盐湖及相关资源开发利用进展(续完)

对近年来国内外盐湖资源开发利用的进展情况加以介绍 ,也涉及到国外钾、锂、镁、硼、碘等相关产品的生产、消费、价格等情况。还对资源开发的可持续发展以及我国盐湖及相关资源开发的某些问题加以讨论     

Lithium extraction from hard rock lithium ores (spodumene,lepidolite, zinnwaldite,petalite): Technology,resources, environment and cost

Lithium production in China mainly depends on hard rock lithium ores, which has a defect in resources,environment, and economy compared with extracting lithium from brine. This paper focuses on the research progress of extracting lithium from spodumene, lepidolite, petalite, and zinnwaldite by acid,alkali, salt roasting, and chlorination methods, and analyzes the resource intensity, environmental impact,and production cost of industrial lithium extraction from spodumene and lepidolite. It is fou...     

柴达木盆地西部油田水钾硼锂富集规律及影响因素研究

在对国家“十五”科技攻关2004BA602B-08项目实施的基础上,通过对柴达木盆地西部主要构造油田水的分布特点分析,研究了油田水中主要组分及钾、硼、锂的富集规律,并进一步指出,气候环境、构造演化是油田卤水中主要物质组分富集最主要的影响因素。     

Geochemical evolution of halogen-enriched granite magmas and mineralizing fluids of the Zinnwald tin-tungsten mining district,Erzgebirge, Germany

We remelted and analyzed crystallized silicate melt inclusions in quartz from a porphyritic albite-zinnwaldite microgranite dike to determine the composition of highly evolved, shallowly intruded, Li- and F-rich granitic magma and to investigate the role of crystal fractionation and aqueous fluid exsolution in causing the extreme extent of magma differentiation. This dike is intimately associated with tin- and tungsten-mineralized granites of Zinnwald, Erzgebirge, Germany. Prior research on Zinnwald granite geochemistry was limited by the effects of strong and pervasive greisenization and alkali-feldspar metasomatism of the rocks. These melt inclusions, however, provide important new constraints on magmatic and mineralizing processes in Zinnwald magmas.The mildly peraluminous granitic melt inclusions are strongly depleted in CAFEMIC constituents (e.g., CaO, FeO, MgO, TiO₂), highly enriched in lithophile trace elements, and highly but variably enriched in F and Cl. The melt inclusions contain up to several thousand ppm Cl and nearly 3 wt% F, on average; several inclusions contain more than 5 wt% F. The melt inclusions are geochemically similar to the corresponding whole-rock sample, except that the former contain much more F and less CaO, FeO, Zr, Nb, Sr, and Ba. The Sr and Ba abundances are very low implying the melt inclusions represent magma that was more evolved than that represented by the bulk rock. Relationships involving melt constituents reflect increasing lithophile-element and halogen abundances in residual melt with progressive magma differentiation. Modeling demonstrates that differentiation was dominated by crystal fractionation involving quartz and feldspar and significant quantities of topaz and F-rich zinnwaldite. The computed abundances of the latter phases greatly exceed their abundances in the rocks, suggesting that the residual melt was separated physically from phenocrysts during magma movement and evolution.Interactions of aqueous fluids with silicate melt were also critical to magma evolution. To better understand the role of halogen-charged, aqueous fluids in magmatic differentiation and in subsequent mineralization and metasomatism of the Zinnwald granites, Cl-partitioning experiments were conducted with a F-enriched silicate melt and aqueous fluids at 2,000 bar (200 MPa). The results of the experimentally determined partition coefficients for Cl and F, the compositions of fluid inclusions in quartz and other phenocrysts, and associated geochemical modeling point to an important role of magmatic-hydrothermal fluids in influencing magma geochemistry and evolution. The exsolution of halogen-charged fluids from the Li- and F-enriched Zinnwald granitic magma modified the Cl, alkali, and F contents of the residual melt, and may have also sequestered Li, Sn, and W from the melt. Many of these fluids contained strongly elevated F concentrations that were equivalent to or greater than their Cl abundances. The exsolution of F-, Cl-, Li-, ± W- and Sn-bearing hydrothermal fluids from Zinnwald granite magmas was important in effecting the greisenizing and alkali-feldspathizing metasomatism of the granites and the concomitant mineralization.Editorial Handling: B. Lehmann     

三元体系LiCl-Li2SO4-H2O和Li2SO4-Na2SO4-H2O 333.15 K相平衡研究

采用等温溶解平衡法研究了三元体系LiCl-Li₂SO₄-H₂O和Li₂SO₄-Na₂SO₄-H₂O在333.15 K下的相平衡关系,测定了333.15 K条件下两个体系平衡溶液的溶解度,根据溶解度数据绘制了两个三元体系的相图。研究发现：在三元体系LiCl-Li₂SO₄-H₂O中,相图由两条单变曲线、一个不变点和两个结晶区组成,平衡固相为LiCl·H₂O和Li₂SO₄·H₂O;在三元体系Li₂SO₄-Na₂SO₄-H₂O中,相图由两个不变点、三条单变曲线和三个结晶区组成,平衡固相分别为Li₂SO₄·H_2...     

水盐体系中有干扰Li+离子存在下测定Mg2+浓度的掩蔽法研究

在水盐体系中,大量Li+的存在,对EDTA络合滴定法测镁有严重的干扰,使滴定结果偏高。采用体积比为1∶9的正丁醇与无水乙醇作掩蔽剂,探究其在不同Li+/Mg2+摩尔比、不同浓度、不同取样量下的适宜加入量,得出混合醇的加入量与Li+/Mg2+摩尔比有较大关系,与溶液浓度、取样量的多少均无明显关系;同时指出在同一Li+/Mg2+摩尔比下混合醇的加入量有个适宜的范围。该方法的相对误差不大于0.3%。对提高含Li+和Mg2+的水盐体系相化学实验研究的可靠性和精度具有重要意义。     

Insights into Li and Li isotope cycling and sub-arc metasomatism from veined mantle xenoliths,Kamchatka

Harzburgitic xenoliths cut by pyroxenite veins from Avachinsky volcano, Kamchatka, are derived from the sub-arc mantle and record element transfer from the slab to the arc. Olivine and orthopyroxene in the harzburgites have Li isotopic compositions (δ⁷Li = +2.8 to +5.6) comparable to estimates of the upper mantle (δ⁷Li ~ +4 ± 2). The pyroxenite veins, which represent modal metasomatism and may therefore provide information about the metasomatic agent, have mantle-normalized trace element characteristics that suggest overprinting of their mantle source by an aqueous, slab-derived fluid. These include relative enrichments of Pb over Ce, U over Th and Sr over Nd. Li is enriched relative to the HREE, and ortho- and clinopyroxene from the veins are in Li elemental and isotopic equilibrium with each other and the surrounding harzburgite. Vein samples (δ⁷Li = +3.0 to +5.0) do not record a significant slab-derived δ⁷Li signature. These observations can be reconciled if slab Li diffusively re-equilibrates in the mantle wedge. Modeling demonstrates that Li equilibration of small (1–2 cm width) veins or melt conduits is achieved at mantle wedge temperatures within 10¹–10⁵ years. We conclude that strongly fractionated Li isotopic signatures cannot be sustained for long periods in the sub-arc mantle, at least at shallow (<70 km) depths. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Towards a Li barometer for bimineralic eclogites: experiments in CMAS

An eclogite barometer has profound importance in the study of upper mantle processes and potential application to diamond prospecting. Studies on the partitioning of Li between clinopyroxene (cpx) and garnet (grt) in natural samples have shown that this particular element is very sensitive to changes in pressure and could be calibrated as the barometer demanded for bimineralic eclogites. Experiments were performed from 4 to 13 GPa and 1,100–1,400°C in the CMAS (CaO, MgO, Al₂O₃, SiO₂) system with Li added as Li₃PO₄ to quantify this pressure dependence into a barometer expressed in the following equation: P = (0.00255T – ln K _d)/0.2351 where P is in GPa, T is in °C and K _d is defined as the partition coefficient of Li (in ppm) between clinopyroxene and garnet. The experimental pressures are reproduced to ±0.38 GPa (1σ) by this equation. This barometer is strictly applicable only to CMAS. Experiments at 1,300°C, 8–12 GPa showed that Henry’s Law is fulfilled for Li partitioning between cpx and grt in the concentration range of approximately 0.01–1 wt% Li. Direct application of the equation to experiments in natural systems performed at 1,300°C from 4 to 13 GPa consistently overestimates pressures by approximately 2 GPa. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Lithium isotopic disequilibrium of minerals in the spinel lherzolite xenoliths from Boeun,Korea

Spinel lherzolite xenoliths found in Boeun, Korea, have protogranular to porphyroclastic textures and are enclosed in a Miocene alkali basalt. The lithium concentration and isotopic compositions of olivine, clinopyroxene, and orthopyroxene separates from the spinel lherzolite, and whole rocks of the spinel lherzolites and alkali basalt were determined by inductively coupled plasma mass spectrometry (ICP-MS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The lithium concentrations of the olivines and orthopyroxenes range from 2.2 to 5.0 ppm and from 2.1 to 6.4 ppm, respectively. In contrast, the clinopyroxenes have larger lithium concentrations, from 2.0 to 8.4 ppm, which reflect their preferential lithium enrichment. The lithium isotopic compositions (δ⁷Li) of olivines (-5.4 to + 3.5‰), orthopyroxenes (-11.4 to -0.1‰), and clinopyroxenes (-14.4 to -4.7‰) range far beyond the average mantle composition of + 4 ± 2‰. The lithium isotopic composition of the host rock, alkali basalt (3.4‰), is within the range of the intraplate and oceanic island basalts. The spinel lherzolites from Boeun exhibits strong elemental and isotopic disequilibria due to the different lithium and lithium isotope diffusion velocities in the olivine, orthopyroxene, and clinopyroxene minerals after eruption and magma cooling.     

http://www.sciencedirect.com/science/article/pii/S1674987110000149

The structural stability of manganese titanate MnTiO3 at high pressure was investigated by X-ray diffraction and Raman spectroscopy with diamond anvil cells. Ilmenite-type MnTiO3 is stable at least to 26.6 GPa, and lithium niobate type MnTiO3 reversibly transforms at room temperature to perovskite at 2.0 GPa. Bulk moduli (K300) of ilmenite, lithium niobate and perovskite are 174(4) GPa, 179(8) GPa, and 208(5) GPa, respectively (at fixed first pressure derivative K′ = 4). The Grüneisen parameter γ has been estimated to be 1.28 for ilmenite and 1.75 for perovskite. In ilmenite phase, TiO6 octahedra become more regular with increasing pressure. In perovskite phase structural distortion increases with pressure increase.