花岗岩风化壳稀土存在形态分析方法研究

研究了一个测定花岗岩风化壳中REE存在形态的方法。以0.2 mol/L MgCl_2,2.5 mol/LHCl,0.5 mol/L NaOH及含15%H_2O_2的2.5 mol/L HCl连续提取风化壳试样中的稀土。经X射线衍射、红外光谱及剖面试样测试,论证了每一提取态的内涵,提出了花岗岩风化壳中非原生矿物相稀土存在活性态、铁铝共沉淀态和有机结合态的新认识。     

乌江流域沉积岩风化过程中稀土元素的富集与释放

以乌江流域石灰岩、白云质灰岩、白云岩、硅质岩、页岩和砂岩等沉积岩的13条风化剖面为对象，运用R型分层聚类分析和质量平衡计算方法，研究了这些岩石风化过程中稀土元素（REE）的富集与释放及其对植物生长和河水REE分布的影响，目的是为河水物质来源研究和为农业生产提供依据。结果表明：（1）乌江流域石灰土中REE的富集程度显著高于各自母岩、黄壤、上陆壳（UCC）、中国土壤（CS）和世界土壤（WS）；（2）沉积岩风化过程中REE的富集特征和机制可能与母岩中REE分布特征以及风化剖面中有机质、铁（氢）氧化物和粘土矿物的吸附有关；（3）沉积岩风化过程中释放的REE可为植物吸收利用；（4）石灰岩等沉积岩风化过程中REE和F。等元素的释放对河水溶解态REE的分布有重要影响。     

江西武山块状硫化物矿石表生风化过程中稀土元素地球化学行为

The behavior of REE during the sulphide weathering is still poorly understood, although REE geochemistry during weathering of igneous rocks has been well documented, in this study, the REE contents of primary sulphide and their weathering products （gossan） of the Wushan copper mine were investigated. The mobility of REE in the weathering profile of sulphide is limited, with the majority of REE retained in the gossans. However, REE are fractionated in the weathering process, with HREE relatively enriched in the gossan samples. Ce is depleted in the gossan, whereas the difference of Eu anomaly of the gossan and primitive sulphide is neglectable.     

湘西地层中的砷锑汞及其赋存特征

湘西是金，砷，锑，汞等有色金属的重要成矿带。区域地层微量元素地球化学研究表明，湘西所出露的地层均显著富集砷，是砷的高区域地球化学异常区，元素存在相态实验进一步表明，新元古界至寒武系中的砷以易迁移形式为主，新元古界至寒武系可能构成砷矿矿源层。其风化所成土壤中砷的含量也一定较高。     

黔西南卡林型金矿床稀土元素地球化学特征

分析了黔西南地区板其、、丫他及戈塘等卡林型金矿床的(La/Yb)N、(La/Sm)N、∑REE及LREE/HREE等稀土元素的含量及参数特征.结果表明,该区金矿床相对富集LREE;该区戈塘金矿具有明显的MREE富集及正Eu异常的特点,表明成矿热液应该是一种还原性流体,来源于深部或至少经历过对富含斜长石源区的水-岩反应矿...     

风化壳淋积型稀土矿评述

对我国特有的风化淋积型稀土矿的科学研究和工业利用进行了评述,阐述了该矿成矿过程,探讨了稀土元素在风化体系中的迁移富集规律,证实稀土配分的铈亏效应、富铕效应、分馏效应和钆断效应,论述了风化壳淋积型稀土矿浸取水动力学、浸取动力学及浸取传质过程。提出了该矿稀土回收中存在的一些问题,建议进一步完善稀土元素地球化学和无机化学的科学体系,开发新浸取剂,特别是组合浸取剂的协同使用,深入研究原地浸出过程中的扩散和传质机理,强化浸取过程和建立相应的数学模型,有效地提高稀土浸出率,从而完善风化壳淋积型稀土矿的原地浸出理论和技术。     

Utilization of instrumental neutron activation analysis (INAA) for geochemical behaviour study of major and trace elements in Bouregreg river basin (Morocco)

The Bouregreg river basin is located in the Moroccan Central Massif which consists mainly of Palaeozoic formations that were subject to the Hercynian orogeny. This study documents the background geochemistry and hydrochemistry of the Bouregreg river basin, focusing on the distribution of major and trace elements. Rock samples were collected at nine locations along the Bouregreg River and its tributaries in the winter of 2005. Major (Al, Fe, Mn, Na, K and Ti) and trace (Rb, Cs, Sr, Sc, Ba, Cr, V, Co, Ni, Zn, As, Sb, La, Ce, Nd, Sm, Tb, Dy, Yb, Lu, Hf, Ta, Mo, Th and U) elements were analysed using instrumental neutron activation analysis. Data show that most of the geochemistry and hydrochemistry are related to regional and local geology. The geochemical heritage of geological environment in the Bouregreg river basin is very important, that results from the more compatible behaviour and the inertia of some elements during the weathering (3d transition elements (Co, Ni, Cr,…), interne transition elements f (lanthanides, Zr, Hf, Nb, Ta,…)). The geochemical homogeneity of the basin shows also heritage during the crustal accretion (magmatism-metamorphism-sedimentation) and the typology of this continental area is the same that the upper continental crust. Some anomalously high heavy metal analyses, particularly for As and Sb, may be related to anthropogenic activities.     

Geochemical behaviour of major and trace elements in dissolved and particulate phases of the Bouregreg river (Morocco)

The Bouregreg river is one of the main rivers of Morocco, Its source being located in the Moroccan Central Massif and flows towards the Atlantic coast through the coastal Meseta. The Bouregreg river basin is located in the Moroccan Central Massif which consists mainly of Palaeozoic formations that were subject to the Hercynian orogeny. To evaluate the environmental status of the Bouregreg river water, sampling of the dissolved (<0.22 μm) and suspended (>0.22 μm) phases was performed at 10 sites along the Bouregreg river and its tributaries in the winter of 2005. Major (Na, Ca, K, Ti, Mn, Al and Fe), trace (As, Ba, Bi, Cd, Co, Cr, Cs, Cu, Hf, Li, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sn, Sr, Ta, Th, U, V, W, Y, Zn and Zr) elements and rare earth elements were analysed. The dissolved and particulate phase of the Bouregreg river draining these contrasting zones show similar characteristics to those observed in other major tropical rivers such as the Congo and Amazon, and vary in composition between the different source areas. Obtained data show that the spectra of the standardized concentrations for all the determined elements in the dissolved and the suspended phase have the same form whatever the station and that the whole of the elements is strongly deficient compared to the upper continental crust. The strong depletion in the suspended phase and the associated enrichment in the dissolved phase suggest that some elements such as Rb, Ba and Sr are the most mobile elements during the weathering processes. The removal of the most mobile elements from the bedrock concentrates all remaining elements in the weathered phases of the soils, from whence it can be removed mechanically. As and Sb are strongly enriched as well in the dissolved load as in the suspended load.     

Activity concentration of226Ra and238U in various soils

The distribution of²²⁶Ra and²³⁸U in various soils has been studied. Supposing that radioactive equilibrium were in existence, the average activities of²²⁶Ra and²³⁸U would show a nearly 11 correlation. As weathering affects radioactive equilibrium in surface soil, radioactive equilibrium was not in existence. Therefore, four kinds of soil were selected from different weathering conditions, viz. river bed soil, paddy field soil, field soil and uncropped soil. The²²⁶Ra/²³⁸U ratio of various soils lies in the range of 1.63 to 2.41. The activity concentrations of²²⁶Ra were greater than²³⁸U in various soils. The ratio²²⁶Ra/²³⁸U can be shown to be a quantitative index of weathering. Phosphatic manure contains²³⁸U and its daughter isotopes in concentrations far exceeding the average abundance in the earth's crust. But the cultivated soils (paddy field soil, field soil) are not affected by fertilizers in Kamisaibara.     

碱熔-标准物质法-电感耦合等离子体发射光谱(ICP-AES)法测定硅酸盐岩中10种主量元素

硅酸盐岩元素的准确测定是其地球化学分析研究的基础,其主量元素含量通常可以采用电感耦合等离子体发射光谱(ICP-AES)法测定,但其测定方法的系统性研究相对缺乏,尤其是样品前处理和基体干扰的有效消除两方面。前处理过程中,考察不同熔剂用量对硅酸盐岩样品的分解能力,发现当熔剂与样品比例达到6:1后,熔珠为纯色透明,经稀硝酸提取后溶液澄清,确定了硅酸盐岩前处理时熔剂与样品的最佳配比。测定过程中,通过考察基体匹配法和标准物质法两种基体干扰消除方法对测定结果的影响,发现当采用与岩性一致或者接近的标准物质绘制校准工作曲线时,基体干扰消除效果更好,更适用于测定硅酸盐岩10种主量元素含量。据此,建立了硅酸盐岩经偏硼酸锂熔融,稀硝酸振荡提取处理,以标准物质法绘制校准工作曲线,采用ICP-AES法同时测定SiO2、Fe2O3、Al2O3、CaO、K2O、MgO、Na2O、TiO2、P2O5、MnO 10种成分含量的方法。对岩石标准物质GBW07107进行分析测定,方法的相对标准偏差(RSD)为0.17%～0.75%,方法检出限为0.001%~0.016%,满足硅酸盐岩样品元素定量分析的要求,而且操作简单快速,环境污染小,适用于大批量样品分析。     

激光剥蚀-电感耦合等离子体质谱研究富钴结壳生长环带的元素分布

建立了以Ti为内标,富钴结壳标准物质GSMC-1为外标,193nmArF准分子激光剥蚀ICP-MS方法研究富钴结壳不同结壳层中元素组成及分布。所建立的定量方法用于GSMC-2和GSMC-3的测定,分析结果的相对标准偏差和相对误差均小于10%;各分析元素的检出限为3.2～191ng/g(除Si外),可以满足富钴结壳原位微区分析的要求。对取自西太平洋麦哲伦海山区富钴结壳样品MDD-42,从核心到最外结壳层以0.5mm的微间距剥蚀并采集140个样品点,不同生长环带的微区分析结果表明,成矿元素和伴生元素在不同结壳层中呈现不同的分布特性,直接反映了结壳形成时期的地质作用和古海洋沉积环境。     

Scherzonen

Within so‐called shear zones, along which variably sized units of the earth crust are subject to a displacement, numerous chemical reactions result in the re‐structuring of the rock mineralogy. This metamorphic transformation is continuously intensified from the rim to the centre of the shear zone and is chiefly controlled by pressure, temperature, and the existence of a fluid phase. As documented with the help of a concrete example chemical mass balancing in a given shear zone requires both the chemical analysis of educt and product and the documentation of eventual changes of rock density and rock volume. The latter changes allow a final distinction between isochemical and anisochemical transformation processes.     

Measurements of Ir concentration in geological standard samples using neutron activation analysis with multiple gamma-ray coincidence method

In this study, the Ir concentrations in some standard rock samples were determined by using the multiple γ-ray detection method. The use of the multiple γ-ray detection method, which was developed for nuclide quantification, yielded better resolution and sensitivity than the ordinary singles γ-ray detection method. Iridium is one of the least abundant elements in Earth’s crust, with an average mass fraction of 0.001 ppm in a crust rock. However, iridium is relatively more abundant (concentration: 0.5 ppm or more) in undifferentiated meteorites. Therefore iridium abundance anomalies in geological samples provide important information about meteorite impact. The standard rock samples used in this study were SARM-76, FC-1 and FC-2. The SARM-76 was prepared from a platinum ore, and issued by the south African bureau of standards. FC-1 and FC-2 were obtained from fish clay sediment samples from Stevens Klint, Denmark.     

Natural and artificial weathering characteristics of stabilized acrylic–urethane paints

Depth-profiling by Fourier transform infrared (FTIR) spectroscopy, dynamic mechanical analysis (DMA), microhardness and scanning electron microscopy (SEM) observations have been used to monitor degradation chemistries in two-package acrylic–urethane coatings when exposed to different exposure conditions. Three artificial and three natural weathering protocols (QUV, ASTM D5894, ISO20340, Pipady (south of France), Bandol (south of France) and Kure Beach (USA)) were selected for this study. The same chemical events were found to occur under all conditions, particularly under natural and artificial exposures. Both loss of the amide II band at 1520 cm⁻¹ and carbonyl growth occurred but at relatively low rate owing to the presence of hindered-amine light stabilizers in the film. A less typical loss of urea biuret linkages also occurs during all exposures and results in a change in the balance between urethane and urea links across the depth of the film during weathering. The chemical degradation of the polymer matrix involves the formation of species that are readily ablated from the surface and results in loss of gloss, increase in hardness and a rougher topology. The dramatic loss of gloss observed after Pipady and Bandol exposures show that loss of gloss should not be systematically correlated to the advance in chemical degradation.     

A study of surface changes of wood-polypropylene composites as the result of exterior weathering

Outdoor applications of composites raised questions about their durability. In this study, the effects of outdoor weathering on the properties of wood-polypropylene composites with and without pigments were examined. The composites were placed outdoors for one year, and their colour changes were evaluated after 1, 3, 6, 9 and 12 months of weathering. The weathering resulted in considerable colour fading of the composites. Composites containing darker colour pigments had better colour stability. Scanning electron microscopy analysis revealed that surface cracks caused by weathering in a wood-polypropylene composite having a higher polypropylene content were less abundant, and the deterioration of the surface layer was lower compared to composites containing less polymer. Measurements of melting temperatures by differential scanning calorimetry gave a consistent picture of polypropylene degradation in the surface layer. After weathering, a decrease in Charpy impact strength was found for composites characterised by higher moisture absorption.     

Mechanical behaviour of a poydimethylsiloxane elastomer after outdoor weathering in two different weathering locations

The degradation of maxillofacial prosthetic elastomers that occur during physical weathering is usually responsible for the replacement of the prosthesis. In this study the mechanical behaviour of a polydimethylsiloxane (PDMS) elastomer was investigated, after 1 year outdoor weathering in two different weathering locations in Greece (Thessaloniki, Athens). The hypothesis investigated was that irradiation time did not affect the measured properties. Specimens (Elastomer 42) were prepared according to manufacturer’s instructions and exposed to solar radiation for 1 year. Compression, tensile and nanoindentation tests were performed before and after the exposure. Compression and tensile data were also subjected to analysis of variance (ANOVA) and Tukey Post hoc tests at a level of α = .05. These properties were selected due to their clinical significance for fabrication and maintenance of a facial prosthesis. According to statistical analysis all the measured properties changed significantly after outdoor weathering. More specifically, most of the properties presented significant changes after six months of weathering. The observed changes also depended on the weathering locations. The hypothesis investigated was rejected. Material A became harder and the observed differences in the mechanical behaviour resulted from photo-degradation and hydrolysis that might occur due to weathering. The study also provides new information about maxillofacial prosthetics serviceability obtained from nanoindentation tests.     

Perylene-based profluorescent nitroxides for the rapid monitoring of polyester degradation upon weathering: An assessment

A profluorescent nitroxide possessing an isoindoline nitroxide moiety linked to a perylene fluorophore was developed to monitor radical mediated degradation of melamine-formaldehyde crosslinked polyester coil coatings in an industry standard accelerated weathering tester. Trapping of polyester-derived radicals (most likely C-radicals) that are generated during polymer degradation leads to fluorescent closed-shell alkoxy amines, which was used to obtain time-dependent degradation profiles to assess the relative stability of different polyesters towards weathering. The nitroxide probe couples excellent thermal stability and satisfactory photostability with high sensitivity and enables detection of free radical damage in polyesters under conditions that mimic exposure to the environment on a time scale of hours rather than months or years required by other testing methods. There are indications that the profluorescent nitroxide undergoes partial photo-degradation in the absence of polymer-derived radicals. Unexpectedly, it was also found that UV-induced fragmentation of the NO–C bond in closed-shell alkoxy amines leads to regeneration of the profluorescent nitroxide and the respective C-radical. The maximum fluorescence intensity that could be achieved with a given probe concentration is therefore not only determined by the amount of polyester radicals formed during accelerated weathering, but also by the light-driven side reactions of the profluorescent nitroxide and the corresponding alkoxy amine radical trapping products. Studies to determine the optimum probe concentration in the polymer matrix revealed that aggregation and re-absorption effects lowered the fluorescence intensity at higher concentrations of the profluorescent nitroxide, but too low probe concentrations, where these effects would be avoided, were not sufficient to trap the amount of polyester radicals formed upon weathering. The optimized experimental conditions were used to assess the impact of temperature and UV irradiance on polymer degradation during accelerated weathering.     

Applying Digital Image Processing to SEM-EDX and BSE Images to Determine and Quantify Porosity and Salts with Depth in Porous Media

 Digital image processing is applied to X-ray element maps and back-scattered electron (BSE) images obtained with scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), to quantify and identify salts and porosity with depth in porous media. Until now, only salt chemical composition with depth has been characterised and salt mineral composition inferred, so that no salt quantification was possible. The method we present can be used stand-alone or integrated with other techniques to fill certain gaps in our knowledge. It can be used to quantify texture and porosity of clay minerals, with implications in petroleum research. Also, salts may be identified and quantified with depth in porous media; this is important when selecting among salt extraction procedures in order to conserve cultural heritage. Finally, the method can help in interpreting salt weathering processes and links between stone decay forms at different scales, with consequences for geomorphology. To demonstrate the method, salt and pore percentages with depth are determined in two limestone types from monuments in the Aunis province, SW France: i) Crazannes sparite, showing alveolisation and black crust, and ii) La Pallice micrite, suffering from micro-delamination. In most of the micrites no salts are identified. Porosity data show that micro-fissures are confined between the surface and 9 mm depth in LPAM5, the only micrite with loading salts with depth (NaCl = 1.9% at the surface versus 1.4% at 18 mm; and Na₂SO₄ · H₂O and MgCl₂ ∼ 0.02% in the first 3 mm). In the sparites, those samples with no crust display an alveolisation zone with lower porosity and higher diversity and percentage of salts. In CRZM6, the stone crust-alveolisation front lies at a depth of 9 mm. In the crust, porosity is lower than in the alveolisation zone (12%). Salt concentration, by contrast, is higher in the crust (2.91% versus 0.14% in the alveolisation zone). Received September 1, 2000 Revision November 2, 2001     

离子吸附型稀土高效提取和分离技术进展

离子吸附型稀土资源(或称风化壳淋积型稀土资源)由于中重稀土含量高而得到国内外的广泛重视。对该类资源的开采和分离加工技术以及相关的环境保护问题进行了述评和讨论,包括矿山提取技术、萃取分离技术、沉淀结晶分离技术、材料前躯体制备技术和环境水处理技术。针对矿山开采中的主要问题,提出了该类稀土实现资源与环境保护性开采的环境工程模式及其对应的技术内涵;根据稀土市场和环境保护要求,讨论了离子吸附型稀土开发过程中今后需要开展的研究工作。     

Evaluation of the performance of microcrystalline cellulose in retarding degradation of two epoxy resin systems

Accelerated weathering studies are necessary to determine future risks arising from the loss of durability of materials under environmental conditions (e.g. ultraviolet irradiation from the sun, moisture from rainfall, temperature cycling). The influence of different accelerated weathering conditions such as UV light and moisture on the properties of two epoxy resin systems incorporating microcrystalline cellulose (MCC) was evaluated. This study aimed to assess changes in chemical properties (FTIR), mechanical properties (tensile tests), thermal properties (TGA and DSC) and morphology (SEM) before and after accelerated weathering. The samples exposed to different accelerated weathering times (1, 2, 3, 4, and 6?months) were based on the diglycidyl ether of bisphenol A, DGEBA, or hydrogenated diglycidyl ether of bisphenol A, HDGEBA, with amine crosslinker (2,2,4-trimethyl-1,6-hexanediamine, TMDA) and 2% MCC. Incorporation of MCC improved thermal stability, reduced surface oxidation, and gave better retention of mechanical properties after accelerated weathering. Both epoxy resins and epoxy composites exhibited a reduction in the tensile strength upon accelerated weathering with the composites showing less reduction in the tensile strength after 6 months. The glass transition temperatures (T_g) before and after accelerated weathering were also measured. DGEBA-TMDA/2%MCC and HDGEBA-TMDA/2% MCC composites reduced the decrease in the T_g after accelerated weathering, compared to that of DGEBA-TMDA and HDGEBA-TMDA samples. Degradation primarily decreased the mechanical properties of the composites, with some damaged specimens showing on the surfaces of DGEBA-TMDA/2% epoxy composites and HGEBA-TMDA/2%MCC composites. Fewer morphological changes with limited voids were seen on the DGEBA epoxy interface for HDGEBA compared to DGEBA composite samples. Incorporation of 2%MCC in DGEBA-TMDA and HDGEBA-TMDA increased resistance to thermal degradation after accelerated weathering.