In situ Agrobiodiversity Conservation for Regional Development in Nepal

The majority of rural communities have limited agricultural development opportunities within the hills and mountains of Nepal. While the dominant development model, which focuses on technology transfer and the evolution of commercial production systems, is effective when access to inputs and markets enables farmers to produce and trade successfully, many communities are marginalised from development opportunities by poverty and poor infrastructure. Complementary development approaches that value, conserve, develop and market agrobiodiversity could alleviate the extreme poverty where these conditions prevail as in the hills and mountains, the rural margins of Nepal. Formalised in situ approaches to agrobiodiversity conservation are in their infancy in Nepal, yet suggest that opportunities exist for a complementary agricultural development approach in the rural margins based on working with the local diversity, rather than its elimination. The obstacles of widespread poverty and inadequate infrastructure ensure that effective in situ agrobiodiversity conservation programs must provide for the needs of local people for sustainable development.     

砂岩型铀矿微区原位U-Pb同位素定年技术方法研究

铀矿物定年一直是成矿年代学中的难点,随着微区原位U-Pb同位素定年技术的发展,可以直接针对矿石矿物(铀矿物)进行同位素定年;但是其中的砂岩型铀矿由于其存在状态复杂,在原位定年中剥蚀要求高,也缺乏合适的外部校正标准物质,所以定年准确度有待提高。本文研究了两种微区原位U-Pb同位素测年的方法,对砂岩型铀矿定年进行了尝试,试图解决铀矿测年中的无基体匹配问题并提高砂岩型铀矿定年水平。一是建立了一种激光剥蚀多接收电感耦合等离子体质谱仪联合电子探针进行微区原位U-Pb同位素测年的技术(LA-MC-ICP-MS&EMPA)。通过优化实验方法,对秦岭陈家庄花岗岩型铀矿进行了测试,获得与同位素稀释热电离质谱法(ID-TIMS)一致的年龄结果,证明了微区原位U-Pb同位素测年无基体匹配标准物质分析的可行性;并利用此法获得鄂尔多斯盆地红庆河和塔然高勒砂岩型铀矿的微区原位U-Pb同位素年龄信息。二是尝试了利用飞秒激光剥蚀多接收电感耦合等离子体质谱法(fsLA-MC-ICP-MS)对红庆河和宁夏宁东砂岩型铀矿样品进行微区原位U-Pb同位素定年,并获得了微区原位U-Pb同位素年龄,表明飞秒激光剥蚀技术在砂岩型铀矿定年中有很好的应用前景。本文提出,比较单一且年龄偏老的单矿物样品可以选择LA-MC-ICP-MS&EMPA联合法进行分析,需要高空间分辨率的样品建议使用fsLA-MC-ICP-MS法。     

In situ laboratory X-ray powder diffraction study of wollastonite carbonation using a high-pressure stage

A high-pressure gas stage, recently developed for in-situ X-ray powder diffraction studies of polymer crystallization under CO_2, has been used to observe the carbonation of wollastonite under various temperature/pressure conditions despite the fact that the stage was not designed for use with moisture-containing samples. The rate of carbonation of wollastonite at 60 °C was found to be pressure-independent. Additional experiments at 34.5 bar between 43 and 73 °C enabled an activation energy of 53 kJ mol⁻¹ to be determined for the rate-limiting step. This value agrees very well with a published value for the leaching of Ca from wollastonite in acidic conditions and suggests that Ca leaching is the rate-limiting step in wollastonite carbonation at these temperatures.     

铁丝原位自转化-固相微萃取新涂层应用于萃取环境水样中多环芳烃的性能研究

多环芳烃(PAHs)是一类具有致癌作用且难以降解的持久性有机污染物,广泛存在于环境中。环境中痕量PAHs的直接分析往往因检测手段的检出限达不到要求而存在困难,需要结合分离富集手段。常规的样品前处理技术如索氏提取、液液萃取等存在耗时长、使用大量有机溶剂等问题。因此为了提高效率、避免对自然环境的二次污染,有必要开发一种简便、环境友好的新型样品前处理技术。固相微萃取(SPME)是一种集采样、富集、进样于一体的无溶剂前处理技术,与气相色谱-质谱(GC-MS)等技术联用可实现复杂基质中痕量有机物的快速富集和检测。目前SPME技术的研究热点主要集中在改善涂层的萃取性能以及提高其机械强度方面。本文采用铁丝(IW)作为载体,同时又提供了铁离子来源,以原位自转化的方式在具有良好机械稳定性的铁丝上生长出一层多孔结构的金属有机骨架化合物多孔膜[MIL-53(Fe)];将其作为固相微萃取涂层[IW@MIL-53(Fe)],以7种难挥发的稠环PAHs作为目标分析物,以浸入式模式进行萃取,并结合GC-MS作为检测手段验证其萃取性能。结果表明:新涂层的萃取性能是商用100μm PDMS涂层的1～2倍,且涂层可稳定使用120次以上。该方法的检出限为0.03～2.25ng/L,线性范围为250～10000ng/L,相关系数为0.9903～0.9991。将建立的方法应用于自然水体中PAHs的检测,加标回收率为80.1%～108.5%。本研究不仅为高性能SPME涂层简单、快速制备提供了新思路,而且所建立的方法有望应用于水体中痕量有机污染物的准确和高灵敏检测。     

含膏盐建造铁矿床中磁铁矿LA-ICP-MS微量元素测定与地球化学特征研究

膏盐建造会影响成矿流体的氧逸度和成矿流体成分,表现在磁铁矿元素组成会发生变化,从而对铁矿床的形成具有重要的指示作用,因此可以应用磁铁矿元素组成变化进行矿床类型划分和成因的厘定。膏盐建造广泛发育在新疆“帕米尔式”铁矿床和长江中下游宁芜铁矿床中,但膏盐建造的控矿机制尚不清楚。本文以新疆“帕米尔式”铁矿床和长江中下游宁芜玢岩铁矿床中的磁铁矿为研究对象,应用激光剥蚀电感耦合等离子体质谱法(LA-ICP-MS)测定其元素组成,分析磁铁矿中微量元素种类、含量及其地球化学特征,进而反演两种类型磁铁矿的成矿过程与形成环境,探讨膏盐建造在磁铁矿床形成过程中的控制作用。结果表明：①宁芜地区磁铁矿主要具有高Ti(平均含量16401μg/g)、V(平均含量2256μg/g)特征,说明其与岩浆作用密切相关。②新疆塔什库尔干地区磁铁矿床中的磁铁矿中Nb、Ta、Zr、Hf等高场强元素(HFSE)含量明显偏低,结合磁铁矿类型判别图将该地区磁铁矿床主要划分为两种成因类型,即与海相火山活动相关的岩浆热液型磁铁矿特征和热液交代矽卡岩型。分析表明两地区膏盐建造控矿作用明显不同：在塔什库尔干地区磁铁矿床形成过程中改变了氧逸度,而在宁芜地区玢岩铁矿形成过程中,为成矿提供了重要成矿物质来源。     

粤北石角围花岗岩型铀矿床沥青铀矿LA-ICP-MS原位U-Pb定年研究

石角围花岗岩型铀矿床位于粤北下庄铀矿田东部,沥青铀矿是矿床的主要矿石矿物,也是厘定成矿年龄的理想对象。前人采用同位素稀释法(ID-TIMS)和电子探针U-Th-totalPb化学定年法获得的成矿年龄为38～138Ma,但前人年龄变化范围大,可靠性有待考究,难以有效约束矿床的成矿时代。本文利用LA-ICP-MS原位微区分析技术,对石角围矿床矿石中沥青铀矿开展了原位U-Pb定年。研究表明:沥青铀矿的206Pb/238U年龄为52. 46～56. 89Ma,加权平均年龄为54. 68±0. 53Ma(MSWD=1. 19,n=18)。本次沥青铀矿原位U-Pb定年与前人相比更好地避免了矿物包裹体、后期次生变化、显微裂隙等因素的影响,获得的沥青铀矿原位U-Pb同位素年龄代表矿床的成矿年龄。本研究获得的石角围矿床成矿年龄(～55Ma)与华南花岗岩型铀矿床主成矿期(～50Ma)相一致,指示石角围矿床铀成矿作用与华南岩石圈局部伸展作用下的断裂构造活动密切相关。     

Diffusive transport of water in porous feldspars from granitic saprolites: In situ experiments using FTIR spectroscopy

A novel experimental cell was developed for in situ measurements of transport phenomena in porous media using Fourier-Transform Infrared (FTIR) Spectroscopy. The technique was employed at ambient pressure in the temperatures range of 11–44 °C to study the H₂O → D₂O exchange between water-saturated weathered feldspars (bulk porosity of 5–19 vol% for feldspar) from granitic saprolites and a surrounding aqueous liquid. Such measurements are an important step for understanding internal weathering reactions of feldspars in soils and aquifers. Effective diffusion coefficients D_eff for water in water-saturated porous feldspars were determined assuming one-dimensional diffusion in a quasi-homogeneous medium. The values of D_eff vary from 7.2 × 10⁻¹⁰ to 1.9 × 10⁻¹¹ m²/s and are 1–2 orders of magnitude lower than the diffusion coefficients (D) of protons and molecular H₂O in liquid water. The activation energy for the H₂O → D₂O exchange process in porous feldspars ranges from 7.8 to 18.8 kJ/mol.The results imply that the effective diffusivity of water is mainly controlled by physical properties of the feldspars like porosity, pore connectivity, pore geometry and distribution. Perthitic feldspars with homogeneous pore distribution in the albitic lamellas have diffusional tortuosity factors X = D/D_eff between 3 and 10 while alkali feldspars with inhomogeneously distributed and disconnected pores have much higher X values up to 129. Diffusion anisotropy has been verified for a vein perthite with diffusion perpendicular to the lamellas being faster by 0.3–0.5 log units than within the lamellas. It has to be emphasized that the study is based only on few selected feldspars, including perthitic feldspar, and additional work on samples with different weathering stages is needed to test the importance of the different parameters controlling diffusive transport in the pore system.     

In situ LA-MC-ICP-MS and ID-TIMS U–Pb geochronology of cassiterite in the giant Furong tin deposit, Hunan Province, South China: New constraints on the timing of tin–polymetallic mineralization

The Furong deposit, located in southern Hunan Province, China, is a newly-discovered giant tin deposit spatially associated with the A-type Qitianling granite. The petrogenetic link between the giant Furong tin deposit and the Qitianling granite batholith remains controversial because of the lack of precise dating for the tin–polymetallic mineralization. Here we report for the first time in-situ U–Pb data on cassiterite obtained by LA-MC-ICP-MS and the results are compared to ID-TIMS data. The in-situ LA-MC-ICP-MS analyses of the cassiterites provide a reliable age constraint for tin–polymetallic mineralization in the Furong deposit, yielding an isochron age of 159.9 ± 1.9 Ma (at 95% confidence level, MSWD = 18), which is indistinguishable from the ID-TIMS ²⁰⁶Pb/²³⁸U weighted mean age of 158.2 ± 0.4 Ma. The in situ U–Pb ages corroborate the Ar–Ar dates published for the Furong tin deposit, which indicate that the mineralization is coeval with the emplacement of the Qitianling granite batholith. These results provide further evidence of a close temporal link between the pluton's emplacement and tin mineralization in the Furong area. The data obtained clearly demonstrate that in-situ LA-MC-ICP-MS U–Pb dating of cassiterite is a robust geochronometer for direct dating of tin–polymetallic mineralization.     

In situ tests on backfilling and surrounding host-rock in the case of a radioactive waste disposal in a layered salt formation

In situ experiments carried out by ANDRA in a deep and homogeneous salt layer of a French mine (Amélie mine — Alsace Potash Mines S.A.) tested the behavior of the different components of a multibarrier system, designed for high-level waste disposal and particularly for heat-generating wastes. Canisters were placed in blind boreholes.

The experimental field is located at a depth of 520 m where two major tests have been carried out since 1987. The first test (1987–1989) tested the backfilling by heating different types of crushed salt (max. 130°C) emplaced in large-diameter boreholes. One hole remained empty as a control. The second experiment started in 1989 with the opening of a gallery and the boring of three different boreholes (7 m depth, 250 mm diameter) where the annulus between the cylindrical heating cell and the salt mass differs fundamentally in configuration: as tight as possible, empty, or backfilled with crushed salt. The first configuration was tested at the end of 1991.

In both test fields, a complete series of measurements has been carried out to record temperatures, pressures and deformations on the heating devices, as well as in the surrounding media. Backfill and host rock are monitored with sensors placed in different boreholes. High-resolution tiltmeters and accurate levelling complete the field of investigations. Thermo-mechanical behavior and the properties of the materials have been considered in detail using laboratory test results. Calculations showed how thermo-mechanical interactions behave and generally agreed in a satisfactory manner with the measurements of the test field.

Finally, after cooling and dismantling of the experiment, the microscopic change of the different crushed salts used for the backfilling is analysed.     

New constraints on UHT metamorphism in the Eastern Ghats Province through the application of phase equilibria modelling and in situ geochronology

High Mg–Al granulites from the Sunki locality in the central portion of the Eastern Ghats Province record evidence for the high-temperature peak and retrograde evolution. Peak metamorphic phase assemblages from two samples are garnet + orthopyroxene + quartz + ilmenite + melt and orthopyroxene + spinel + sillimanite + melt, respectively. Isochemical phase diagrams (pseudosections) based on bulk rock compositions calculated in the chemical system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) and Al contents in orthopyroxene indicate peak UHT metamorphic conditions in excess of 960 °C and 9.7 kbar. Microstructures and the presence of cordierite interpreted to record the post-peak evolution show that the rocks underwent decompression and minor cooling from conditions of peak UHT metamorphism to conditions of ~ 900 °C at ~ 7.5 kbar. In situ U–Pb isotope analyses of monazite associated with garnet and cordierite using the Sensitive High Resolution Ion Microprobe (SHRIMP) yield a weighted mean ²⁰⁷Pb/²³⁵U age of ca. 980 Ma, which is interpreted to broadly constrain the timing of high-temperature monazite growth during decompression and melt crystallization at ~ 900–890 °C and 7.5 kbar. However, the range of ²⁰⁷Pb/²³⁵U monazite ages (from ca. 1014 Ma to 959 Ma for one sample and ca. 1043 Ma to 922 Ma for the second sample) suggest protracted monazite growth during the high-temperature retrograde evolution, and possibly diffusive lead loss during slow cooling after decompression. The results of the integrated petrologic and geochronologic approach presented here are inconsistent with a long time gap between peak conditions and the formation of cordierite-bearing assemblages at lower pressure, as proposed in previous studies, but are consistent with a simple evolution of a UHT peak followed by decompression and cooling.     

滇西北休瓦促钼钨矿床白钨矿原位微量和Sr同位素特征及其对成矿作用的指示

滇西北休瓦促钼钨矿床是义敦岛弧Cu-Mo成矿带南缘典型的热液石英脉型钼钨矿床,目前前人对该矿床主要开展了成岩-成矿年代学、岩石成因、动力学过程等研究。本文以白钨矿为研究对象,利用原位微量LA-ICP-MS以及原位Sr同位素LA-MC-ICP-MS测试技术对成矿流体演化及成矿物质来源开展了系统研究。白钨矿的产状和阴极发光图像显示其存在早中晚三个阶段,以中阶段白钨矿最为发育。早阶段白钨矿稀土配分与斑状二长花岗岩相似,呈轻稀土富集的右倾模式,Eu具有中等负异常（δEu=0.42）,Mo平均含量为3.0%,⁸⁷Sr/⁸⁶Sr平均值为0.7098,与斑状二长花岗岩（0.7075~0.7098）接近;与早阶段相比,中阶段白钨矿轻稀土含量降低,Eu也具有中等负异常（δEu=0.37）,Mo平均含量降低至2445μg/g,⁸⁷Sr/⁸⁶Sr值升高至0.7113;晚阶段白钨矿稀土配分呈中稀土相对富集的拱形模式,Eu基本无异常（δEu=0.93）,Mo平均含量降低至56μg/g,⁸⁷Sr/⁸⁶Sr平均值为0.7083。从早到晚,白钨矿中轻稀土元素尤其是La和Ce的逐渐亏损表明存在氟碳铈镧矿的结晶;δEu升高和Mo急剧降低指示成矿流体从氧化到还原的转换;Sr同位素组成的变化指示了成矿物质来源的转变,早阶段岩浆流体贡献大,在中阶段白钨矿岩浆热液与围岩地层大规模作用下,地层为白钨矿的形成提供了大量Ca,表明强烈的水岩交互作用对矿床的形成发挥了重要作用。     

Generalized numerical error analysis with applications to geochronology and thermodynamics

A general numerical error propagation procedure is developed to calculate the error in a quantity derived from measurements which are subject to errors. It is an alternative to computer intensive techniques such as Monte Carlo and can be applied to quite complex analytical problems where correlation among the measurement errors and among the final errors in results are present. Previous formulations have usually ignored correlated errors. Some of the assumptions involved in error propagation can also be checked numerically. This is an advantage over analytical formulations which cannot assess the validity of the calculated errors. Formulation as computer subroutines permits the analysis to be added to existing programs. Examples from the fields of geochronology and thermodynamics are used to highlight the advantages and the flexibility of the method.     

A review of lognormal estimators forin situ reserves

The term lognormal kriging does not correspond to a single well defined estimator. In fact, several types of lognormal estimators forin situ reserves are available, and this may cause confusion. These estimators are based on different assumptions—that is, different models. This paper presents a review of these estimators.     

Petrology and 40Ar/39Ar geochronology of some hellenic sub-ophiolite metamorphic rocks

Whole rock, electron microprobe analyses and ⁴⁰Ar/³⁹Ar geochronology of certain ophioliterelated metamorphic rocks from beneath the Pindos, Vourinos, Othris and Euboea ophiolites of Greece show that they were formed mainly from ocean-type basalts, in part under P-T conditions of the upper mantle and that they have ages between 170–180 m.y. The evidence presented is inconsistent with the view that these sub-ophiolite metamorphic rocks were produced by the obduction of ocean-type crust onto a continental margin, or that they are remnant slices of Palaeozoic ‘basement’, but is consistent with their formation by thrusting and related metamorphism occurring within ocean lithosphere during the Lower to Middle Jurassic. It is proposed that this intraoceanic metamorphism was caused by the inception of a fault zone which subsequently became the transport surface for the main phase of ophiolite emplacement that occurred in the Hellenides from the Late Jurassic to Early Cretaceous.     

Carbon in solid solution in forsterite—a key to the untractable nature of reduced carbon in terrestrial and cosmogenic rocks

Carbon is an incompatible element in oxide and silicate lattices. Until now it has been believed to exist only in the form of CO^2?₃ ions, molecularily dissolved CO₂ or graphitic inclusions. Recently it has been shown that carbon can dissolve in refractory oxides, like MgO and CaO, in the form of carbon atoms.The experimental results obtained with carbonaceous MgO are reviewed and new results are presented which demonstrate that synthetic forsterite and natural olivines can also take up atomic carbon in solid solution. The incorporation of the carbon atoms is treated thermodynamically. Near the melting point they probably occupy cation vacancies, but with decreasing temperature they are progressively transferred on interstitial sites. On these sites they are very mobile and tend to segregate into the elastically relaxed subsurface zone, but exsolution to graphite is prevented by the strain fields surrounding each carbon atom.Upon heating, however, the atomic carbon may react with lattice oxygen to give CO₂ and with co-dissolved hydrogen to give a wide variety of hydrocarbons. The underlying reaction mechanisms, involving the formation and decay of O^? ions, are discussed in view of the so-called ‘carbonatic carbon’ and ‘reduced carbon’ in magmatic minerals and meteorites, in view of the diamond genesis and also in view of the reversible CO₂ solubility in silicate magmas at high pressures and temperatures.     

40Ar/39Ar age spectra of some undisturbed terrestrial samples

⁴⁰Ar/³⁹Ar age spectra and ⁴⁰Ar/³⁶Ar vs ³⁹Ar/³⁶Ar isochrons were determined by incremental heating for 11 terrestrial rocks and minerals whose geology indicates that they represent essentially undisturbed systems. The samples include muscovite, biotite, hornblende, sanidine, plagioclase, dacite, diabase and basalt and range in age from 40 to 1700 m.y. For each sample, the ⁴⁰Ar/³⁹Ar ratios, corrected for atmospheric and neutron-generated argon isotopes, are the same for most of the gas fractions released and the age spectra, which show pronounced plateaus, thus are consistent with models previously proposed for undisturbed samples. Plateau ages and isochron ages calculated using plateau age fractions are concordant and appear to be meaningful estimates of the crystallization and cooling ages of these samples. Seemingly anomalous age spectrum points can be attributed entirely to small amounts of previously unrecognized argon loss and to gas fractions that contain too small (less than 2 per cent) a proportion of the ³⁹Ar released to be geologically significant. The use of a quantitative abscissa for age spectrum diagrams is recommended so that the size of each gas fraction is readily apparent. Increments containing less than about 4–5 per cent of the total ³⁹Ar released should be interpreted cautiously. Both the age spectrum and isochron methods of data reduction for incremental heating experiments are worthwhile, as each gives slightly different but complementary information about the sample from the same basic data. Use of a least-squares fit that allows for correlated errors is recommended for ⁴⁰Ar/³⁶Ar vs ³⁹Ar/³⁶Ar isochrons. The results indicate that the ⁴⁰Ar/³⁹Ar incremental heating technique can be used to distinguish disturbed from undisturbed rock and mineral systems and will be a valuable geochronological tool in geologically complex terranes.     

氧化物型含铀矿物微区原位Hf同位素分析技术研究进展

近二十年来,Lu-Hf同位素分析技术得到了快速发展,为探讨岩石成因、物质来源及壳幔演化过程提供了重要手段。其中,锆石微区原位Hf同位素测定方法已经被广泛应用于同位素地球化学研究中。然而,金红石、锡石和铌铁矿等氧化物型含铀矿物激光剥蚀多接收等离子体质谱(LA-MC-ICPMS)Hf同位素测定方法发展较为缓慢。本文结合近年来相关研究工作,简要介绍副矿物Lu-Hf同位素分析技术的发展历史,系统梳理了金红石、锡石和铌铁矿等氧化物型含铀矿物原位Hf同位素测定方法研究的最新进展以及存在的问题。基于该方法目前存在的同质异位数干扰校正策略、质量监控标样的缺乏以及较低的Hf含量如何提高分析灵敏度等技术难点进行了详细论述。氧化物型含铀矿物的Hf含量普遍不高,在测试时需要更大的剥蚀束斑直径。而飞秒激光具有剥蚀的样品粒径细小且均匀的特点,采用飞秒激光与LA-MC-ICPMS(fs-LA-MC-ICPMS)相结合,可以减小剥蚀束斑从而提高原位分析的空间分辨率,是未来氧化物型含铀矿物原位Hf同位素分析的发展方向。     

油气成藏过程中的同位素测年方法评述

笔者对国内外同位素测定年在确定油气成藏方面的应用现状进行评述的基础上,重点分析了K-Ar法,Ar-Ar法,U-Pb法,Rb-Sr法等方法所存在的问题,认为自生伊利石⁴⁰Ar-³⁹Ar法在不断克服技术难题之后,仍是油气成藏年代学不可缺少的重要手段;激光微区探针⁴⁰Ar-³⁹Ar法与流体包裹体技术相结合,是油气多期成藏⁴⁰Ar-³⁹Ar年代学研究取得成功的突破点;利用沥青和干酪根中微量金属U-Pb,Pb-Pb,Rb-Sr,Sm-Nd和Re-Os体系的同位素分析方法获得油气生成、运移的年龄,是成熟的放射性同位素方法在石油地质学中的应用;晶洞充填物U-Pb测年,可能是碳酸盐岩储层油气成藏年代学研究又一新的突破点。