内蒙古敖包吐萤石矿床地质和地球化学特征

笔者总结了敖包吐萤石矿床的地质特征,并通过萤石的稀土元素的地球化学和Nd同位素研究,探讨了该矿床的成矿作用和成矿物质来源。敖包吐萤石矿床产出于下二叠统大石寨组火山—沉积岩与燕山中期花岗岩的接触带,为单一萤石矿床。萤石矿石的稀土元素的含量(∑REE)变化范围为(8.04～30.04)×10-6,平均为19.42×10-6;轻重稀土LREE/HREE值0.24～0.65,平均0.52;LaN/YbN为0.07～0.62,平均0.26;δEu为0.42～0.90,平均0.60,具Eu负异常和明显重稀土富集的特征。岩矿石的Nd同位素研究表明,萤石矿石的εNd(t)都表现为很大的负值,以成矿主期年龄138Ma计算的εNd(138Ma)为-7.30～-30.55,具有古陆壳的演化特征,暗示其成矿的物质来源主要是壳源物质。在Moller的Tb/La-Tb/Ca成因判别图解中,敖包吐矿床的萤石的结晶作用表现为重新活化的趋势,反映流体具有混源的特征,既有热液成因,又有沉积成因。二叠世的海相火山活动通过海底喷气和喷流的作用形成了初始矿源层,而燕山中期花岗岩浆的侵位与结晶分异,又对初始矿源层的活化和富集提供了流体和热能的来源。成矿流体在经历了长期的演化后在大石寨组的构造薄弱破碎的的部位沉淀析出,形成敖包吐萤石矿床。     

湘南新田岭白钨矿床He,Ar同位素特征及Rb-Sr测年

新田岭白钨矿床是湘南W-Sn多金属矿集区中的一个大型矽卡岩型矿床,产于骑田岭岩体北接触带.本文对矽卡岩矿石中1件黄铁矿样品进行了流体包裹体He、Ar同位素测定,获得3He/4He值为4.08 Ra,40Ar/36Ar为342,反映了在矽卡岩矿床的成矿流体中亦有地幔流体的显著参与;运用石英Rb-Sr法获得成矿等时线年龄为(157.4±3.2)Ma(2σ)(MSWD=1.6),87Sr/86Sr初始值为0.71044±0.00012,该年龄值与柿竹园超大型钨多金属矿床及芙蓉大型锡矿等的成矿年龄在测试误差范围内基本一致,表明中侏罗世是湘南地区钨锡成矿的高峰期.     

黑河下游河岸林植物水分来源初步研究

通过分析黑河下游极端干旱区荒漠河岸林植物木质部水及其不同潜在水源稳定氧同位素组成(δ18O),应用"同位素质量守恒多元"分析方法初步研究了不同潜在水源对河岸林植物的贡献.结果表明:在黑河下游荒漠河岸林生态系统,在河水转化为地下水和土壤水及水分在土壤剖面再分配的过程中均存在强烈的同位素分馏.对植物水δ18O而言,胡杨、柽柳和苦豆子的δ18O分别为-6.43‰、-6.28‰～和-6.61‰,较苦苣菜(-5.14‰)和蒲公英(-5·52‰)明显偏负.柱状频率图显示胡杨最多能利用93%的地下水,柽柳最多利用90%的地下水.而苦豆子97%水分来源于80 cm土层范围内的土壤水.除0～20 cm土层内的土壤水外,苦苣菜和蒲公英可能还有其他潜在水源.即在黑河下游天然河岸林乔木和灌木较多地利用地下水,而草本植物仍然以地表水为主.     

天然水铬污染与其同位素组成的相关性研究

Cr(Ⅵ)作为水体中重要的污染物质,其同位素组成对水体环境变化具有较强的敏感性.铬在氧化还原过程中产生明显的同位素分馏作用,根据水体中铬的同位素组成可指示水环境中Cr(Ⅵ)的还原程度.笔者以黄石某无机盐厂周围污染水体为例,对天然水体中的铬污染及其同位素组成的相关性进行了分析研究.     

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.     

酸性矿山废水中生物成因次生高铁矿物的形成及环境工程意义

酸性矿山废水(acid mine drainage,AMD)是一类pH低并含有大量有毒金属元素的废水。AMD及受其影响的环境中次生高铁矿物类型主要包括羟基硫酸高铁矿物(如黄铁矾和施威特曼石等)和一些含水氧化铁矿物(如针铁矿和水铁矿等),而且这些矿物在不同条件下会发生相转变,如施氏矿物向针铁矿或黄铁矾矿物相转化。基于酸性环境中生物成因次生矿物的形成会"自然钝化"或"清除"废水中铁和有毒金属这一现象所获得的启示,提出利用这些矿物作为环境吸附材料去除地下水中砷,不但吸附量大(如施氏矿物对As的吸附可高达120mg/g),而且可直接吸附As(III),还几乎不受地下水中其他元素影响。利用AMD环境中羟基硫酸高铁矿物形成的原理,可将其应用于AMD石灰中和主动处理系统中,构成"强化微生物氧化诱导成矿-石灰中和"的联合主动处理系统,以提高AMD处理效果和降低石灰用量。利用微生物强化氧化与次生矿物晶体不断生长的原理构筑生物渗透性反应墙(PRB)并和石灰石渗透沟渠耦联,形成新型的AMD联合被动处理系统,这将有助于大幅度增加处理系统的寿命和处理效率。此外,文中还探讨了上述生物成因矿物形成在AMD和地下水处理方面应用的优点以及今后需要继续研究的问题。     

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.     

Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.