Some specific features of genesis of microdiamonds of octahedral and cubic habit from kimberlites of the Udachnaya pipe (Yakutia) inferred from carbon isotopes and main impurity defects

Microdiamonds (crystals smaller than 1 mm) of octahedral and cubic habit from Udachnaya kimberlite pipe (Yakutia) have been compared in order to distinguish genetic features inferred from carbon isotopic composition and impurity defects. Microdiamonds of cubic habit from the Udachnaya kimberlite pipe have a fibrous internal structure and a high content of nitrogen impurity (400–3000 ppm). Octahedral microdiamonds from the same deposit are distinguished by a low nitrogen content of 0 to 500 ppm and zoning structure. The isotopic composition of carbon (δ¹³C is –4.7‰ for octahedra and –4.5‰ for cuboids) suggests a common source of carbon for these morphologic groups. The studied characteristics can be due to crystallization of octahedra from carbon dissolved in the melt, and cuboids, under the conditions of the hampered diffusion of carbon.     

Crystal morphological evolution of growth and dissolution of curve-faced cubic diamonds from placers of the Anabar diamondiferous region

In this paper, we consider an ontogenic model for the formation of morphological types of growth and dissolution of cubic diamonds of variety II by Yu.L. Orlov from placers of the Anabar diamondiferous region. The following ontogenic domains of crystals and corresponding evolutionary stages of growth accompanying a general decrease in supersaturation in the crystallization medium were distinguished: microblock mosaic cuboids with defects produced by the mechanism of rotational plastic deformation–cuboids with linear translation deformations–cuboids and antiskeletal growth forms of cuboids composed of octahedral growth layers–pseudocubic growth forms of a flat-faced octahedron. The crystal morphological evolution of cuboids during the bulk dissolution of individuals in fluid-bearing melt transporting them to the surface was traced. The investigation of transitional forms of cuboid diamond dissolution showed that the final form of diamond dissolution is a rounded tetrahexahedroid independent of the combination of cuboid faces with subordinate faces of octahedron, rhombododecahedron, and tetrahexahedron observed on resorbed crystals of cubic habit. It was found that the final stages of cuboid dissolution produced disk-shaped microrelief features on the diamond surface in the form of randomly distributed ideal rounded etch pits resulting from interaction with microscopic cavitation gas bubbles released during the decompression of ascending kimberlite melt.     

Origin of sub-lithospheric diamonds from the Juina-5 kimberlite (Brazil): constraints from carbon isotopes and inclusion compositions

Forty-one diamonds sourced from the Juina-5 kimberlite pipe in Southern Brazil, which contain optically identifiable inclusions, have been studied using an integrated approach. The diamonds contain <20 ppm nitrogen (N) that is fully aggregated as B centres. Internal structures in several diamonds revealed using cathodoluminescence (CL) are unlike those normally observed in lithospheric samples. The majority of the diamonds are composed of isotopically light carbon, and the collection has a unimodal distribution heavily skewed towards δ¹³C ~ ?25 ‰. Individual diamonds can display large carbon isotope heterogeneity of up to ~15 ‰ and predominantly have isotopically lighter cores displaying blue CL, and heavier rims with green CL. The light carbon isotopic compositions are interpreted as evidence of diamond growth from abiotic organic carbon added to the oceanic crust during hydrothermal alteration. The bulk isotopic composition of the oceanic crust, carbonates plus organics, is equal to the composition of mantle carbon (?5 ‰), and we suggest that recycling/mixing of subducted material will replenish this reservoir over geological time. Several exposed, syngenetic inclusions have bulk compositions consistent with former eclogitic magnesium silicate perovskite, calcium silicate perovskite and NAL or CF phases that have re-equilibrated during their exhumation to the surface. There are multiple occurrences of majoritic garnet with pyroxene exsolution, coesite with and without kyanite exsolution, clinopyroxene, Fe or Fe-carbide and sulphide minerals alongside single occurrences of olivine and ferropericlase. As a group, the inclusions have eclogitic affinity and provide evidence for diamond formation at pressures extending to Earth’s deep transition zone and possibly the lower mantle. It is observed that the major element composition of inclusions and isotopic compositions of host Juina-5 diamonds are not correlated. The diamond and inclusion compositions are intimately related to subducted material and record a polybaric growth history across a depth interval stretching from the lower mantle to the base of the lithosphere. It is suggested that the interaction of slab-derived melts and mantle material combined with subsequent upward transport in channelised networks or a buoyant diapir explains the formation of Juina-5 diamonds. We conclude that these samples, despite originating at great mantle depths, do not provide direct information about the ambient mantle, instead, providing a snapshot of the Earth’s deep carbon cycle.     

Nitrogen isotopes in the recent solar wind from the analysis of Genesis targets: Evidence for large scale isotope heterogeneity in the early solar system

We have analyzed nitrogen, neon and argon abundances and isotopic ratios in target material exposed in space for 27 months to solar wind (SW) irradiation during the Genesis mission. SW ions were extracted by sequential UV (193 nm) laser ablation of gold-plated material, purified separately in a dedicated line, and analyzed by gas source static mass spectrometry. We analyzed gold-covered stainless steel pieces from the Concentrator, a device that concentrated SW ions by a factor of up to 50. Despite extensive terrestrial N contamination, we could identify a non-terrestrial, ¹⁵N-depleted nitrogen end-member that points to a 40% depletion of ¹⁵N in solar-wind N relative to inner planets and meteorites, and define a composition for the present-day Sun (¹⁵N/¹⁴N = [2.26 ± 0.67] × 10⁻³, 2σ), which is indistinguishable from that of Jupiter’s atmosphere. These results indicate that the isotopic composition of nitrogen in the outer convective zone of the Sun has not changed through time, and is representative of the protosolar nebula. Large ¹⁵N enrichments due to e.g., irradiation, low temperature isotopic exchange, or contributions from ¹⁵N-rich presolar components, are therefore required to account for inner planet values.     

Isotopic fractionation of nitrogen and carbon in Paleoarchean cherts from Pilbara craton, Western Australia: Origin of N-depleted nitrogen

Nitrogen and carbon isotopic compositions, together with mineralogy and trace element geochemistry, were studied in a few kerogen-rich Paleoarchean cherts, a barite and a dolomitic stromatolite belonging to the eastern (Dixon Island Formation) and western (Dresser and Strelley Pool Chert Formations; North Pole Dome and Marble Bar) terranes of Pilbara Craton, Western Australia. The aim of the study was to search for ¹⁵N-depleted isotopic signatures, often found in kerogens of this period, and explain the origin of these anomalies. Trace elements suggest silica precipitation by hydrothermal fluids as the main process of chert formation with a contamination from volcanoclastic detritus. This is supported by the occurrence of hydrothermal-derived minerals in the studied samples indicating precipitation temperatures up to 350 °C. Only a dolomitic stromatolite from Strelley Pool shows a superchondritic Y/Ho ratio of 72 and a positive Eu/Eu^* anomaly of 1.8, characteristic of chemical precipitates from the Archean seawater. The bulk δ¹³C vs. δ¹⁵N values measured in the cherts show a roughly positive co-variation, except for one sample from the North Pole (PI-85-00). The progressive enrichment in ¹⁵N and ¹³C from a pristine source having δ¹³C ? −36‰ and δ¹⁵N ? −4‰ is correlated with a progressive depletion in N content and to variations in Ba/La and Co/As ratios. These trends have been interpreted as a progressive hydrothermal alteration of the cherts by metamorphic fluids. Isotopic exchange at 350 °C between NH₄⁺_(rock) and N_2(fluid) may explain the isotopic and elemental composition of N in the studied cherts. However, we need to assume isotopic exchange at 350 °C between carbonate C and graphite to explain the large ¹³C enrichment recorded. Only sample PI-85-00 shows a large N loss (90%) with a positive δ¹⁵N value (+11‰), while C (up to 120 ppm and δ¹³C −38‰) seems to be unaffected. This pattern has been interpreted as the result of devolatilization and alteration (oxidation) of graphite by low-temperature fluids. The ¹⁵N-¹³C-depleted pristine source has δ ¹⁵N values from −7‰ to −4‰ and ⁴⁰Ar/³⁶Ar ratios from 30,000 to 60,000, compatible with an inorganic mantle N source, although the elemental abundance ratios N/C and ⁴⁰Ar/C are not exactly the same with the mantle source. The component alternatively could be explained by elemental fractionation from metabolic activity of chemolithoautotrophs and methanogens at the proximity to the hydrothermal vents. However, ambiguities between mantle vs organic sources of N subsist and need further experimental work to be fully elucidated.     

黔南坳陷油苗来源:碳、硫同位素及生物标志物证据

为明确黔南坳陷不同层位油苗来源,在广泛采集不同层位烃源岩、油苗样品的基础上,采用GC、GC-MS及GC-IRMS等方法对其碳、硫同位素及生物标志物特征进行系统分析,进而开展了油源对比.结果表明:油苗的δ13C值为-33.04‰～-31.63‰,平均-32.26‰(n=18);δ34S值为+16.06‰～+23.06‰,平均+18.99‰(n=4);油苗遭受不同程度生物降解,常规甾、萜烷面貌特征差异较大,但普遍含有较丰富的三环萜烷、伽玛蜡烷、三芳甾烷、芳基类异戊二烯烃、惹烯和硫芴;C25三环萜烷/C24四环萜烷值、二苯并噻吩/菲与Pr/Ph相关图表明油苗为典型海相原油;Ts/(Ts +Tm)、C29甾烷20S/(20S+ 20R)及甲基菲指数等均表明油苗为成熟-高熟原油.研究区下寒武统牛蹄塘组黑色泥岩干酪根δ13C值为-35.79‰～-29.88‰,平均-32.85‰(n=35),与油苗相关性良好,而泥盆系、石炭系和二叠系烃源岩δ13C值显著偏重,均大于-29‰;下寒武统牛蹄塘组黑色泥岩干酪根δ34S值为+ 14.78‰～+ 17.60‰,平均+16.32‰(n=4),与油苗具有很好的可比性,而下、中泥盆统黑色泥岩干酪根δ34S值分别为-9.10‰～-6.78‰和+0.63‰～ +7.93‰,二叠系煤系地层有机质δ34S值为-7.40‰～+4.00‰,均显著偏轻.此外,下寒武统黑色泥岩普遍含有较丰富的伽玛蜡烷、三芳甾烷、芳基类异戊二烯烃和惹烯,三芴系列中硫芴含量极高,其它几套黑色泥岩则不合或贫含三芳甾烷和惹烯,伽玛蜡烷和硫芴含量亦较低.综合认为油苗具相同来源,且均与研究区下寒武统黑色泥岩具有较好亲缘关系.     

A hydrothermal origin for the large Xinqiao Cu-S-Fe deposit,Eastern China: Evidence from sulfide geochemistry and sulfur isotopes

The Xinqiao Cu-S-Fe deposit in the Tongling ore district, Middle-Lower Yangtze River Valley Metallogenic Belt (MLYB; Eastern China), is located along the northern margin of the Yangtze Craton. The stratiform- and skarn-type Xinqiao mineralization comprises five stages, namely the early skarn (Stage I, garnet and diopside), late skarn (Stage II, epidote-dominated), iron oxides (Stage III, hematite and magnetite), colloform pyrite (Stage IV) and quartz-sulfides (Stage V). There are three pyrite types at Xinqiao, i.e., colloform (Py1; Stage IV), fine-grained (Py2, from Py1 recrystallization; Stage V) and coarse-grained (Py3; Stage V) pyrites.Scanning Electron Microscope (SEM) imagery for Py1 reveals that they are cubic microcrystalline pyrite aggregates, and the EDS and XRD data indicate that some Py1 contain minor siderite impurities. Electron Microprobe Analysis (EMPA) and LA-ICP-MS geochemical data demonstrate that the three pyrite types have relatively high Fe/S ratios and distinctly high Mn, Cu and As concentrations. Compared to Py2 and Py3, Py1 has higher Pb, Bi and Ag, but lower Co, Ni, Se, Cd, Te and Au. Ratios of Fe/S (0.837 to 0.906), Se/Te (2.39 to 14.50) and Co/Ni (0.67 to 4.67) of the Xinqiao pyrites resemble typical hydrothermal pyrites. δ³⁴S_CDT of Py1 (− 0.6‰ to 2.7‰, average 0.58‰), Py2 (1.8‰ to 2.5‰, average 2.1‰) and Py3 (1.9‰ to 4.4‰, average 3.5‰) are close to those of the Xinqiao skarn-type orebodies (1.3‰ to 4.1‰), but distinct from those of the Upper Carboniferous Huanglong Formation limestone (− 9.5‰ to − 15.4‰), suggesting that the three pyrite types (especially Py1) were genetically linked to the Yanshanian (Jurassic-Cretaceous) magmatic-hydrothermal events, with Py1 probably reflecting rapid crystallization during fluid mixing. We interpret that the Xinqiao stratiform mineralization may have been associated with the Jitou quartz diorite stock, as may be the case also for the skarn-type mineralization hosted in the contact between the Yanshanian Jitou stock and the Lower Permian Qixia Formation limestone. Overall, the Xinqiao Cu-S-Fe mineralization may have been generated by the Jurassic-Cretaceous tectono-thermal event in Eastern China.     

Terrestrial alteration of carbonate in a suite of Antarctic CM chondrites: Evidence from oxygen and carbon isotopes

The oxygen (δ¹⁸O, δ¹⁷O) and carbon (δ¹³C, FMOD¹⁴C-the fraction of modern ¹⁴C) isotopic compositions of carbonate were measured for a set of paired Antarctic CM chondrites (EET 96006, EET 96016, EET 96017, and EET 96019). While the oxygen isotopic compositions do not plot on the terrestrial fractionation line and indicate that a component of the carbonate minerals has an extraterrestrial origin, they also do not fall on the array defined for carbonates by CM falls and are thus consistent with the presence of a terrestrial carbonate component. The δ¹³C and FMOD¹⁴C measurements of carbonate suggest the presence of at least two carbon sources: carbonate derived from atmospheric CO₂ that is inferred to have been produced as a result of silicate weathering reactions and carbonate derived from another carbon source that is either old or non-atmospheric. The relationships between oxygen and carbon isotope data provide additional constraints on the weathering process, and allow the possibility that rock-dominated weathering of the meteorite caused the oxygen isotopic composition of Antarctic water added to the meteorite to evolve away from the terrestrial mass-fractionation array, leading to formation of low temperature terrestrial alteration products that do not lie on the terrestrial fractionation line.     

Middle to Late Pleistocene environments based on stable organic carbon and nitrogen isotopes of loess-palaeosol sequences from the Carpathian Basin

Stable organic carbon and nitrogen isotopes can be used to interpret past vegetation patterns and ecosystem qualities. Here we present these proxies for two loess-palaeosol sequences from the southern Carpathian Basin to reconstruct the palaeoenvironment during the past 350 ka and establish regional commonalities and differences. Before now, isotopic studies on loess sequences from this region were only conducted on deposits from the last glacial cycle. We conducted methodological tests involving the complete decalcification of the samples prior to stable isotope analyses. Two decalcification methods (fumigation method and wet chemical acidification), different treatment times, and the reproducibility of carbon isotope analyses were tested. Obtained results indicate that the choice of the decalcification method is important for organic carbon stable isotope analyses of loess-palaeosol sequences because ratios vary by more than 10‰ between the wet chemical and fumigation methods, due to incomplete carbonate removal by the latter. Therefore, we suggest avoiding the fumigation method for studies on loess-palaeosol sequences. In addition, our data show that samples with TOC content <0.2% bear increased potential for misinterpretation of their carbon isotope ratios. For our sites, C₃-vegetation is predominant and no palaeoenvironmental shifts leading to a change of the dominant photosynthesis pathway can be detected during the Middle to Late Pleistocene. Furthermore, the importance of further stable nitrogen isotope studies is highlighted, since this proxy seems to reflect past precipitation patterns and reveals favourable conditions in the southern Carpathian Basin, especially during interstadials.     

生物气CO2还原途径中碳同位素分馏作用研究及应用

地质历史中,CO2/H2还原产甲烷作用对生物气的形成具有十分重要的意义。中国柴达木盆地第四系生物气主要为CO2/H2还原型生物气。笔者以CO2/H2还原生气理论为指导,进行不同初始碳同位素值和不同赋存状态碳源的生物模拟实验,研究CO2/H2还原产气过程中发生的碳同位素分馏作用。实验结果表明,产物中δ13CH4值与底物的δ13C值呈很好的正相关关系;在反应母质过量的情况下,碳源的赋存状态可以影响产物甲烷的碳同位素组成。以游离形式CO2还原产生的甲烷δ13C值,相对于以HCO3-、CO23-离子形式产生的甲烷δ13C值轻。通过柴达木盆地东部第四系生物气田实例分析,探讨了该区生物气的主要底物CO2的来源及赋存状态,对评价盆地生物气资源和有利勘探区预测有重要的参考价值。     

Rate of growth of the preserved North American continental crust: Evidence from Hf and O isotopes in Mississippi detrital zircons

Detrital zircons from the Mississippi River have been analyzed for U-Th-Pb, Lu-Hf and O isotopes to constrain the rate of growth of the preserved North American continental crust. One hundred and forty two concordant zircon U/Pb dates on grains mounted in epoxy, obtained by Excimer laser ablation ICP-MS method, resolved six major periods of zircon crystallization: 0-0.25, 0.3-0.6, 0.95-1.25, 1.3-1.5, 1.65-1.95 and 2.5-3.0 Ga. These age ranges match the ages of the recognized lithotectonic units of the North American continent in the hinterland of the Mississippi River. Ninety-six zircons mounted on tape, which show no age zonation and were within 7.5% of concordance, were selected to represent the six U/Pb age time intervals and analyzed for Lu-Hf and O isotope by laser ablation MC-ICP-MS and SHRIMP II, respectively. The δ¹⁸O values of the zircons show a small step increase in the maximum δ¹⁸O values at the Archean-Proterozoic boundary from 7.5‰ in the Archean to 9.5‰, and rarely 13‰, in the Proterozoic and Phanerozoic. However, the average value of δ¹⁸O in zircons changes little with time, showing that the increase in the maximum δ¹⁸O values between 2.5 and 2.0 Ga, which can be attributed to an increase in the sediment content of the source regions of younger granitoids, is largely balanced by an increase in zircons with anomalously low δ¹⁸O, which can be attributed to hydrothermally altered crust in the granitoid source region.εHf_i values for the zircons range from 13.1 to −26.9. Zircons derived from juvenile crust, which we define as having mantle δ¹⁸O (4.5-6.5‰) and lying within error of the Hf depleted mantle growth curve, are rare or absent in the Mississippi basin. The overwhelming majority of zircons crystallized from melted pre-existing continental crust, or mantle-derived magmas that were contaminated by continental crust. The average time difference between primitive crust formation and remelting for each of the recognized lithotectonic time intervals, which is defined as crustal incubation time in this study, is 890 ± 460 Myr. There is also a suggestion that the crustal incubation time increases with decreasing age in the Mississippi basin, which is consistent with the declining role of radioactive heat production in the lower crust with time.The average Hf model age (1.94 Ga), weighted by fraction of zircons in the river load is in reasonable agreement with the Nd model age (1.7 Ga) for the Mississippi River. However, if the zircons are weighted by the area of North America covered by the six recognized periods of zircon crystallization the average model age is 2.35 Ga, which compares favorably with an area weighted Nd model age of 2.36 Ga. Our preferred approach is to use the measured O isotope values to constrain variations in the ¹⁷⁶Lu/¹⁷⁷Hf ratio of the granitic source region from which the zircons crystallized, making the assumption that zircons with mantle-like O isotopic ratios have higher ¹⁷⁶Lu/¹⁷⁷Hf than zircons with higher O isotope values. This method gives an average Hf model age of 2.53 Ga, which is 180 Myr older than the constant ¹⁷⁶Lu/¹⁷⁷Hf calculation.The area weighted zircon Hf model ages show two distinct periods of crust formation for the North American continent, 1.6-2.2 and 2.9-3.4 Ga. At least 50% of the preserved North American continental crust was extracted from the mantle by 2.9 Ga and 90% by 1.6 Ga. Two similar periods of crustal growth are also recognized in Gondwana (Hawkesworth C. J. and Kemp A. I. S. (2006) Using hafnium and oxygen isotopes in zircons to unravel the record of crustal evolution. Chem. Geol.226, 144-162.), suggesting that these may be periods of global continental crustal growth. However, we stress that more data from other continents are required before the hypothesis of episodic global continental growth can be accepted with confidence.     

The genesis of calcite in carbonate rocks of the sedimentary basins: Evidence from the stable carbon and oxygen isotopes composition

The distributions of stable carbon and oxygen isotopes in modern and ancient limestones of various types were studied. Carbonate samples from modern sediments were collected in the Black and Barents Seas. Ancient carbonates were represented by Upper Jurassic (Kimmeridgian-Tithonian) limestones from the central part of the West Siberian basin. Carbonate samples include remains of modern and Upper Jurassic fauna, carbonate crust from sediments of the Black Sea, carbonate tube from sediments of the Barents Sea, and Upper Jurassic limestone from the carbonate layer found at top of Abalak, bottom of Bazhenov deposits in the central part of the West Siberian basin. According to the results of the isotope analysis and comparison with modern carbonates, Upper Jurassic limestones of the West Siberian basin belong to the group of methane-derived carbonates and precipitated as a result of anaerobic oxidation of methane (AOM). Fractures in limestones are filled with secondary calcite.     

山东沂南金铜铁矿床中的液态不混溶作用与成矿：流体包裹体和氢氧同位素 证据

沂南矽卡岩型金铜铁矿床产于燕山期中酸性侵入岩与新太古界—寒武系地层接触带附近。氢、氧同位素研究表明,早期干矽卡岩阶段(Ⅰ)和湿矽卡岩-磁铁矿阶段(Ⅱ)的成矿流体主要为岩浆水,晚期石英-硫化物阶段(Ⅲ)和碳酸盐阶段(Ⅳ)的成矿流体则显示有大气降水混入的岩浆水特点。流体包裹体研究表明,成矿各阶段热液矿物中的包裹体类型丰富,以气液两相盐水包裹体、含子晶多相包裹体和CO2-H2O包裹体为主,次为纯液相水包裹体和纯气相水包裹体,偶见晶质熔融包裹体。由Ⅰ→Ⅱ→Ⅲ→Ⅳ阶段,气液水包裹体均一温度(520～430℃→430～340℃→250～190℃→190～130℃)呈现逐渐降低的趋势。在Ⅰ、Ⅱ阶段的石榴子石和绿帘石中,晶质熔融包裹体与同期次捕获的具不同气相分数的气液水包裹体及含子晶的多相包裹体共生,表明它们被捕获时是一种熔体与流体共存的不混溶状态。在Ⅲ阶段的石英(少量Ⅱ阶段的绿帘石)中,常见气相充填度变化很大的气液水包裹体与同期次捕获的纯液相水包裹体、纯气相水包裹体、含子晶的多相包裹体以及CO2-H2O包裹体共生,且共生的不同类型包裹体均一温度相近,表明此阶段成矿流体曾发生过广泛的沸腾(不混溶)。因而认为,在沂南矿床由岩浆...     

Diamonds from the Poiskovaya,Zapolyarnaya, and Leningrad kimberlite pipes,Northern Yakutia: Correlation of carbon isotopic composition and nitrogen content as an indicator of fluid diamond formation

Compared to most studied kimberlite pipes of the Yakutian province, diamonds from the Poiskovaya, Zapolyarnaya, and Leningrad pipes (about 100 determinations) are characterized by a decrease in the average δ¹³C (−4.59, −4.50,−4.04‰) and by relatively low average nitrogen contents (93, 254, 304 ppm, respectively). These pipes also differ in the relative abundance of alpha-1 group crystals in Galimov’s classification. Based on a stable combination of morphology and properties, we distinguished diamond populations of the common origin. All of them have significant a negative correlation between δ¹³C and the nitrogen content. This correlation is considered to be a result of synchronous and progressive loss of nitrogen and the light isotope ¹²C in the medium during the diamond formation. The conclusion is drawn that the alpha-1 crystals were formed in the open fluid system. The pyrolysis of ethane—C₂H₆ → CH₄ + H₂ + C_diam—is assumed to be a model of diamond precipitation from fluid. The pressure release due to extension deformation of the mantle under tectonic action might be a factor shifting this reaction toward diamond formation.