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。     

Towards a nonperturbation transport theory in hetereogeneous aquifers

A large body of existing theories of flow and contaminant transport in aquifers ignore the presence of recharge, eliminate the boundary conditions, neglect transient conditions in groundwater flow, conceive hydraulic gradients as linear, and require parameter variability to be stationary and Gaussian. The most outstanding and difficult to justify assumption is the subjective small size of the stochastic terms (i.e., small perturbation methods), which usually is forced by considering the logarithm of the hydraulic conductivity. Several problems in flow and contaminant subsurface hydrology, such as the enhanced dispersion parameters with plume size or time after injection, remain to be observed in the light of a stochastic theory that allows a more realistic consideration of physical and hydrologic properties. In this article, an attempt is made to reformulate a contaminant transport equation (the variable dispersion equation, VDE) with transport parameters in terms of regional hydrologic and aquifer hydraulic properties, such as recharge rate, spatially random transmissivity, hydraulic gradient, aquifer thickness, and soil porosity. Subsequently, a general analytic procedure, the method of decomposition, is used to derive a solution to the VDE. This procedure does not require small perturbation, logarithmic transformations, or specific probability law assumptions. Comparison tests with existing theoretical and field results are given. The tests illustrate the enhanced dispersion and shifting concentration effects produced by the variable dispersion equation. Finally a generalization of the method to nonstationary dispersion in three-dimensional domains is proposed.     

Laboratory simulation of geogas microbubble flow

Preliminary laboratory tests provided first data on the behavior of gas microbubbles through porous media in the framework of the geogas theory. Under experimented conditions with laboratory equipment arranged for pressure controlled gas-tracer injection and sampling, gas microbubbles moved up to ten times faster than singlephase flow in dry media under the same injection pressure. Microbubbles were determined to be very sensitive to changes in injection pressure and their terminal velocity seems to be described with good approximation by the Stokes formula. The capability of microbubbles to pick up and transport upward for short distances solid ultra-small particles (metallic and radionuclide compounds) has been proved. Results are consistent with a time-dependent process linked to the transport properties of microbubbles (e.g., flotation), such as that reported by some authors.     

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.     

冀西北长城纪宣龙式铁矿层中微体植物化石的发现及其意义

本文研究的是笔者等在冀西北长城系串岭沟组宣龙式铁矿层中发现的微体植物化石,这些化石都保存在铁质叠层石(肾状赤铁矿)和铁质核形石(鲕状赤铁矿)的基本层中。微化石以丝状体为主,部分为球状体。归属于原核生物蓝藻门颤藻科的两个属和色球藻科的一个属。化石层同位素年龄约在1800—1757Ma。这些化石与北美冈弗林特组微化石比较,既有些相似,又有些区别。该化石的发现为研究铁矿的成因,指示沉积环境及层位对比都很有意义。     

Visualization experiments of iron precipitates: Application for in-situ arsenic remediation

Laboratory experiments were carried out to acquire more insight and understanding of the phenomena associated with the in-situ arsenic remediation. Visualization techniques are the most informative for the detection of Fe(II) while flowing in soils. Green Rust (GR) was considered as representative of in-situ iron precipitates. In a visualization flat cell, the change in color of GR to orange, due to oxidation, was monitored by a digital camera and the images were analyzed giving the spatial and temporal distribution of Fe(II). Moreover, both oxygen and pH changes in time were recorded in two sections along the flow direction in the cell. The measured and calculated concentration profiles were compared and the actual reaction rates were predicted. The reaction rate constants measured in this study, under flowing conditions, are in a good agreement with the values obtained from batch experiments reported in the literature.     

Semi-analytical solutions of a contaminant transport equation with nonlinear sorption in 1D

A new method to determine semi-analytical solutions of one-dimensional contaminant transport problem with nonlinear sorption is described. This method is based on operator splitting approach where the convective transport is solved exactly and the diffusive transport by finite volume method. The exact solutions for all sorption isotherms of Freundlich and Langmuir type are presented for the case of piecewise constant initial profile and zero diffusion. Very precise numerical results for transport with small diffusion can be obtained even for larger time steps (e.g., when the Courant-Friedrichs-Lewy (CFL) condition failed).     

Speciation of adsorbed arsenate on the surface of hydrous iron oxide

Adsorption of arsenate on hydrous iron oxide is an important process controlling geochemical cycling of arsenic in environment as well as the fate of arsenic-bearing mining wastes. The widely accepted view on the mechanism of adsorption is that arsenate is adsorbed via bidentate binuclear inner-sphere complexation. In this study, we characterized the arsenate-hydrous iron oxide sorption solids synthesized at pH=3-8 using Fourier transformed infrared spectroscopy （FTIR） and X-ray diffraction （XRD）. It has been determined that poorly crystalline ferric arsenate developed on the surface of iron oxide when arsenate was sorbed at acidic pH, while at alkaline pH the adsorption of arsenate was via bidentate complexation.