From surface acidity to surface reactivity; inhibition of oxide dissolution

Paul Schindler's early work on the acid-base chemistry of oxides was instrumental for the development of the concept of surface complexation. This approach has not only been important in establishing a theory on the adsorption of metal ions and ligands as a function of pH and solution variables, but has become essential in establishing surface speciation (coordinative structural and electronic arrangement at the solidwater interface) which in turn determines surface reactivity. The factors that affect dissolution of Fe(III) (hydr)oxides and inhibition of dissolution are discussed. A few examples for the inhibition of reductive and ligand-promoted dissolution by binuclear complexes of oxoanions (phosphate, borate) and of protonpromoted dissolution by Cr(III) are given.     

Petrology and Fe–Ti oxide reequilibration of the 1991 Mount Unzen mixed magma

A dacitic magma (64.5 wt.% SiO₂), a mixture of phenocryst-rich rhyodacite and an aphyric mafic magma, was erupted during the recent 1991–1995 Mount Unzen eruptive cycle. The experimental and analytical results of this study reveal additional details about conditions in the premixing and postmixing magmas, and the nature of the mixing process. The preeruption rhyodacitic magma was at a temperature of 790±20°C according to Fe–Ti oxide phenocryst cores, and at a depth of 6 to 7 km (160 MPa) according to Al-in-hornblende geobarometry. The mafic magma that mixed with the rhyodacite is found as andesitic (54 to 62 wt.% SiO₂) enclaves in the erupted magma and was essentially aphyric when intruded. Phase equilibria indicate that an aphyric andesite at 160 MPa is >1030°C (H₂O-saturated) and possibly as high as 1130°C (2 wt.% H₂O). The composition of the rhyodacite which was mixed with the andesite is estimated to lie between 67 and 69 wt.% SiO₂. Using these compositions and temperatures, the temperature of the Unzen magma after mixing is estimated to be at least 850° to 870°C. The groundmass Fe–Ti oxide microphenocrysts and those in pargasite-bearing reaction zones around biotite phenocrysts both give 890±20°C temperatures; the oxide–oxide contacts give temperatures of 910±20°C. The 900±30°C postmixing temperatures are consistent with phase-equilibria experiments which show that the magma was not above 930°C at 160 MPa. Our Fe–Ti oxide reequilibration experiments suggest that the mixing of the two magmas began within a few weeks of the eruption, which is a shorter time than is calculated using available diffusion data. There is also evidence that some mixing took place much closer to the time of extrusion based on the presence of unrimmed biotite phenocrysts in the magma.     

青海玛温根矿区氧化铅银矿工艺矿物学特性及分析研究

结合光学显微镜鉴定、扫描电镜、X射线能谱探针、筛析等技术手段,系统研究了青海省玛温根矿区产出的有代表性的氧化铅矿石的工艺矿物学特征。结果表明:矿石主要有价元素是Pb(2. 76%)和Ag(204. 4×10-6);矿石中铅的赋存状态较复杂,主要赋存于铅铁矾等难溶铅中,其次赋存于氧化铅、硫酸铅中,矿石中的铅矿物主要是铅矾、白铅矿、砷铅铁矾,少量方铅矿、砷铅矿等;银的赋存状态亦较为复杂,独立银矿物为硫铜银矿,含量甚微,部分银呈类质同像赋存于其他的金属硫化物中。通过偏光显微镜和扫描电镜分析发现,主要的铅矿物如铅矾、白铅矿等相互交代连生现象明显,且嵌布粒度细小,这与筛析检测结果相一致,同时矿石中As含量较高,达到了5. 43%,含砷矿物主要为毒砂、臭葱石,经X射线能谱分析,部分铅矿物与砷元素关系密切,并形成了砷铅铁矾、砷铅矿等复杂砷铅矿物。所以预测在选矿过程中,砷会随铅矿物同步富集,银的独立银矿物主要是硫铜银矿,且嵌布粒度微细,大部分银矿物以微细粒包裹态赋存于石英、褐铁矿等硅酸盐或氧化物中。根据以上研究成果,可判定该氧化铅银矿属于极难选矿石,建议采用浮选-化学选矿工艺综合回收铅、银金属的技术路线。     

安徽宣城第四纪红土剖面的全氧化铁含量及其古环境意义

对宣城第四纪红土剖面的研究表明,全氧化铁含量能够较好地指示中国南方第四纪气候的波动。与北方黄土古土壤序列相比,宣城剖面的全氧化铁明显较高,指示了南方地区更强的风化成壤作用。     

A new hydrous phase δ-AlOOH synthesized at 21 GPa and 1000 °C

A new phase of AlOOH (tentatively called δ-AlOOH) was synthesized at 21?GPa and 1000?°C and its crystal structure was identified by a powder X-ray diffraction method. Rietveld refinement revealed that this aluminum oxide hydroxide has an orthorhombic unit cell, a?=?4.7134(1) Å, b?=?4.2241(1) Å, c?=?2.83252(8) Å, V?=?56.395 (5) ų, and Z?=?2 in the space group of P2₁?nm. A calculated density is 3.533?g?cm^?3, which is about 4.48 and 15.04% denser than that of diaspore and boehmite, respectively. The δ-[Al_0.86Mg_0.07Si_0.07]OOH is also stable at 21?GPa and 1000?°C, coexisting with majorite and phase egg, and its cell parameters are a?=?4.710(1) Å, b?=?4.215(1) Å, c?=?2.839(1) Å, and V?=?56.37(1) ų.     

新疆哈密香山西铜镍-钛铁矿床系同源岩浆分异演化产物——矿相学、锆石U-Pb年代学及岩石地球化学证据

香山西岩体是东天山地区发现的唯一的一个铜镍-钛铁复合型含矿岩体,前人对香山西铜镍-钛铁矿床成因认识一直存在争议。本次通过矿相学研究结合电子探针分析,在香山西铜镍矿石中发现了铜镍硫化物与钛铁氧化物共生的现象,并首次测定了香山西钛铁辉长岩的SIMS锆石U-Pb年龄为278.6±1.8Ma(MSWD=1.2),与前人测得香山中岩体角闪辉长岩的锆石U-Pb年龄基本一致,证实了香山西铜镍矿与钛铁矿为共生关系,两者空间上渐变过渡。岩石地球化学研究表明,香山岩体(包括钛铁辉长岩)为同源岩浆经结晶分异作用形成的一套镁铁-超镁铁质岩体,具有拉斑玄武质岩浆分异演化趋势,并且经历了与地壳物质的混染。与中段和东段岩石相比,香山西辉长岩类具有相对高的REE、SiO₂(平均48.99%)、K₂O+Na₂O(平均3.43%)、TiO₂(平均1.26%)和明显低的Mg^#值(平均62.4),表现出分异演化程度高于中段和东段。经反演得出香山岩体原始岩浆含MgO约10%,FeO约9%,TiO₂约1.14%,与同一成矿带内其它含铜镍矿岩体原始岩浆成份相近,应为 普通的拉斑玄武质岩浆。因此,香山西钛铁矿床的形成机制可能是由普通的拉斑玄武质岩浆,经历了较高程度的分异演化导致钛铁氧化物在残余岩浆中逐步富集,岩浆在上升侵位过程中与地壳物质的混染,不仅促使了岩浆中硫化物的饱和,同时提高了岩浆体系的氧逸度,进而促使了钛铁氧化物结晶沉淀。对香山西钛铁矿床成因研究的启示意义在于,除我国攀西地区高钛的玄武质岩浆外,普通的拉斑玄武质岩浆,在有利的分异演化条件下(如初始低氧逸度、相对高度的分异演化、后期与地壳物质混染)也有可能形成大型钛铁矿床。     

氧化铜-磷酸盐无机胶粘剂的制备工艺研究

研究了氧化铜粉粒径、磷酸盐密度、调胶比、固化时间及固化温度等对氧化铜-磷酸盐无机胶粘剂粘接性能的影响。实验结果表明,采用粒径为55~65μm的氧化铜粉,适当提高磷酸的聚合程度,调胶比R=4~5.5 g/m l时,胶粘剂可以获得良好粘接性能。同时采用80℃左右的固化温度,保持不小于3 h的固化时间,则是胶粘剂发挥最佳效能的决定性因素。同时添加合适的改性剂如氢氧化铝能够有效地改善胶粘剂粘接性能。     

微波溶样-自动电位滴定法测定铬矿石中三氧化二铬

样品经硫酸-磷酸-氟硼酸分解,在30～60 kPa条件下进行微波溶样,用自动电位滴定仪测定铬矿石中三氧化二铬的含量。对两个不同三氧化二铬含量的铬矿石国家一级标准物质测定20次,测定的平均值与标准值的相对误差为0.015%～0.021%,相对标准偏差为0.09%～0.10%。选取主要进口国的不同含量的铬矿石进行主含量的测定,与经典法对比,分析结果均在合理允差范围之内。方法具有简便、快速、低耗、污染小等优点,可应用于大批铬矿石样品的分析及检测。     

Greenhouse gas emissions from soils—A review

Soils act as sources and sinks for greenhouse gases (GHG) such as carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). Since both storage and emission capacities may be large, precise quantifications are needed to obtain reliable global budgets that are necessary for land-use management (agriculture, forestry), global change and for climate research. This paper discusses exclusively the soil emission-related processes and their influencing parameters. It reviews soil emission studies involving the most important land-cover types and climate zones and introduces important measuring systems for soil emissions. It addresses current shortcomings and the obvious bias towards northern hemispheric data.When using a conservative average of 300 mg CO₂e m⁻² h⁻¹ (based on our literature review), this leads to global annual net soil emissions of ≥350 Pg CO₂e (CO₂e = CO₂ equivalents = total effect of all GHG normalized to CO₂). This corresponds to roughly 21% of the global soil C and N pools. For comparison, 33.4 Pg CO₂ are being emitted annually by fossil fuel combustion and the cement industry.     

PbO中层错及共生氧化物的电子显微术研究

在含于磁铁矿中的四方对称结构氧化铅中观察到柏格斯矢量为２／１１（３１０）的（１１）层错，这些层错平行排列并相互交截，穿插形成沿（１００）方向的调制结构，调制波的平均波长约为１００ｎｍ同时，由多相关性区域的选区电子衍射图测定了磁铁矿中四方和正交氧化铅及方铁矿的取向关系。