好氧不产氧光合细菌反馈作用下的五里峡水库坝前水体化学特征研究

微生物是水体生物地球化学循环的主要驱动者,也是能量代谢的主要参与者,在水体生态系统多样性与稳定性方面发挥着举足轻重的作用。好氧不产氧光合细菌(AAPB)是水体中一类分布广泛的重要功能类群,它们可利用光能补充自身能量代谢,并影响水体化学组分,其重要性被人们广泛认可并深入研究。为探讨岩溶区AAPB反馈作用下的五里峡水库坝前水体化学特征,本文对坝前不同层位水体进行实地监测,在获得不同层位水体溶解有机碳和颗粒有机碳稳定碳同位素特征的基础上,采用荧光定量PCR技术检测、研究了坝前水体不同层位AAPB分布规律。结果表明:取样期五里峡水库坝前水体为HCO_3~--Ca~(2+)-Mg~(2+)贫-中营养型;通过水体溶解氧、δ~(13)CPOC、δ~(13)CDOC和碳氮比综合分析得出,坝前水体有机碳主要由微型生物产生;AAPB占总浮游细菌的相对丰度范围在1.33%~1.60%,且AAPB在不同层位的丰度变化强度要高于总浮游细菌的丰度变化强度,表明相较于总浮游细菌,AAPB对水化学特征的反馈作用更加敏感;使用典范对应分析可揭示水体理化性质与AAPB的内在联系,结果显示AAPB和总浮游细菌均受浊度的影响较大,故基于颗粒沉降的海洋微生物泵作用也适用于陆地岩溶水库。因而,AAPB反馈作用下的水化学特征对揭示CO_2-水-碳酸盐岩-微生物代谢体系具有重要的启示意义。     

Determination of Sm‐Nd Isotopic Compositions in Fifteen Geological Materials Using Laser Ablation MC‐ICP‐MS and Application to Monazite Geochronology of Metasedimentary Rock in the North China Craton

In this study, we report both ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd values in twelve minerals (apatite, titanite, monazite and eudialyte) based on analyses over 4 years using LA‐MC‐ICP‐MS. The positive correlation between the measured β_Sm and β_Nd (r² = 0.9981) over this time in our laboratory demonstrates the excellent long‐term stability of the method. Compared with the normal method, Sm and Nd signal intensities were improved by a factor of 2.9 with the use of X skimmer and Jet sample cones in combination with the addition of nitrogen at 3–6 ml min^?1 to the central gas flow. The enhancement of signal intensity benefits the accurate in situ determination of the Sm‐Nd isotopes of samples poor in these elements. ¹⁴³Nd/¹⁴⁴Nd values were also determined in two manganese nodules and GSMC Co‐rich crust with low mass fractions of Nd (94–293 μg g^?1). Generally, most of the obtained Sm‐Nd isotopic compositions in these geological materials are consistent with published values. ‘External reproducibility’ (2s) of ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd was typically better than 0.06‰ and 2.5‰, respectively, demonstrating that the Durango, Otter Lake, NW‐1 and MAD apatites, the Khan, and OLT‐1 titanites, MGMH#117531 monazite and LV01 eudialyte are promising candidate reference materials for in situ Sm‐Nd isotopic determinations. The Trebilcock, Mae Klang and 44069 monazites are only suitable for in situ Nd isotopic determinations because of their heterogeneous Sm/Nd compositions. The heterogeneous Sm‐Nd composition of titanite BLR‐1 demonstrates that it is not a suitable reference material for in situ Sm‐Nd isotopic determinations. Deep‐sea samples (NOD‐A‐1 and NOD‐P‐1 manganese nodule, GSMC Co‐rich crust) with low mass fractions of Nd also show homogenous Nd isotopic compositions. Sm‐Nd isotopic ratios of a monazite (MQG‐22) from the North China Craton were measured as a case study and gave a ¹⁴⁷Sm‐¹⁴³Nd isochron age of 1792 ± 35 Ma (MSWD = 3.2) consistent with the published metamorphic age of the host metasedimentary rocks. The results for both candidate reference materials and geological samples demonstrate that the in situ LA‐MC‐ICP‐MS analytical protocol described is feasible and robust for research in geological evolution.     

Rhenium‐Osmium Isotope Measurements of Geological Reference Material BIR‐1a: Evaluation of Homogeneity and Implications for Method Validation and Quality Control

To evaluate the homogeneity of geological reference material BIR‐1a (basalt; United States Geological Survey, USGS) for Re‐Os isotopic studies at the 0.2–1.0 g test portion size level, sixty‐three precise measurement results of Re and Os mass fractions and isotope amount ratios were obtained over an 18‐month period. These data reveal that the reference material has higher Re (0.691 ± 0.022 ng g^?1, 2s, n = 63) and lower Os mass fractions (0.343 ± 0.089 ng g^?1, 2s, n = 63) than UB‐N (serpentinite, CRPG) and is homogeneous in ¹⁸⁷Os/¹⁸⁸Os isotope amount ratio (0.13371 ± 0.00092, 2s, n = 63) at the 0.2–1.0 g test portion size level. The results are essentially consistent with previous views indicating that BIR‐1a gives precise measurement results for Re‐Os isotope amount ratio measurements at the 1 g test portion size level (Ishikawa et al., Chemical Geology, 2014, 384, 27–46; Meisel and Horan, Reviews in Mineralogy and Geochemistry, 2016, 81, 89–106). Based on these new Re‐Os data and previous studies, we propose BIR‐1a as a useful reference material that can be used in method validation and quality control and interlaboratory comparisons for studies dealing with mafic geological samples at test portion sizes of > 0.4 g.     

Evaluation of the effects of alteration and leaching on Sm–Nd and Lu–Hf systematics in submarine mafic rocks

Nd and Hf isotope systematics of oceanic basaltic rocks are often assumed to be largely immune to the effects of hydrothermal alteration. We have tested this assumption by comparing Nd and Hf isotope data for acid-leached Cretaceous oceanic basalts from Gorgona and DSDP Leg 15 with unleached data on the same rocks. Hf isotope values and Lu/Hf ratios are relatively unaffected by leaching, but ¹⁴³Nd/¹⁴⁴Nd values of leached samples are significantly higher than those of unleached fractions of the same sample in most cases. Furthermore, the Sm/Nd ratios of the majority of leached samples are 10–40% greater than those of unleached samples. X-ray diffraction studies indicate that selective removal of secondary minerals, such as smectite, during the acid leaching process is responsible for the fractionation of Sm/Nd ratios. These results have implications for interpretation of the Hf–Nd isotope systematics of ancient submarine rocks (older than ~ 50 Ma), as (1) the age-corrected ¹⁴³Nd/¹⁴⁴Nd ratio may not be representative of the primary magmatic signature and (2) the uncertainty of the age-corrected ε_Nd value may exceed the assumed analytical precision.     

Precise Determination of Sm and Nd Concentrations and Nd Isotopic Compositions in Highly Depleted Ultramafic Reference Materials

In this study, a high‐precision method for the determination of Sm and Nd concentrations and Nd isotopic composition in highly depleted ultramafic rocks without a preconcentration step is presented. The samples were first digested using the conventional HF + HNO₃ + HClO₄ method, followed by the complete digestion of chromite in the samples using HClO₄ at 190–200 °C and then complete dissolution of fluoride formed during the HF decomposition step using H₃BO₃. These steps ensured the complete digestion of the ultramafic rocks. The rare earth elements (REEs) were separated from the sample matrix using conventional cation‐exchange chromatography; subsequently, Sm and Nd were separated using the LN columns. Neodymium isotopes were determined as NdO⁺, whereas Sm isotopes were measured as Sm⁺, both with very high sensitivity using single W filaments with TaF₅ as an ion emitter. Several highly depleted ultramafic rock reference materials including USGS DTS‐1, DTS‐2, DTS‐2b, PCC‐1 and GSJ JP‐1, which contain extremely low amounts of Sm and Nd (down to sub ng g^?1 level), were analysed, and high‐precision Sm and Nd concentration and Nd isotope data were obtained. This is the first report of the Sm‐Nd isotopic compositions of these ultramafic rock reference materials except for PCC‐1.     

The Diamantina Monazite: A New Low‐Th Reference Material for Microanalysis

Most monazite reference materials (RMs) for in situ U‐Pb geochronology are rich in Th; however, many hydrothermal ore deposits contain monazite that is low in trace element contents, including Th, U and Pb. Because of potential problems with matrix effects and the lack of appropriate matrix‐matched RMs, such variations can bias dating of hydrothermal deposits. In this paper, we describe a polycrystalline low‐U and low‐Th Diamantina monazite from the Espinhaço Range, SE Brazil. It has a U‐Pb ID‐TIMS weighted mean ²⁰⁷Pb^*/²³⁵U ratio of 0.62913 ± 0.00079, ²⁰⁶Pb^*/²³⁸U of 0.079861 ± 0.000088 and ²⁰⁷Pb^*/²⁰⁶Pb^* of 0.057130 ± 0.000031, yielding a weighted mean ²⁰⁶Pb^*/²³⁸U date of 495.26 ± 0.54 Ma (95% c.l.). In situ dates acquired with different methods (LA‐(Q, SF, MC)‐ICP‐MS and SIMS) are within uncertainty of the ID‐TIMS data. U‐Pb LA‐(Q, MC)‐ICP‐MS runs, using Diamantina as a primary RM, reproduced the ages of other established RMs within < 1% deviation. The LA‐MC‐ICP‐MS analyses yielded homogeneous Sm‐Nd isotopic compositions (¹⁴³Nd/¹⁴⁴Nd = 0.511427 ± 23, 2s; ¹⁴⁷Sm/¹⁴⁴Nd = 0.1177 ± 13, 2s) and εNd_(495 Ma) of ?18.7 ± 0.5 (2s). SIMS oxygen isotope determinations showed measurement reproducibility better than ± 0.3‰ (2s), confirming Diamantina's relative homogeneity at test portion masses below 1 ng.     

High-precision Measurements of the 143Nd/144Nd Isotope Ratio in Certified Reference Materials without Nd and Sm Separation by MC-ICP-MS

A precise and accurate method for the determination of 143 Nd/144 Nd isotope ratio without Nd and Sm separation by multiple collector inductively coupled plasma mass spectrometry is demonstrated in this paper.     

Antarctic Ice‐Core Water (USGS49) – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice‐core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual‐inlet isotope‐ratio mass spectrometry. The δ²H and δ¹⁸O values of USGS49 are ?394.7 ± 0.4 and ?50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), respectively, relative to VSMOW, on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5 mUr. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95% probability of encompassing the true value. This isotopic reference material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope‐ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.     

Re-evaluating Nd/Nd in lunar mare basalts with implications for the early evolution and bulk Sm/Nd of the Moon

The Moon likely accreted from melt and vapor ejected during a cataclysmic collision between Proto-Earth and a Mars-sized impactor very early in solar system history. The identical W, O, K, and Cr isotope compositions between materials from the Earth and Moon require that the material from the two bodies were well-homogenized during the collision process. As such, the ancient isotopic signatures preserved in lunar samples provide constraints on the bulk composition of the Earth. Two recent studies to obtain high-precision ¹⁴²Nd/¹⁴⁴Nd ratios of lunar mare basalts yielded contrasting results. In one study, after correction of neutron fluence effects imparted to the Nd isotope compositions of the samples, the coupled ¹⁴²Nd-¹⁴³Nd systematics were interpreted to be consistent with a bulk Moon having a chondritic Sm/Nd ratio [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372]. The other study found that their data on the same and similar lunar mare basalts were consistent with a bulk Moon having a superchondritic Sm/Nd ratio [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516]. Delineating between these two potential scenarios has key ramifications for a comprehensive understanding of the formation and early evolution of the Moon and for constraining the types of materials available for accretion into large terrestrial planets such as Earth.To further examine this issue, the same six lunar mare basalt samples measured in Rankenburg et al. [Rankenburg K., Brandon A. D. and Neal C. R. (2006) Neodymium isotope evidence for a chondritic composition of the Moon. Science312, 1369-1372] were re-measured for high-precision Nd isotopes using a multidynamic routine with reproducible internal and external precisions to better than ±3 ppm (2σ) for ¹⁴²Nd/¹⁴⁴Nd ratios. The measurements were repeated in a distinct second analytical campaign to further test their reproducibility. Evaluation of accuracy and neutron fluence corrections indicates that the multidynamic Nd isotope measurements in this study and the 3 in Boyet and Carlson [Boyet M. and Carlson R. W. (2007) A highly depleted Moon or a non-magma origin for the lunar crust? Earth Planet. Sci. Lett.262, 505-516] are reproducible, while static measurements in the previous two studies show analytical artifacts and cannot be used at the resolution of 10 ppm to determine a bulk Moon with either chondritic or superchondritic Sm/Nd ratios. The multidynamic data are best explained by a bulk Moon with a superchondritic Sm/Nd ratio that is similar to the present-day average for depleted MORB. Hafnium isotope data were collected on the same aliquots measured for their ¹⁴²Nd/¹⁴⁴Nd isotope ratios in order to assess if the correlation line for ¹⁴²Nd-¹⁴³Nd systematics reflect mixing processes or times at which lunar mantle sources formed. Based on the combined ¹⁴²Nd-¹⁴³Nd-¹⁷⁶Hf obtained we conclude that the ¹⁴²Nd-¹⁴³Nd correlation line measured in this study is best interpreted as an isochron with an age of 229⁺²⁴₋₂₀Ma after the onset of nebular condensation. The uncertainties in the data permit the sources of these samples to have formed over a 44 Ma time interval. These new results for lunar mare basalts are thus consistent with a later Sm-Nd isotope closure time of their source regions than some recent studies have postulated, and a superchondritic bulk Sm/Nd ratio of the Moon and Earth. The superchondritic Sm/Nd signature was inherited from the materials that accreted to make up the Earth-Moon system. Although collisional erosion of crust from planetesimals is favored here to remove subchondritic Sm/Nd portions and drive the bulk of these bodies to superchondritic in composition, removal of explosive basalt material via gravitational escape from such bodies, or chondrule sorting in the inner solar system, may also explain the compositional features that deviate from average chondrites that make up the Earth-Moon system. This inferred superchondritic nature for the Earth similar to the modern convecting mantle means that there is no reason to invoke a missing, subchondritic reservoir to mass balance the Earth back to chondritic for Sm/Nd ratios. However, to account for the subchondritic Sm/Nd ratios of continental crust, a second superchondritic Sm/Nd mantle reservoir is required.     

Natural Titanite Reference Materials for In Situ U‐Pb and Sm‐Nd Isotopic Measurements by LA‐(MC)‐ICP‐MS

Titanite is a common accessory mineral that preferentially incorporates considerable amounts of U and light rare earth elements in its structure, making it a versatile mineral for in situ U‐Pb dating and Sm‐Nd isotopic measurement. Here, we present in situ U‐Pb ages and Sm‐Nd isotope measurement results for four well‐known titanite reference materials (Khan, BLR‐1, OLT1 and MKED1) and eight titanite crystals that could be considered potential reference material candidates (Ontario, YQ‐82, T3, T4, TLS‐36, NW‐IOA, Pakistan and C253), with ages ranging from ~ 20 Ma to ~ 1840 Ma. Results indicate that BLR‐1, OLT1, Ontario, MKED1 and T3 titanite have relatively homogeneous Sm‐Nd isotopes and low common Pb and thus can serve as primary reference materials for U‐Pb and Sm‐Nd microanalysis. YQ‐82 and T4 titanite can be used as secondary reference materials for in situ U‐Pb analysis because of their low common Pb. However, internal structures and mineral inclusions in YQ‐82 will require careful selection of suitable target domains. Pakistan titanite is almost concordant with an age of 21 Ma and can be used as a reference material when dating Cenozoic titanite samples.     

In search of a hidden long-term isolated sub-chondritic Nd/Nd reservoir in the deep mantle: Implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic ¹⁴²Nd/¹⁴⁴Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic ¹⁴³Nd/¹⁴⁴Nd and high ²⁰⁷Pb/²⁰⁶Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic ¹⁴²Nd/¹⁴⁴Nd.High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable ¹⁴²Nd/¹⁴⁴Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle.We then evaluate mass balance in the Earth with respect to both ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε¹⁴³Nd estimates of the reservoirs in the μ¹⁴²Nd = 0 Earth, where μ¹⁴²Nd is ((measured ¹⁴²Nd/¹⁴⁴Nd/terrestrial standard ¹⁴²Nd/¹⁴⁴Nd)−1 * 10⁻⁶) and the μ¹⁴²Nd = 0 Earth is the proportion of the silicate Earth with ¹⁴²Nd/¹⁴⁴Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd unless the μ¹⁴²Nd = 0 Earth has a ε¹⁴³Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age ¹⁴²Nd-¹⁴³Nd isochron for the Earth intersects μ¹⁴²Nd = 0 at ε¹⁴³Nd of +8 ± 2 providing a minimum ε¹⁴³Nd for the μ¹⁴²Nd = 0 Earth. The high ε¹⁴³Nd of the μ¹⁴²Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε¹⁴³Nd.If the EER formed early after solar system formation (0-70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ¹⁴²Nd = 0 Earth must have a bulk ε¹⁴³Nd more radiogenic than DMM and additional high ε¹⁴³Nd material is required to balance the Nd isotope systematics of the Earth.     

岩石铷-锶和钐-钕同位素标准物质的研制

通常样品的⁸⁷Sr/⁸⁶Sr和¹⁴³Nd/¹⁴⁴Nd同位素比值分析采用SRM9⁸⁷、JNdi-1作为标准物质,它们分别是纯的碳酸盐和氧化物,适用于监控质谱测试过程。中国现有的钐-钕地质和铷-锶年龄标准物质,分别为玄武岩和钾长石,它们与很多地质样品的基质存在差别。仅有这两种基质的标准物质不能有效地监控不同地质样品Rb-Sr、Sm-Nd同位素分析过程,因此研制不同岩性的Rb-Sr、Sm-Nd同位素标准物质具有重要现实意义。本文采集中国典型地区的橄榄岩、榴辉岩和花岗岩作为候选物,严格按照《一级标准物质技术规范》(JJF 1006-1994)和《标准物质定值的通用原则及统计学原理》(JJF 1343-2012)等相关标准物质国家计量技术规范和国家标准,研制了橄榄岩、榴辉岩和花岗岩铷-锶、钐-钕同位素标准物质(编号为GBW04139、GBW04140、GBW04141),其中橄榄岩标准物质适用于高Mg、Fe,低Rb、Nd含量样品的分析,榴辉岩和花岗岩标准物质适用于含有难溶副矿物的岩石样品的分析。每个标准物质具有6个特性量值,Rb、Sr、Sm和Nd含量分布分别为0.16~64μg/g、12~560μg/g、0.1~3.2μg/g和0.3~15.3μg/g,⁸⁷Sr/⁸⁶Sr比值分布为0.70446~0.71309,¹⁴³Nd/¹⁴⁴Nd比值分布为0.51115~0.51267,同位素比值精度达到或优于同类标准物质。这些特性量值更接近实际样品,使用时将更加有效和方便。该系列标准物质可用于校准仪器和评价方法,并能有效监控实验室此类样品的铷-锶、钐-钕同位素分析过程。     

Fluorite as an Sm–Nd geochronometer of hydrothermal processes: Dating of mineralization hosted in the Strel’tsovka uranium ore field,eastern Baikal region

The possibility of using hydrothermal fluorite as an Sm–Nd geochronometer is based on the results of an REE pattern study of this mineral (Chernyshev et al., 1986). As a result of REE fractionation, in many cases, the Sm/Nd ratio achieves a multifold increase compared with its level in terrestrial rocks, and the radiogenic shift of the ¹⁴³Nd/¹⁴⁴Nd isotope ratio reaches 10–20 ε_Nd units over a short time interval (as soon as tens of Ma). This is a necessary prerequisite for Sm–Nd isochron dating of fluorite. Zonal polychrome fluorite from a vein referred to the final stage of large-scale uranium mineralization at the Sterl’tsovka deposit in the ore field of the same name located in the eastern Transbaikal region has been dated using the ¹⁴³Nd/¹⁴⁴Nd method. To optimize isochron construction, local probes with high and contrasting Sm/Nd ratios have been sampled from the polished surfaces of two samples, taking into account the REE pattern of zonal fluorite. Sm–Nd isochron dating has been carried out separately for each sample. The ¹⁴⁷Sm/¹⁴⁴Nd и ¹⁴³Nd/¹⁴⁴Nd ratios vary within the intervals 0.5359–2.037 and 0.512799–0.514105, respectively. Two isochrons, each based on six fluorite probes, have been obtained with the following parameters, which coincide within 2σ uncertainty limits: (1) t = 134.8 ± 1.3 Ma, (¹⁴³Nd/¹⁴⁴Nd)₀ = 0.512310 ± 13, MWSD = 0.43 and (2) t = 135.8 ± 1.6 Ma, (¹⁴³Nd/¹⁴⁴Nd)₀ = 0.512318 ± 10, MWSD = 1.5. The mean age of fluorite based on two isochron datings is 135.3 ± 1 Ma. Comparison of this value with the most precise dating of pitchblende related to the ore stage in the Strel’tsovka ore field (135.5 ± 1 Ma) shows that four mineralization stages, distinguished by geological and mineralogical data, that were completed with the formation of polychrome fluorite veins 135.3 ± 1 Ma ago, represent a single and indivisible hydrothermal process whose duration does not exceed 1 Ma.     

USGS46 Greenland Ice Core Water – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual‐inlet isotope‐ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ²H and δ¹⁸O values of this reference water were ?235.8 ± 0.7‰ and ?29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95‐percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.     

Barium Isotopic Compositions of Geological Reference Materials

The interest in variations of barium (Ba) stable isotope amount ratios in low and high temperature environments has increased over the past several years. Characterisation of Ba isotope ratios of widely available reference materials is now required to validate analytical procedures and to allow comparison of data obtained by different laboratories. We present new Ba isotope amount ratio data for twelve geological reference materials with silicate (AGV‐1, G‐2, BHVO‐1, QLO‐1, BIR‐1, JG‐1a, JB‐1a, JR‐1 and JA‐1), carbonate (IAEA‐CO‐9) and sulfate matrices (IAEA‐SO‐5 and IAEA‐SO‐6) relative to NIST SRM 3104a. In addition, two artificially fractionated in‐house reference materials BaBe12 and BaBe27 (δ^137/134Ba = ?1.161 ± 0.049‰ and ?0.616 ± 0.050‰, respectively) are used as quality control solutions for the negative δ‐range. Accuracy of our data was assessed by interlaboratory comparison between the University of Bern and the United States Geological Survey (USGS). Data were measured by MC‐ICP‐MS (Bern) and TIMS (USGS) using two different double spikes for mass bias correction (¹³⁰Ba–¹³⁵Ba and ¹³²Ba–¹³⁶Ba, respectively). MC‐ICP‐MS measurements were further tested for isobaric and non‐spectral matrix effects by a number of common matrix elements. The results are in excellent agreement and suggest data accuracy.     

Non-chondritic Sm/Nd ratio in the terrestrial planets: Consequences for the geochemical evolution of the mantle-crust system

Super-chondritic ¹⁴²Nd signatures are ubiquitous in terrestrial, Martian and lunar samples, and indicate that the terrestrial planets may have accreted from material with Sm/Nd ratio higher than chondritic. This contradicts the long-held view that chondrites represent a reference composition for the ¹⁴⁷Sm-¹⁴³Nd system. Using coupled ¹⁴⁶Sm-¹⁴²Nd and ¹⁴⁷Sm-¹⁴³Nd systematics in planetary samples, we have proposed a new set of values for the ¹⁴⁷Sm/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios of the bulk silicate Earth (Caro et al., 2008). Here, we revise the Bulk Silicate Earth estimates for the ⁸⁷Rb-⁸⁷Sr and ¹⁷⁶Lu-¹⁷⁶Hf systems using coupled Sr-Nd-Hf systematics in terrestrial rocks. These estimates are consistent with Hf-Nd systematics in lunar samples. The implications of a slightly non-chondritic silicate Earth with respect to the geochemical evolution of the mantle-crust system are then examined. We show that the Archean mantle has evolved with a composition indistinguishable from that of the primitive mantle until about 2 Gyr. Positive ε¹⁴³Nd and ε¹⁷⁶Hf values ubiquitous in the Archean mantle are thus accounted for by the non-chondritic Sm/Nd and Lu/Hf composition of the primitive mantle rather than by massive early crustal formation, which solves the paradox that early Archean domains only have a limited extension in the present-day continents. The Sm-Nd and Lu-Hf evolution of the depleted mantle for the past 3.5 Gyr can be entirely explained by continuous extraction of the continents from a well-mixed mantle. Thus, in contrast to the chondritic Earth model, Sm-Nd mass balance relationships can be satisfied without the need to call upon hidden reservoirs or layered mantle convection. This new Sm-Nd mass balance yields a scenario of mantle evolution consistent with trace element and noble gas systematics. The high ³He/⁴He mantle component is associated with ¹⁴³Nd/¹⁴⁴Nd compositions indistinguishable from the bulk silicate Earth, suggesting that the less degassed mantle sources did not experience significant fractionation for moderately incompatible elements.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

High-precision Nd/Nd measurements in terrestrial rocks: Constraints on the early differentiation of the Earth’s mantle

We present new ultra-high precision ¹⁴²Nd/¹⁴⁴Nd measurements of early Archaean rocks using the new generation thermal ionization mass spectrometer Triton. Repeated measurements of the Ames Nd standard demonstrate that the ¹⁴²Nd/¹⁴⁴Nd ratio can be determined with external precision of 2 ppm (2σ), allowing confident resolution of anomalies as small as 5 ppm. A major analytical improvement lies in the elimination of the double normalization procedure required to correct our former measurements from a secondary mass fractionation effect. Our new results indicate that metasediments, metabasalts, and orthogneisses from the 3.6 to 3.8 Ga West Greenland craton display positive ¹⁴²Nd anomalies ranging from 8 to 15 ppm. Using a simple two-stage model with an initial ε¹⁴³Nd value of 1.9 ± 0.6 ε-units, coupled ¹⁴⁷Sm-¹⁴³Nd and ¹⁴⁶Sm-¹⁴²Nd chronometry constrains mantle differentiation to 50-200 Ma after formation of the solar system. This chronological constraint is consistent with differentiation of the Earth’s mantle during the late stage of crystallization of a magma ocean. We have developed a two-box model describing ¹⁴²Nd and ¹⁴³Nd isotopic evolution of depleted mantle during the subsequent evolution of the crust-mantle system. Our results indicate that early terrestrial protocrust had a lifetime of ca. 0.7-1 Ga in order to produce the observed Nd isotope signature of Archaean rocks. In the context of this two box mantle-crust system, we model the evolution of isotopic and chemical heterogeneity of depleted mantle as a function of the mantle stirring time. Using the dispersion of ¹⁴²Nd/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios observed in early Archaean rocks, we constrain the stirring time of early Earth’s mantle to 100-250 Ma, a factor of 5 shorter than the stirring time inferred from modern oceanic basalts.     

Correlated nucleosynthetic isotopic variability in Cr, Sr, Ba, Sm, Nd and Hf in Murchison and QUE 97008

Acid leaching of the primitive C-chondrite Murchison and O-chondrite QUE 97008 reveal nucleosynthetic anomalies in Cr, Sr, Ba, Nd, Sm and Hf. The anomalies in all but Cr and Sm are best explained by variable additions of pure s-process nuclides to a background nebular composition slightly enriched in r-process isotopes compared to average Solar System material. Leaching leaves a residue in Murchison that is strongly enriched in s-process nuclides with depletions of over 0.1% in ¹³⁵Ba and seven parts in 10,000 in ⁸⁴Sr. If there are p-process anomalies in these two elements, they are lost in the variability caused by different r-, s-process contributions to the normalizing isotopes. The concentration and isotope systematics are consistent with the Ba and Sr isotopic composition in the Murchison residue being strongly influenced by s-process-rich presolar SiC. In general, the nucleosynthetic isotope anomalies are 2- to 5-fold smaller in QUE 97008 than in Murchison. The different magnitudes of isotope anomalies are similar to the difference in matrix abundance between CM and O chondrites consistent with the suggestion that the carriers of nucleosynthetically anomalous material preferentially reside in the matrix and that some of this material has been distributed throughout the O-chondrite minerals as a result of thermal metamorphism.Neodymium, Sm and Hf display variable s-, r-process nuclide abundances as in Ba and Sr, but the anomalies are much smaller (e.g. ε¹⁴⁸Nd, ε¹⁴⁸Sm = −5.7, 2.1, respectively, in Murchison and −0.43, 0.16, respectively in QUE 97008 residues). After correcting Nd and Sm for s-, r-process variability, Sm in whole rock chondrites shows variable relative abundances of the p-process isotope ¹⁴⁴Sm that correlate weakly with ¹⁴²Nd suggesting that the direct p-process contribution to ¹⁴²Nd is small (∼7-9%). Nucleosynthetic variability in Nd explains the range in ¹⁴²Nd/¹⁴⁴Nd seen between C and O, E-chondrites, but not the difference between chondrites and all modern Earth rocks, leaving decay of ¹⁴⁶Sm and a superchondritic Sm/Nd ratio as the likely explanation for Earth’s high ¹⁴²Nd/¹⁴⁴Nd.     

利用套柱法快速分离提纯Sr和Nd元素

样品放射性成因Sr-Nd同位素比值受控于源区初始同位素组成、放射性元素母体与子体相对丰度,以及衰变时间等因素。它们具有极强的示踪能力,因而在地质学领域有广泛的应用。传统的Sr-Nd同位素分析使用的是阳离子树脂,提纯Nd元素时往往涉及有机试剂以及调节pH值等操作,其分析效率较低。近年来特效树脂的出现使得分离这些元素变得简单,但是受硫酸根等因素影响,特效树脂使用次数有限。为了提高分析效率,缩短分析时间,本文开发了一种套柱法,该方法结合阳离子树脂和特效树脂,实现了Sr-Nd元素的快速分离,并且能延长特效树脂的使用寿命。实验采用阳离子树脂、Sr特效树脂和LN稀土特效树脂对玄武岩BCR-2标样进行了分析。Sr-Nd回收率均90%,BCR-2玄武岩~(87)Sr/~(86)Sr比值为0.705016±0.000016(n=36,1SD),~(143)Nd/~(144)Nd比值为0.512624±0.000012(n=39,1SD),与前人TIMS法获得的结果吻合(~(87)Sr/~(86)Sr:0.705000～0.705023;~(143)Nd/~(144)Nd:0.512630～0.512650)。最终分离提纯的溶液中~(85)Rb/~(86)Sr值小于0.01,~(147)Sm/~(144)Nd值小于0.001,表明该方法可以高效分离Rb-Sr和Sm-Nd,实现Sr、Nd同位素的准确分析。