邻菲啰啉在测定亚铁中的保护效果

样品在分解过程中 ,亚铁易被空气部分氧化 ,致使测试结果偏低 ,采用在HF H2 SO4溶矿过程中加入邻菲卟罗啉 ,与亚铁形成络合物 ,对保护亚铁具有较好的效果。拟定了在塑料坩埚中加邻菲卟罗啉、H2 SO4及HF ,中高温电热板溶矿 ,容量法测定样品中的亚铁 ,方法精密度为 0 .2 3% ,样品加标准回收率 98.8%～ 10 1.9%。此方法具有较好的应用效果     

Ab initio infra-red spectra of iron-polycyclic aromatic hydrocarbon compounds: a model case

C₁₀H₆-Fe⁺ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C₁₀H₆-Fe⁺ systems are models for larger PAHs-Fe⁺ complexes, which are believed to play a key rôle in space chemistry.     

能量色散X射线荧光光谱法测定钼矿石中钼铅铁铜

建立了能量色散X射线荧光光谱法测定钼矿石中钼、铅、铁、铜的方法,讨论了粒度效应、矿物效应的影响因素,确定了采取粉末样品,用系列标准样品建立工作曲线,通过元素间相互校正消除基体效应,用内控标准样品考察了方法的精密度(RSD,n=11)为0.44%～15.4%。实际样品的测定结果和化学法相符,可满足日常分析工作需要。     

青海南部熔积岩的发现:对寻找VMS型矿床的重要启示

熔积岩指的是侵入、混合到未固结或弱固结的湿沉积物中的熔浆分解、原位形成的一类特殊岩石。正确地认识该类岩石,有利于增进人们对岩浆-水(沉积物)相互作用过程的理解,恢复古环境。在青海南部沱沱河地区发现了一套角砾为撕片状、锯齿状及浑圆状的安山岩,胶结物为铁硅质组合的特殊熔积岩。研究表明,该熔积岩的角砾为岩浆遇水后快速淬火、裂解的产物,铁硅质组合为海底喷气沉积形成的含铁建造;且安山岩与含铁建造发生混合时,含铁建造尚未固结。该套熔积岩的发现,改变了长期以来对开心岭铁矿为火山热液交代安山岩而形成的认识,对于在矿区寻找VMS型矿床、区域内寻找海底热水喷流沉积型矿床具有重要的启示意义。     

新疆阿尔泰蒙库铁矿床的成矿流体及成矿作用

蒙库大型铁矿床赋存于上志留统—下泥盆统康布铁堡组变质火山-沉积岩系中,容矿岩石为石榴子石矽卡岩、变粒岩、浅粒岩和大理岩。矿体总体顺层分布,空间上与矽卡岩密切相关。研究表明,矽卡岩期石榴子石以发育玻璃质熔融包裹体、流体熔融包裹体和流体包裹体为特征,晚期矽卡岩阶段矿物中发育液相包裹体,变质期矿物中主要发育液相包裹体和含子矿物包裹体。矽卡岩期熔融包裹体的均一温度为1100℃,早期矽卡岩阶段流体包裹体均一温度变化于193～499℃,在450℃、350℃和230℃出现峰值。中期矽卡岩阶段均一温度变化于236～550℃,峰值为350℃。区域变质期均一温度介于132～513℃,在350℃、230℃和190℃出现峰值。流体包裹体的盐度w(NaCleq)介于1.23%～60.31%,流体密度变化于0.60～1.16g/cm3。石榴子石、石英和方解石的δ18OSMOW变化于0.2‰～8.4‰,δ18OH2O介于-5.1‰～5.33‰,δD为-127‰～-81‰,表明矽卡岩期成矿流体主要是岩浆水,混合少量大气降水;变质期流体主要为大气降水,为混合变质水。方解石δ13CPDB变化于-6.1‰～-2.3‰,表明流体中碳来自深部或地幔。成矿时代为早泥盆世早期(略晚于404～400Ma),成矿作用与矽卡岩的退化变质作用有关。     

山东省济宁强磁异常区深部铁矿初步验证及其意义

山东省济宁磁异常是一个重、磁同源体,面积大于100 km2,磁异常峰值为3800nT。钻探验证在孔深1041.57～1796.54m位置发现铁矿体,矿体总厚度74.04～220m,磁性铁平均品位15.89～25.19%。矿石类型有条带状方解磁铁石英岩和条带状磁铁石英大理岩,矿石的主要组成矿物为石英、方解石、磁铁矿、磁赤铁矿、菱铁矿。矿体产于济宁岩群浅变质岩系中,矿床特征与条带状铁建造（BIF）铁矿或鞍山式铁矿有明显区别,铁矿成因类型属与千枚岩、变质中酸性火山岩、大理岩有关的沉积变质型铁矿床。该区铁矿资源潜力巨大。     

合浦珠母贝铁的穆斯堡尔谱学研究

应用^57Fe穆斯堡尔谱学的方法研究了四个不同生长期合浦珠母贝铁的化学状态和Fe^2 /Fe^3 的值，它们的Fe^2 和Fe^3 的相对含量分别为4.1%～29.4%和76.6%～95.9%,Fe^2 /Fe^3 值的变化为0.043～0.42。3个月龄的Fe^2 /Fe^3 值大于10个月龄，从10个月龄到22个月龄的Fe^2 /Fe^3 值呈增加的趋势，这可能反映了不同生长期合浦珠母贝对不同价态的铁的需求。     

Community Structure and Dynamics of Phytoplankton in the Western Subarctic Pacific Ocean: A Synthesis

The phytoplankton community in the western subarctic Pacific (WSP) is composed mostly of pico- and nanophytoplankton. Chlorophyll a (Chl a) in the <2 μm size fraction accounted for more than half of the total Chl a in all seasons, with higher contributions of up to 75% of the total Chl a in summer and fall. The exception is the western boundary along the Kamchatka Peninsula and Kuril Islands and the Oyashio region where diatoms make up the majority of total Chl a during the spring bloom. Among the picophytoplankton, picoeukaryotes and Synechococcus are approximately equally abundant, but the former is more important in term of carbon biomass. Despite the lack of a clear seasonal variation in Chl a concentration, primary productivity showed a large seasonal variation, and was lowest in winter and highest in spring. Seasonal succession in the phytoplankton community is also evident with the abundance of diatoms peaking in May, followed by picoeukaryotes and Synechococcus in summer. The growth of phytoplankton (especially >10 μm cell size) in the western subarctic Pacific is often limited by iron bioavailability, and microzooplankton grazing keeps the standing stock of pico- and nano-phytoplankton low. Compared to the other HNLC regions (the eastern equatorial Pacific, the Southern Ocean, and the eastern subarctic Pacific), iron limitation in the Western Subarctic Gyre (WSG) may be less severe probably due to higher iron concentrations. The Oyashio region has similar physical condition, macronutrient supply and phytoplankton species compositions to the WSG, but much higher phytoplankton biomass and primary productivity. The difference between the Oyashio region and the WSG is also believed to be the results of difference in iron bioavailability in both regions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Rare Earth Deposits of North America

Rare earth elements (REE) have been mined in North America since 1885, when placer monazite was produced in the southeast USA. Since the 1960s, however, most North American REE have come from a carbonatite deposit at Mountain Pass, California, and most of the world’s REE came from this source between 1965 and 1995. After 1998, Mountain Pass REE sales declined substantially due to competition from China and to environmental constraints. REE are presently not mined at Mountain Pass, and shipments were made from stockpiles in recent years. Chevron Mining, however, restarted extraction of selected REE at Mountain Pass in 2007. In 1987, Mountain Pass reserves were calculated at 29 Mt of ore with 8.9% rare earth oxide based on a 5% cut‐off grade. Current reserves are in excess of 20 Mt at similar grade. The ore mineral is bastnasite, and the ore has high light REE/heavy REE (LREE/HREE). The carbonatite is a moderately dipping, tabular 1.4‐Ga intrusive body associated with ultrapotassic alkaline plutons of similar age. The chemistry and ultrapotassic alkaline association of the Mountain Pass deposit suggest a different source than that of most other carbonatites. Elsewhere in the western USA, carbonatites have been proposed as possible REE sources. Large but low‐grade LREE resources are in carbonatite in Colorado and Wyoming. Carbonatite complexes in Canada contain only minor REE resources. Other types of hard‐rock REE deposits in the USA include small iron‐REE deposits in Missouri and New York, and vein deposits in Idaho. Phosphorite and fluorite deposits in the USA also contain minor REE resources. The most recently discovered REE deposit in North America is the Hoidas Lake vein deposit, Saskatchewan, a small but incompletely evaluated resource. Neogene North American placer monazite resources, both marine and continental, are small or in environmentally sensitive areas, and thus unlikely to be mined. Paleoplacer deposits also contain minor resources. Possible future uranium mining of Precambrian conglomerates in the Elliott Lake–Blind River district, Canada, could yield by‐product HREE and Y. REE deposits occur in peralkaline syenitic and granitic rocks in several places in North America. These deposits are typically enriched in HREE, Y, and Zr. Some also have associated Be, Nb, and Ta. The largest such deposits are at Thor Lake and Strange Lake in Canada. A eudialyte syenite deposit at Pajarito Mountain in New Mexico is also probably large, but of lower grade. Similar deposits occur at Kipawa Lake and Lackner Lake in Canada. Future uses of some REE commodities are expected to increase, and growth is likely for REE in new technologies. World reserves, however, are probably sufficient to meet international demand for most REE commodities well into the 21st century. Recent experience shows that Chinese producers are capable of large amounts of REE production, keeping prices low. Most refined REE prices are now at approximately 50% of the 1980s price levels, but there has been recent upward price movement for some REE compounds following Chinese restriction of exports. Because of its grade, size, and relatively simple metallurgy, the Mountain Pass deposit remains North America’s best source of LREE. The future of REE production at Mountain Pass is mostly dependent on REE price levels and on domestic REE marketing potential. The development of new REE deposits in North America is unlikely in the near future. Undeveloped deposits with the most potential are probably large, low‐grade deposits in peralkaline igneous rocks. Competition with established Chinese HREE and Y sources and a developing Australian deposit will be a factor.     

On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.