Nuclear field shift effects on stable isotope fractionation: a review     

Sha Yang  Yun Liu 《中国地球化学学报》2016,35(3):227-239

An anomalous isotope effect exists in many heavy element isotope systems (e.g., Sr, Gd, Zn, U). This effect used to be called the “odd–even isotope effect” because the odd mass number isotopes behave differently from the even mass number isotopes. This mass-independent isotope fractionation driving force, which originates from the difference in the ground-state electronic energies caused by differences in nuclear size and shape, is currently denoted as the nuclear field shift effect (NFSE). It is found that the NFSE can drive isotope fractionation of some heavy elements (e.g., Hg, Tl, U) to an astonishing degree, far more than the magnitude caused by the conventional mass-dependent effect (MDE). For light elements, the MDE is the dominant factor in isotope fractionation, while the NFSE is neglectable. Furthermore, the MDE and the NFSE both decrease as temperatures increase, though at different rates. The MDE decreases rapidly with a factor of 1/T², while the NFSE decreases slowly with a factor of 1/T. As a result, even at high temperatures, the NFSE is still significant for many heavy element isotope systems. In this review paper, we begin with an introduction of the basic concept of the NSFE, including its history and recent progress, and follow with the potential implications of the inclusion of the NFSE into the kinetic isotope fractionation effect (KIE) and heavy isotope geochronology.  相似文献   

华南大规模低温成矿的主要科学问题   总被引：9，自引：7，他引：2  

胡瑞忠  付山岭  肖加飞 《岩石学报》2016,32(11):3239-3251

大面积低温成矿是全球独特的重要成矿事件。华南地区扬子地块西南部面积约50万平方千米的广大范围,低温矿床广泛发育,包括卡林型金矿床、MVT型Pb-Zn矿床和脉型锑、汞、砷等矿床,构成华南低温成矿域。该成矿域由川滇黔接壤区的Pb-Zn、右江盆地Au-Sb-As-Hg和湘中盆地Sb-Au等三个矿集区组成。其中的矿床主要赋存于沉积岩中,受断裂构造控制,形成于100~250℃的低温条件下。以往的研究取得了重要进展,但成矿时代、成矿动力学背景、成矿物质基础和成矿过程等关键科学问题一直悬而未决。近年的研究表明,这些矿床可能形成于200~230Ma(印支期)和130~160Ma(燕山期)两个时期,除川滇黔Pb-Zn矿集区由盆地卤水演化成矿外,其余两个矿集区的形成可能均受印支期和燕山期的深部岩浆活动驱动,尽管成矿流体中的水主要是大气成因地下水。本专题报道了近年来这些方面的最新研究进展,包括20篇文章,主要涉及这些低温矿床的地质地球化学特征、成矿时代、矿床成因和成矿动力学背景等。  相似文献   

滇东南安那金矿床成矿流体地球化学研究   总被引：1，自引：1，他引：0  

董文斗  沈能平  苏文超  蔡佳丽 《岩石学报》2016,32(11):3321-3330

云南安那金矿床位于右江盆地南缘,产于二叠纪辉绿岩侵入体之中,广泛发育乳白色石英网脉,蚀变辉绿岩体即为金矿体。与右江盆地以沉积岩为容矿岩石的卡林型金矿床类似,具有硅化、粘土化、碳酸盐化和硫化物化等热液蚀变特征。本文对安那金矿床石英中的流体包裹体岩相学、显微测温学、激光拉曼光谱以及氢氧同位素组成进行了分析,发现成矿期石英中的流体包裹体主要为富含CO_2气-液两相或三相流体包裹体,其均一温度范围为208~312℃(平均254℃),盐度很低,变化范围为0~2%Na Cleqv,成矿溶液的密度为0.88~0.98g/cm~3,表明形成安那金矿床的成矿流体属于中温、低盐度、中-低密度的流体。激光拉曼光谱分析显示,石英中包裹体的气相成分富含CO_2、N_2以及微量CH_4等挥发分。成矿流体的氢氧同位素组成显示变质流体成因,结合矿石显微岩相学结构,认为流体溶蚀交代辉绿岩中的含Ti-Fe辉石或者钛铁矿,溶解Fe的硫化作用过程是含Au黄铁矿和毒砂沉淀富集的重要机制。成矿作用可能与右江盆地南缘印支期造山事件有关。  相似文献   

湘中龙山大型金锑矿床成矿时代研究——黄铁矿Re-Os和锆石U-Th/He定年   总被引：4，自引：4，他引：0  

付山岭  胡瑞忠  陈佑纬  骆金诚 《岩石学报》2016,32(11):3507-3517

龙山金锑矿床是湘中锑-金矿集区最重要的矿床之一,因缺少适合传统放射性同位素定年的矿物,其成矿时代以往未得到很好的限定,制约了对矿床成因的认识。由于分析测试技术的进步,Re-Os同位素定年技术得到了发展,可对热液矿床中形成的低Re、Os含量的硫化物进行较准确可靠的年龄测定,从而可为低温热液矿床的形成时代提供有效制约。锆石U-Th/He同位素定年,也是近年发展和成熟起来的定年技术,对低温热事件极其敏感,同样是约束低温成矿年龄的重要手段之一。本文采用矿床中黄铁矿Re-Os同位素和蚀变围岩中受成矿热事件影响的锆石U-Th/He同位素定年技术,对龙山金锑矿床的成矿时代进行了研究。定年结果显示:热液成因黄铁矿的Re-Os等时线年龄为195±36Ma,对应于印支晚期;锆石U-Th/He年龄为51.2~133.3Ma,经Ft校正后,U-Th/He年龄分布于93.78~258.29Ma之间,平均值为160.7±7.3Ma,对应于燕山早期。该矿床可能发生了200Ma和160Ma的两次成矿作用;或者矿床形成于200Ma左右,但是受到了160Ma左右岩浆热事件的改造,黄铁矿Re-Os年龄代表成矿年龄,而锆石U-Th/He年龄则代表第二期热事件发生的时间。无论是200Ma左右一次成矿,还是另有160Ma左右的成矿作用叠加,这两个年龄分别与区内两期岩浆活动的时间相当,这表明岩浆事件对驱动矿床的形成发挥了重要的作用。  相似文献   

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry          下载免费PDF全文

Wen Zhang  Liang Qi  Zhaochu Hu  Cunjiang Zheng  Yongsheng Liu  Haihong Chen  Shan Gao  Shenghong Hu 《Geostandards and Geoanalytical Research》2016,40(2):195-216

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.  相似文献   

Constraints of molybdenite Re–Os and scheelite Sm–Nd ages on mineralization time of the Kukaazi Pb–Zn–Cu–W deposit,Western Kunlun,NW China     

Chengbiao Leng  Yuhui Wang  Xingchun Zhang  Jianfeng Gao  Wei Zhang  Xinying Xu 《中国地球化学学报》2018,37(1):47-59

The Kukaazi Pb–Zn–Cu–W polymetallic deposit, located in the Western Kunlun orogenic belt, is a newly discovered skarn-type deposit. Ore bodies mainly occur in the forms of lenses and veins along beddings of the Mesoproterozoic metamorphic rocks. Three ore blocks, KI, KII, and KIII, have been outlined in different parts of the Kukaazi deposit in terms of mineral assemblages. The KI ore block is mainly composed of chalcopyrite, scheelite, pyrrhotite, sphalerite, galena and minor pyrite, arsenopyrite, and molybdenite, whereas the other two ore blocks are made up of galena, sphalerite, magnetite and minor arsenopyrite and pyrite. In this study, we obtained a molybdenite isochron Re–Os age of 450.5 ± 6.4 Ma (2σ, MSWD = 0.057) and a scheelite Sm–Nd isochron age of 426 ± 59 Ma (2σ, MSWD = 0.49) for the KI ore block. They are broadly comparable to the ages of granitoid in the region. Scheelite grains from the KI ore block contain high abundances of rare earth elements (REE, 42.0–95.7 ppm) and are enriched in light REE compared to heavy REE, with negative Eu anomalies (δEu = 0.13–0.55). They display similar REE patterns and Sm/Nd ratios to those of the coeval granitoids in the region. Moreover, they also have similar Sr and Nd isotopes [⁸⁷Sr/⁸⁶Sr = 0.7107–0.7118; ε_Nd(t) = ?4.1 to ?4.0] to those of such granitoids, implying that the tungsten-bearing fluids in the Kukaazi deposit probably originate from the granitic magmas. Our results first defined that the Early Paleozoic granitoids could lead to economic Mo–W–(Cu) mineralization at some favorable districts in the Western Kunlun orogenic belt and could be prospecting exploration targets.  相似文献   

The effects of clay minerals and organic matter on nanoscale pores in Lower Paleozoic shale gas reservoirs,Guizhou, China     

Yuantao Gu  Quan Wan  Wenbin Yu  Xiaoxia Li  Zhongbin Yu 《中国地球化学学报》2018,37(6):791-804

In organic-rich gas shales, clay minerals and organic matter (OM) have significant influences on the origin, preservation, and production of shale gas. Because of the substantial role of nanoscale pores in the generation, storage, and seepage of shale gas, we examined the effects of clay minerals and OM on nanoscale pore distribution characteristics in Lower Paleozoic shale gas reservoirs. Using the Niutitang and Longmaxi shales as examples, we determined the effects of clay minerals and OM on pores through sedimentation experiments. Field emission–scanning electron microscopy combined with low-pressure N₂ adsorption of the samples before and after sedimentation showed significant differences in pore location and pore size distribution between the Niutitang and Longmaxi shales. Nanoscale pores mostly existed in OM in the Longmaxi shale and in clay minerals or OM–clay composites in the Niutitang shale. The distribution differences were attributed largely to variability in thermal evolution and tectonic development and might account for the difference in gas-bearing capacity between the Niutitang and Longmaxi reservoirs. In the nanoscale range, mesopores accounted for 61–76% of total nanoscale pore volume. Considerably developed nanoscale pores in OM were distributed in a broad size range in the Longmaxi shale, which led to good pore connectivity and gas production. Numerous narrow pores (i.e., pores?<?20 nm) in OM–clay composites were found in the Niutitang shale, and might account for this shale’s poor pore connectivity and low gas production efficiency. Enhancing the connectivity of the mesopores (especially pores?<?20 nm and those developed in OM–clay composites) might be the key to improving development of the Niutitang shale. The findings provide new insight into the formation and evolutionary mechanism of nanoscale pores developed in OM and clay minerals.  相似文献   

Theoretical calculation of equilibrium Mg isotope fractionation between silicate melt and its vapor     

Haiyang Luo  Huiming Bao  Yuhong Yang  Yun Liu 《中国地球化学学报》2018,37(5):655-662

Isotope fractionation during the evaporation of silicate melt and condensation of vapor has been widely used to explain various isotope signals observed in lunar soils, cosmic spherules, calcium–aluminum-rich inclusions, and bulk compositions of planetary materials. During evaporation and condensation, the equilibrium isotope fractionation factor (α) between high-temperature silicate melt and vapor is a fundamental parameter that can constrain the melt’s isotopic compositions. However, equilibrium α is difficult to calibrate experimentally. Here we used Mg as an example and calculated equilibrium Mg isotope fractionation in MgSiO₃ and Mg₂SiO₄ melt–vapor systems based on first-principles molecular dynamics and the high-temperature approximation of the Bigeleisen–Mayer equation. We found that, at 2500 K, δ²⁵Mg values in the MgSiO₃ and Mg₂SiO₄ melts were 0.141?±?0.004 and 0.143?±?0.003‰ more positive than in their respective vapors. The corresponding δ²⁶Mg values were 0.270?±?0.008 and 0.274?±?0.006‰ more positive than in vapors, respectively. The general \(\alpha - T\) equations describing the equilibrium Mg α in MgSiO₃ and Mg₂SiO₄ melt–vapor systems were: \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.264 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\) and \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.340 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\), respectively, where m is the mass of light isotope ²⁴Mg and m′ is the mass of the heavier isotope, ²⁵Mg or ²⁶Mg. These results offer a necessary parameter for mechanistic understanding of Mg isotope fractionation during evaporation and condensation that commonly occurs during the early stages of planetary formation and evolution.  相似文献   

U–Pb zircon age of the base of the Ediacaran System at the southern margin of the Qinling Orogen     

Lecai Xing  Taiyi Luo  Zhilong Huang  Zhikuan Qian  Mingzhong Zhou  Hongtao He 《中国地球化学学报》2018,37(3):414-421

Global abrupt climate change from Marinoan snowball Earth to greenhouse Earth, recorded as cap carbonate overlain on diamictite, had shed the first light on Cambrian bio-radiation. The most documented cap carbonate sections are typical with comprehensive δ¹³C negative values and ubiquitous sedimentary structures, such as tepee-like, sheet-crack etc., which are associated with successive glacial eustatic variation caused by isostatic rebound in shallow-water facies. Here we report a deep-water basinal cap carbonate section with strong negative δ¹³C values in the southern margin of the Qinling Orogen, Heyu, Chengkou County, Chongqing in China, which consists of massive dolostone with abundant carbonaceous laminae. However, it lacks the sedimentary structure as mentioned above and is overlain by thin-bedded silicious shales and cherts. A K-bentonite bed was discovered within the base of cap carbonates, about 0.7 m above the top of the Marinoan diamictite. Magmatic zircons that were separated from the K-bentonite bed yield a SIMS concordia U–Pb age of 634.1 ± 1.9 Ma (1σ, MSWD_CE = 0.31, Probability_CE = 1.000, n = 20). The age is in good agreement with previously reported TIMS U–Pb ages for the termination of Marinoan glaciation and provides a geochronological constraint for the Ediacaran successions in the Qinling Orogen.  相似文献   

Assessment of trace metals contamination in stream sediments and soils in Abuja leather mining,southwestern Nigeria     

Abiola Oyebamiji  Adegbola Odebunmi  Hu Ruizhong  Atta Rasool 《中国地球化学学报》2018,37(4):592-613

This study is aimed at determining the level of environmental degradation as well as the concentration of trace elements in soil and stream sediments in order to evaluate the environmental impact of the mining operation. Twenty-five (25) soils and ten (10) stream sediment samples were collected from the study area. The physicochemical parameters were determined using appropriate instrumentation with the aid of a digital pH meter (Milwaukee meter) to measure the pH and electrical conductivity, total dissolved solids, moisture content and loss on ignition of the soil and stream sediment samples. The pH of the soil sample ranged from (6.10 to 7.19); Electrical conductivity ranged from (21.3 to 279.4 µS/cm), moisture content varied from (0.60% to 7.20%), and the LOI ranged from (2.03% to 18.62%). The results of the analysis showed that the concentrations of the trace elements in the soils and stream sediment samples were slightly higher than the background values. Plots of the trace elements in stream sediment samples show moderate, consistent decrease downstream except at points where there was mine water discharge into the main river. The pollution levels of heavy metals were examined in stream sediment and soil samples using different assessable indices, such as the enrichment factor, which showed significant-moderate enrichment for Cr, Th, Nb, Zn, Pb, Y and Zr and the geo-accumulation index, which showed practically moderate contamination with Cr, Ni and Sr based on regional background reference values. Geo-accumulation index and contamination index for soils and stream sediment revealed uncontaminated to moderate contamination. Likewise, elements with moderate contamination were Cr, Ni and Sr. The Pearson correlation showed that there were significant positive associations among selected metals in soil and stream sediment samples.  相似文献