations in the biogeochemical cycling of cobalt in two urban estuaries: Hudson River Estuary and San Francisco Bay

Despite the fact that Co is an essential trace element for the growth of marine phytoplankton, there is very limited information on the cycling of this trace metal in the marine environment. We report here the distribution of dissolved (<0.4 μm) and particulate (>0.4 μm) Co in surface waters of the Hudson River Estuary (HRE) and San Francisco Bay (SFB). Samples were collected during several cruises (from 1990 to 1995 in SFB and from 1995 to 1997 in the HRE) along the whole salinity gradient. Dissolved Co concentrations (mean±1 standard deviation) were nearly identical in magnitude in both estuaries despite differences in climate, hydrography, riverine-flow conditions and land-usage (HRE=0.91±0.61 nM; SFB=1.12±0.69 nM). Dissolved Co levels in each system showed non-conservative distributions when plotted as a function of salinity, with increasing concentrations downstream from the riverine end-members. Desorption from suspended particulates and sewage inputs, therefore, seems to be the major processes responsible for the non-conservative behavior of Co observed. Mass balance estimates also indicated that most of the estuarine Co is exported out of both estuaries, indicating that they and other estuarine systems are principal sources of this essential trace element to the open ocean.     

河北中关矽卡岩铁矿床钴元素分布规律与沉淀机制研究及意义

河北中关铁矿是“邯邢式”矽卡岩铁矿的代表矿床,本文将中关铁矿床成矿过程划分为5个阶段：干矽卡岩阶段、湿矽卡岩阶段、氧化物阶段、铁铜硫化物阶段和铅锌硫化物阶段。对湿矽卡岩阶段、氧化物阶段和铁铜硫化物阶段的金属矿物（包括黄铁矿、磁铁矿、赤铁矿等）开展电子探针测试,并且对这三个成矿阶段的代表性磁铁矿进行LA-ICP-MS微量元素测试,旨在查明中关铁矿床中Co的赋存状态以及在矿床不同成矿阶段的分布规律,探讨Co元素迁移演化-沉淀机制。研究结果表明,Co主要以类质同象的形式存在于黄铁矿中。不同成矿阶段的Co元素分布不均匀,氧化物阶段黄铁矿和磁铁矿中的Co含量最高,分别为0.12%~1.39%、41×10-6~76×10-6;铁铜硫化物阶段黄铁矿大量出现,且Co含量相对较高,为BDL~0.45%,同时期条带状磁铁矿为32×10-6~71×10-6,故此阶段为Co元素最主要的富集阶段。湿矽卡岩阶段为较高温、弱氧化条件,氧化物阶段温度逐渐降低,氧逸度增加,Co可能主要以CoCl42?形式络合迁移;铁铜硫化物阶段温度进一步降低,但还原性增加,Co可能主要以CoCl42?和Co(HS)+形式络合迁移。温度降低以及氧化还原条件的变化可能是控制Co沉淀的重要因素。     

极限平衡方法在夏日哈木镍钴矿山拟建露天采场边坡角优化中的应用

夏日哈木镍钴矿为大型镍钴硫化物矿床,现拟建大型露天采场,边坡采用分台阶式高边坡,最高边坡高度超过600m。该工程具有开挖成本高,边坡一但失稳后果严重的特点。为此需要选择一个即节约经济成本又保障整体边坡稳定的最佳边坡角。本文采取Geostudio软件中的Slope模块极限平衡方法对拟建露天采场假设开挖边坡角的整体边坡稳定性进行分析,提出最佳设计边坡角。　本次边坡角优化的思路：首先根据场地工程地质条件和拟建边坡的高度等因素将拟建边坡划分为5个区,选择典型边坡工程地质剖面并进行工程地质岩体分段,然后通过岩石强度指标折减计算（本文采用费辛柯法、M.Georgi法和经验法）给各分段的岩体赋予凝聚力、内摩擦角等计算参数,采用极限平衡方法（Geostudio软件中的Slope模块法）对不同角度下对各分区边坡的破坏形式及安全系数进行计算,最后提出了各分区边坡的最佳设计边坡角。     

攀西红格钒钛磁铁矿矿田富钴硫化物中钴的地球化学特征及其地质意义

攀西红格钒钛磁铁矿矿田白草矿区发育富钴硫化物矿物,关于其成因和形成环境方面的研究较为薄弱。本文采用矿物学、矿物化学、地球化学等方法对其进行系统研究。矿石中主要富钴硫化物为磁黄铁矿（Po）、黄铁矿（Py）、镍黄铁矿（Pn）、硫钴镍矿（Se）。磁黄铁矿Co、Ni平均质量分数分别为0.21%、0.42%,Co/Ni平均值为1.10;黄铁矿Co、Ni平均质量分数分别为0.18%、0.29%,Co/Ni平均值为0.77;镍黄铁矿Co、Ni平均质量分数分别为2.67%、34.30%,Ni/Fe平均值为1.08、S/Fe平均值为1.91、M/S^#平均值为1.13;硫钴镍矿Co、Ni平均质量分数分别为24.30%、22.90%,Co/Ni平均值为1.06。根据Po-Py矿物温度计,白草矿区富钴硫化物结晶温度在267~490℃之间,表明其形成于中高温的条件。通过与地幔包体镍黄铁矿S/Fe、M/S^#特征值的对比,结合磁黄铁矿具有陨硫铁（Tr）同质多象晶体的特征,认为白草矿区硫化物具有地幔源的特征,说明成矿物质来源于地幔。白草矿区钴地球化学特征研究表明,在硫化物熔体分离过程中,钴迁移至单硫化物固溶体形成Po-Py固溶体,再由Po-Py固溶体中迁移至Pn、Se,形成了Se、Pn、Po-Py、Ccp（黄铜矿）中Co质量分数依次递减的现象。     

中非赞比亚成矿带谦比希铜钴矿床钴的赋存状态与成矿规律

谦比希铜钴矿床是中非赞比亚成矿带重要的超大型铜钴矿床之一,由主矿体、西矿体和东南矿体3部分组成,赋矿层位主要为下罗安亚群敏多拉组和基特韦组,岩性包括泥质板岩、泥质石英岩、板岩、石英砂岩等.现有资料对于矿床中钴的赋存状态和含钴矿物成因的研究较为薄弱,这也直接制约了对钴矿的成因认识及今后找矿方向.本次研究聚焦谦比希矿床中的...     

ANC,BNC and mobilization of Cr from polluted sediments in function of pH changes

During the manufacturing of chromate salts (1972–1992) large quantities of Chromite Ore Processing Residue (COPR) were released into a decantation pond east of the former chemical plant of Porto-Romano (Durres, Albania), giving rise to yellow colored pond sediments. These Cr(VI) bearing sediments were deposited upon Quaternary silty-clay lagoonal sediments rich in iron oxides and organic matter. The pH values in these lagoonal sediments vary around 6.6, while in the pond sediments, it is mainly acidic (due to the presence of the sulfur stock piles in the area and the release of the H₂SO₄ from the activity of the former chemical plant), varying between 1.4 and 3.8. Continuous leaching of the COPR waste resulted in yellow-colored surface water runoff. The prediction of pH changes in the different types of sediments based upon acid/base neutralizing capacity (ANC/BNC) jointly with the quantitative data on release of heavy metals and especially Cr is considered an important advantage of the pH_stat leaching test if compared to conventional leaching procedures. Thus, factors controlling the leaching of Cr(VI), Cr(III), Ca, Al, Fe, Mg from the COPR were investigated by means of pH_stat batch leaching tests and mineralogical analysis. Moreover, mathematical and geochemical modeling complemented the study. The COPR in the area contain very high concentrations of chromium 24,409 mg/kg, which mainly occurs as Cr(III) (75–90%) as well as Cr(VI) (25–10%). The leaching of Cr(VI) occurs in all the range (2–10) of the tested pH values, however, it decreases under acidic conditions. Beside some reduction of Cr(VI) to Cr(III), the Cr(VI) content of the leachtes remains relatively high in the acidic environment, while the limning of Cr(VI) pond sediments will increase the release of the latter specie. The leaching of the Cr(III) occurs strictly under acidic conditions, whereby limning of these sediments will give rise to the lower solubility of Cr(III). The key mineral phases responsible for the fast release of the Cr(VI) are: the chromate salts (i.e. sodium chromate and sodium dichromate), while sparingly soluble chromatite (CaCrO₄) and hashemite (BaCrO₄) release Cr(VI) very slowly. Thus, pH and mineral solubility have been identified as key factors in the retention and the release of the hexavalent CrO₄ ²⁻ and Cr₂O₇ ⁻ from the COPR-rich pond sediments.     

钴矿石浸取液中Co、Cu、Fe的萃取分离

探讨了钴矿石浸出液中Co、Cu、Fe的萃取分离 ,以及不同萃取剂萃取上述元素时的影响因素。提取液用P2 0 4 、LIX984 和正辛酸分别萃取Fe、Cu和Co ,萃取率分别为 99.9%、99.4%和 98.1%。成功地实现了复杂钴矿石中Co、Cu、Fe的分离与提纯     

Flotation Separation of Trace Elements from Alkaline-Earth Matrices by Co(III) Hexamethylenedithiocarbamate before ICP-AES Determination

A method for the selective separation of Ag, Cd, Cr, Cu, Ni, Pb and Zn in traces from solutions of calcite (CaCO₃), dolomite (CaMg(CO₃)₂) and gypsum (CaSO₄.2H₂O) before their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) is presented. The expected interferences of Ca and Mg on intensities of trace analytes were removed by collecting the elements of interest with cobalt(III) hexamethylenedithiocar-bamate, Co(HMDTC)₃. The flotation of aqueous solutions (1 l) of calcite, dolomite and gypsum was performed at pH 6.0, by 1.5 mg l⁻¹ Co and 0.6 mmol l⁻¹ HMDTC⁻. To minimise the effect of the reaction between Ca/Mg, which restrains the function of the surfactant, careful selection of the most suitable foaming reagent was necessary. The accuracy of the method was established by analysing natural alkaline-earth minerals by the standard addition method as well as using the dolomite reference materials GBW 07114 and GSJ JDo-1. The ICP-AES limits of detection following flotation on different minerals were found to be 0.080 μg g⁻¹ for Cd, 0.105 μg g⁻¹ for Ag, 0.142 μg g⁻¹ for Cu, 0.195 μg g⁻¹ for Cr, 0.212 μg g⁻¹ for Ni, 0.235 μg g⁻¹ for Zn and 0.450 μg g⁻¹ for Pb.     

我国钴矿矿产资源及其成矿作用

钴广泛应用于军事、钢铁、电器、机械等方面，它具有亲铁亲硫的双重性，在各类岩浆岩中的分布不均匀，由超基性岩向酸性岩，钴的含量迅速降低。我国钻矿资源呈现富矿少、贫矿多的特点，并且铬矿主要分布在甘肃、青海、新疆、吉林、陕西、云南、四川等地。按照矿床形成的成矿环境、矿床岩石组合，矿床类型划分为：与镁铁质-超镁铁质岩有关的硫化物钻矿、与海相火山喷发有关的钻多金属矿、与斑岩有关的铜钻矿、与砂岩有关的钻矿、与中酸性侵入岩有关的矽卡岩铁钻矿、与风化作用有关的钴矿等六类。     

Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions

To get deeper insight into the phase relations in the end-member system Fe₂SiO₄ and in the system (Fe, Mg)₂SiO₄ experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO₂ corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe₂SiO₄ + O₂ = 6 FeSiO₃ + 5 Fe_2.40Si_0.60O₄. Refinement of site occupancies in combination with stoichiometric Fe³⁺ calculations show that 32% of the total Fe is incorporated as Fe³⁺ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe³⁺ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe³⁺ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K _D independent on composition and a bulk composition of x _Fe = 0.44 this fractionation would stabilize spl with x _Fe = 0.72. Thus, spl could be a potential Fe³⁺ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.