我国铬铁矿未来供需态势与调控政策分析

通过对我国铬铁矿资源的未来供需态势分析,得知它不仅现在远远满足不了消费的要求,而且随着需求的扩张,它的未来供需矛盾将不断加深,对外依存度会不断升级,为此开辟国外铬铁矿资源的供应已是形势所迫.为了保障它的供应安全而促进我国不锈钢等相关产业的健康发展,文章就促进铬铁矿资源可持续安全供应的调控政策的几个问题作了简要分析.     

Speciation Study of Cr in a Geochemical Reference Material Sediment Series Using Sequential Extraction and XANES Spectroscopy

Speciation of Cr in geochemical reference materials was characterised by sequential extraction and X‐ray absorption near‐edge structure (XANES) spectroscopy to identify Cr(III) resulting from the reduction of pollutant Cr(VI). Sequential extraction suggested that the amount of Cr associated with an acetic acid soluble fraction was low; Cr associated with a reducible phase and an oxidisable phase was extracted at 5–10% of the total Cr concentration, and the residual phase was found to be the dominant Cr‐containing fraction. Cr speciation in soil artificially doped with Cr(VI) and sediment samples collected from highly populated and industrialised areas was different from that in naturally occurring materials. Substantial Cr was extracted as a reducible phase (15–30%) and an oxidisable phase (30–60%) for these samples. Through subsequent XANES spectroscopy analysis, the reducible phase was explained by Cr bound to Fe hydroxide, while the oxidisable phase was a mixture of Cr bound to humic substances and Cr hydroxides. That is, Cr(VI) present as a contaminant in sediments and soils was reduced to Cr(III), which then bound to Fe hydroxide and humic substances, precipitating as a hydroxide. Thus, a combination of sequential extraction and XANES spectroscopy allows for effective identification and quantification of the chemical forms of Cr in sediments and soils.     

稳定同位素53Cr在地下水污染研究中的应用

铬是地表水和地下水中的常见污染物，它被广泛应用于电镀、制革和防腐。在氧化条件下，Cr以Cr(Ⅵ)的阴离子铬酸盐（CrO2-4）和重铬酸盐（HCrO-4）形式存在，有很高的溶解性和流动性。Cr(Ⅵ)是一种可疑的致癌物。在还原条件下，Cr的分馏。所有地下水Cr(Ⅲ),它不溶解，并且强烈地吸附在固体表面上，而且毒性很小。Cr(Ⅵ)的还原作用可导致Cr稳定同位素轻同位素。因此，稳定铬同位素比值可以用作地下水中Cr(Ⅵ)还原程度的指示剂。笔者使用方程（1）确定了两个地下水样（MW-6和MW-12）的还原程度，它们分别为31%和68%。     

天然黄铁矿除Cr（Ⅵ）中Cr2S3物相的发现

利用天然黄铁矿处理含Cr(Ⅵ)废水实验,在反应中与反应后黄铁矿表面和胶体沉淀物中明显出现Cr2p的XPS能谱峰,能拟合出574.7～575.1eV、576.6～576.9eV和578.2～578.7eV3个峰位,分别代表Cr2S3、Cr2O3和CrO3物相。在实验过程中新发现Cr2S3沉淀物相,表明在常温常压下的水溶液介质中也能产生铬的硫化物物相。充分利用这些含铬物相,能使天然黄铁矿包括天然磁黄铁矿在还原Cr(Ⅵ)的同时,无需加碱就可将Cr(Ⅲ)沉淀转移到胶体沉淀物中,处理后的上清液中全Cr含量低于1.5mg/L的国家允许排放标准。天然黄铁矿自身溶解出的重金属含量很低,不影响处理后的出水水质。开发利用Cr2S3等含铬沉淀物相,便于推广应用天然黄铁矿和磁黄铁矿还原Cr(Ⅵ)同时沉淀Cr(Ⅲ)的一步法除铬新工艺。     

油田污水中Fe2+,S2-,DO及pH值对无机交联体系HPAM-Cr3+CDG成胶性能影响的研究

在对河南油田下二门矿区油田污水进行全面分析的基础上，研究了污水中Fe^2 ，S^2-，溶解氧（DO）及污水的pH值对无机交联体系聚丙烯酰胺（HPAM）－Cr^3 胶成分散凝胶（CDG）成胶性能的影响。研究结果表明，对于HPAM－Cr^3 体系，污水中Fe^2 ，DO对其成胶性能没有影响；S^2-和污水的pH值对其成胶性能有影响。pH值增大，凝胶强度增强；S^2-浓度增加，则凝胶强度减弱。     

热致死小球藻生物富集Cr3+的研究

研究了热致死小球藻对微量Cr^3 的生物吸附富集和机理。结果表明，培养72h左右的热致死小球藻吸附富集Cr^3 的能力最强；当pH为4．5—5．0，藻浓度为1—2g／L时，死体藻对Cr^3 有较好的生物吸附作用；随着Cr^3 浓度增加，单位质量藻的Cr^3 吸附量呈上升趋势，但其Cr^3 吸附率却急剧下降。热致死小球藻对Cr^3 的吸附可以用Freundlich模型描述，拟合方程为：q＝5．3369C11/2.6295，R^2＝0．9974；在生物吸附的起始阶段，藻体对Cr^3 的吸附较快，40min左右时藻体达到最大吸附量。     

雅鲁藏布江缝合带东段杰莎蛇绿岩中铬铁矿特征及其构造背景

雅鲁藏布江缝合带东段加查县杰莎岩体主要由蚀变较强的方辉橄榄岩和纯橄岩、豆荚状铬铁矿组成。铬铁矿矿体呈东西向,倾向北西,矿体的围岩为纯橄岩及方辉橄榄岩,长20~40m,宽1~3m。镜下特征和电子探针分析结果显示铬铁矿中铬尖晶石的Cr#=67.9~88.5,Mg#值变化在64.6~68.2之间,TiO2含量为0.06%~0.18%,Al2O3含量为13.1%~16.5%,表明杰莎铬铁矿为高铬型铬铁矿。方辉橄榄岩中橄榄石、斜方辉石和单斜辉石的矿物化学特征表明杰莎岩体既具有深海地幔橄榄岩特征,也具有岛弧地幔橄榄岩的特点。并且依据铬尖晶石-橄榄石/单斜辉石的矿物化学成分,识别出杰莎岩体至少经历了2期过程,包括早期部分熔融(20%~30%)和晚期的岩石/熔体反应作用(35%)。因此,杰莎地幔橄榄岩和铬铁矿可能与雅鲁藏布江缝合带中其他岩体一样,经历了洋中脊及俯冲带的多阶段叠加的过程。     

Geochemical Baselines of Nickel and Chromium in Various Surficial Materials in the Barents Region, NW Russia and Finland

The geochemical baselines of nickel and chromium were studied from the data produced by the Barents Ecogeochemistry project, a large international regional geochemical mapping exercise. The project surveyed major and trace element distributions in stream water, organic and mineralogically-modified soil horizons, and terrestrial moss in the northwestern part of Russia and in Finland. Other materials were collected during the pilot phase and later from thirty special sites. The results on respective materials by XRF, ICP-MS and ICP-AES showed that both geological and anthropogenic factors have an influence on the geochemical baseline concentrations of Ni and Cr in organic soil and stream water. The main explanation of the observed distribution patterns in terrestrial moss is human activity, but geological factors can also affect the baselines. The variation of geochemical baselines in the mineral-rich soil horizon depends only on variations in bedrock. The mineralogy of samples mainly controls the leachability properties of soil samples.     

Polarographische Bestimmung von Nickel und Chrom in Klärschlämmen Polarographic Determination of Nickel and Chromium in Sewage Sludge

The contents of Ni and Cr in sewage sludge with high and low amounts of heavy metals were investigated by polarography. The DIN-digestion (aqua regia) was used, and the resulting solution was treated with H₂O₂/UV (90 °C, 60 min) for further destroying of the organic material. Besides, the solution of the DIN-digestion was examined with AAS (flame) and ICP-OES. With the determination of Ni it was shown that after digestion with aqua regia no further treatment with H₂O₂/UV is necessary. Contrariwise it was found that for the determination of Cr a H₂O₂/UV photolysis is necessary followed by further steps to get good agreement with AAS and ICP results as well as with the certified values of a sludge of the Community Bureau of Standards.     

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.