Mercury isotope variations in surface soils in different contaminated areas in Guizhou Province, China

Guizhou Province is known as a heavily Hg-polluted area in China due to its special geochemical background and complicated Hg emission sources.In this study,we investigated the Hg isotope compositions of surface soil samples in the Hg mining area,zinc smelting area,coal combustion area,which are known to be the typical pollution regions of Hg in this province.We also compared the Hg isotopic fingerprints of primary Hg sources,such as hydrothermal Hg-bearing ores,coals and atmospheric Hg samples.According to our study,Hg stored in surface soils in different pollution regions in Guizhou Province displays a wide range of both mass dependent fractionation(MDF,δ202Hg) and mass independent fractionation(MIF,△199Hg).δ 202 Hg varies by 2.0‰ and △199Hg varies by 0.25‰ in the investigated surface soils.This study demonstrated that using a "MDF-MIF" two dimensional Hg isotope system could be particularly useful in discriminating Hg sources in soils.     

基于稳定同位素的SPAC系统水分转化研究进展

大气-土壤-植被连续体(soil-plant-atmosphere continuum, SPAC)系统水分转化过程是生态水文学重要的研究内容。稳定同位素作为天然的示踪剂能有效示踪、整合和指示SPAC系统中的水分输入、输出以及转化过程。笔者在简述稳定同位素应用原理的基础上，以垂直方向上SPAC系统水分运移的视角，阐释基于稳定同位素技术的土壤-根系界面水分运移、植物传输水分中存在的分馏和植物冠层-大气界面水分交换的研究进展，探讨了SPAC系统水分转化研究中稳定同位素技术在分馏机制、时间分辨率与空间异质性方面的局限性。认为未来基于稳定同位素的SPAC水分转化研究还需着重在以下3个方面进行：(1)借助广泛应用于其他领域的便携式同位素分析仪对各种同位素水池同位素组成进行原位观测；(2)结合多种同位素分析水体同位素组成来分析土壤-根系界面水分运移过程，进一步确定树木水分来源，提高识别和划分的准确性，并以此完善稳定同位素应用模型；(3)利用同位素标记盆栽实验精准控制叶片吸水的水源，高分辨率地解析叶片吸水的发生位置以及时间；(4)结合控制性同位素标记实验并利用离心技术提取木质部导管中的汁液水，对比分...     

Temperature-induced fractionation of oxygen isotopes of diatom frustules and growth water in Lake Sihailongwan in Northeast China

Diatom oxygen isotopes have been widely applied in quantitative reconstruction of the paleoclimate and paleoenvironment, but have rarely been reported in China. In the present study, Lake Sihailongwan in Northeast China was selected for detailed investigation of oxygen isotopic fractionation between diatom frustules and lake water induced by growth temperature. This study involved a 2-year period of field monitoring of the lake water temperature at multiple depths and biweekly collections of traps for both sediment and water at shallow and bottom depths (7 and 49 m below the lake surface, respectively), diatom separation and purification of the trap sediments, and oxygen isotope measurement for diatom silica and lake water samples. The conditioned experiment conducted herein demonstrated that the laboratory device, methods and techniques used in this study were capable of generating reliable data for the typical oxygen isotope composition of diatom frustules. The data obtained revealed a prominent linear relationship between the oxygen isotope composition of the modern diatom and lake temperature during growth. The fractionation coefficient was about −0.185‰/°C−0.238‰/°C in the temperature range of 3.6–24°C, which is consistent with the observations from various aquatic environments and laboratory culture with different diatom taxa. These findings provide strong support for the dominant control of the growth temperature on the oxygen isotope fractionation between the diatom frustules and ambient water. A notable difference in the fractionation coefficient was observed between the surface and bottom diatom oxygen isotopes, suggesting that various depositional processes and taphonomic effects influenced the surface and bottom trap samples. Another factor leading to this difference may be that enrichment by evaporation and dilution by rainfall have a stronger influence on the surface. Overall, the results presented here demonstrate significant progress in evaluation of diatom oxygen isotopes in China and draw attention to the differences between surface and bottom diatom oxygen isotope compositions.     

Anomalous 17O compositions in massive sulphate deposits on the Earth

The variation of delta 18O that results from nearly all physical, biological and chemical processes on the Earth is approximately twice as large as the variation of delta 17O. This so-called 'mass-dependent' fractionation is well documented in terrestrial minerals. Evidence for 'mass-independent' fractionation (delta 17O = delta 17O-0.52 delta 18O), where deviation from this tight relationship occurs, has so far been found only in meteoritic material and a few terrestrial atmospheric substances. In the rock record it is thought that oxygen isotopes have followed a mass-dependent relationship for at least the past 3.7 billion years, and no exception to this has been encountered for terrestrial solids. Here, however, we report oxygen-isotope values of two massive sulphate mineral deposits, which formed in surface environments on the Earth but show large isotopic anomalies (delta 17O up to 4.6%). These massive sulphate deposits are gypcretes from the central Namib Desert and the sulphate-bearing Miocene volcanic ash-beds in North America. The source of this isotope anomaly might be related to sulphur oxidation reactions in the atmosphere and therefore enable tracing of such oxidation. These findings also support the possibility of a chemical origin of variable isotope anomalies on other planets, such as Mars.     

<Emphasis Type="Italic">In situ</Emphasis> boron isotope measurements of natural geological materials by LA-MC-ICP-MS

There are two main methods to determine boron isotopic composition. One is the solution method, in which boron is purified after the samples are dissolved in solution and the boron isotope ratios are determined by thermal ionization mass spectrometry (P-TIMS and N-TIMS) or multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). The other is an in-situ analysis method, in which the in-situ boron isotopic ratios in minerals are analyzed directly using secondary ion mass spectrometry (SIMS) or laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). In the in-situ analysis method for boron isotopes, the multifarious chemical purification and separation processes of the solution method are avoided, with increased work efficiency. In addition, the microzones and microbeddings of minerals can be analyzed in-situ to reveal the fine processes and conditions of mineral formation. In this study, using the standard-sample-bracketing (SSB) method, mass bias of the instrument and the fractionation of isotopes were calibrated, and the in-situ determination method of LA-MC-ICP-MS for boron isotopes was established. Through detailed analyses on a series of boron isotope standards and samples, a matrix effect was assessed but not detected, and the analysis results were in accordance with the formerly reported values or P-TIMS determined values, within the error range. The analytical results for IAEA B4 and IMR RB1 with relatively high boron contents were δ¹¹B = –(8.36±0.58)‰ (2σ, n=50) and δ¹¹B = –(12.96±0.97)‰ (2σ, n=57), respectively; the analytical result for IAEA B6 with relatively low boron content was δ¹¹B = –(3.29±1.12)‰ (2σ, n=35). In-situ measurements for B isotopes were performed on geological samples such as tourmaline, ulexite, ludwigite, inyoite and ascharite, with the results consistent with those determined by P-TIMS, within the error range.     

Efficient mixing of the solar nebula from uniform Mo isotopic composition of meteorites

The abundances of elements and their isotopes in our Galaxy show wide variations, reflecting different nucleosynthetic processes in stars and the effects of Galactic evolution. These variations contrast with the uniformity of stable isotope abundances for many elements in the Solar System, which implies that processes efficiently homogenized dust and gas from different stellar sources within the young solar nebula. However, isotopic heterogeneity has been recognized on the subcentimetre scale in primitive meteorites, indicating that these preserve a compositional memory of their stellar sources. Small differences in the abundance of stable molybdenum isotopes in bulk rocks of some primitive and differentiated meteorites, relative to terrestrial Mo, suggest large-scale Mo isotopic heterogeneity between some inner Solar System bodies, which implies physical conditions that did not permit efficient mixing of gas and dust. Here we report Mo isotopic data for bulk samples of primitive and differentiated meteorites that show no resolvable deviations from terrestrial Mo. This suggests efficient mixing of gas and dust in the solar nebula at least to 3 au from the Sun, possibly induced by magnetohydrodynamic instabilities. These mixing processes must have occurred before isotopic fractionation of gas-phase elements and volatility-controlled chemical fractionations were established.     

热液矿床中气相成矿作用

气相成矿作用是人们早已注意的问题 ,但在矿床学研究中没有给予应有的重视。文章从金属成矿物质的气相迁移、气 -液相转变对成矿的作用初步探讨了气相成矿作用问题。提出热液矿床成矿过程中必然存在由于气 -液相转变而产生的氢氧同位素瑞利分馏 ,在应用氢氧同位素示踪热液成矿流体来源时必须考虑成矿流体气 -液相转变引起的同位素分馏效应 ,只有这样才能正确示踪成矿流体的来源 ,合理分析热液矿床的成矿机制。     

Mo isotopes in the Lower Cambrian formation of southern China and its implications on paleo-ocean environment

Over the past decade, as one of nontraditional stable isotopes, Mo isotope has developed rapidly and now become an important geochemical proxy to trace paleo-oceanic and atmospheric evolution through geological history. In this paper, Early Cambrian formations in southern China are investigated. The results indicate that δ 97/95Mo values of Early Cambrian seawater may have been larger than 1.4‰, values that are close to those of the modern ocean. It was also found that the variations in Mo isotope composition in samples from two sections （Huangjiawan and Gezhongwu in Guizhou） were closely related to changes in redox conditions during sedimentary processes. Combining our results with existing data, a preliminary model for the evolution of seawater Mo isotope composition through geological history was provided. It indicated that Mo isotopic variations were generally consistent with the evolution of atmospheric oxygen.     

氧同位素标准样品的研制

使用高纯同位素物质精确配制同位素混合物,作为标准物,确定质谱仪器的系统误差。本工作用天然丰度水定量稀释高浓重氧水,制取从0.1982至96.92原子％~(18)O的氧同位素标准水样,用来校准质谱仪器。 实验采用BrF_5将水样转化成O_2。用质谱峰高法测定(18)~O和(17)~O丰度。比较质谱测定值和计算得到的丰度值C,求出质谱仪固有偏差校正系数K、并得到K与C的线性相关关系。 共得到16个具有准确丰度值的氧同位素标准水样。     

稻叶分段硅同位素组成及硅、钾、钠、钙、镁分布特征

 稳定性硅同位素在植物体内的组成模式对研究硅生物循环、植物硅积累的机理具有重大意义。通过水培试验,研究了成熟期水稻叶内硅同位素组成及Si、K、Na、Ca和Mg营养元素的分布情况。试验结果表明,将水稻叶沿长轴按叶鞘、叶片基段、叶片中段和叶片顶段4部分划分后,各段的Si质量分数和δ³⁰Si值都存在显著差异,并呈现从叶下部到上部逐渐增加的一致趋势。在测定的其它营养元素中,只有Ca在水稻叶中的分布与Si类似,K和Na在叶鞘中的质量分数高于叶片,Mg在叶不同部位质量分数没有显著差异。本试验中水稻叶不同部位δ³⁰Si值变化范围是-0.25%～0.23%,超出了目前已知陆生植物样品δ³⁰Si值的变化范围（-0.17%～0.25%）。试验结果显示了水稻叶内硅分布主要受蒸腾作用的影响,硅同位素在叶中的分馏属于同位素动力学分馏。     

镁同位素研究进展及在沉积地质学中的应用前景

Mg同位素作为一种新的稳定同位素研究手段,正日益显示出其潜在的研究价值。从Mg同位素在地球各主要储库中以及各主要地质体中的分布,到Mg同位素的各种分馏机理,近期的研究工作都取得了巨大的进展,尤其是Mg同位素在地表的分布行为的控制因素及其在各碳酸盐矿物之间的分馏作用机理研究。     

美国Wallapai矿区Mineral Park斑岩型矿床早期矿脉中硬石膏的氧同位素组成

本文报道了美国亚利桑那Wallapai矿区Mineral Park斑岩型矿床早期矿脉(AM和AC)中硬石膏的氧同位素组成,依据包体均一温度及硫同位素温度计算成矿溶液的δ~(12)O值(纯水),运用同位素分馏理论讨论AM和AC矿脉成矿溶液的来源和演化。     

CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula

The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.     

Isotopic homogeneity of iron in the early solar nebula.

The chemical and isotopic homogeneity of the early solar nebula, and the processes producing fractionation during its evolution, are central issues of cosmochemistry. Studies of the relative abundance variations of three or more isotopes of an element can in principle determine if the initial reservoir of material was a homogeneous mixture or if it contained several distinct sources of precursor material. For example, widespread anomalies observed in the oxygen isotopes of meteorites have been interpreted as resulting from the mixing of a solid phase that was enriched in 16O with a gas phase in which 16O was depleted, or as an isotopic 'memory' of Galactic evolution. In either case, these anomalies are regarded as strong evidence that the early solar nebula was not initially homogeneous. Here we present measurements of the relative abundances of three iron isotopes in meteoritic and terrestrial samples. We show that significant variations of iron isotopes exist in both terrestrial and extraterrestrial materials. But when plotted in a three-isotope diagram, all of the data for these Solar System materials fall on a single mass-fractionation line, showing that homogenization of iron isotopes occurred in the solar nebula before both planetesimal accretion and chondrule formation.     

Calcium isotope fractionation and its controlling factors over authigenic carbonates in the cold seeps of the northern South China Sea

In this study, we analyzed stable calcium isotope results of authigenic carbonates from two cold seep areas of the Dongsha area and the Baiyun Sag in the northern South China Sea. The stable isotopes of carbon and oxygen as well as the mineral composition of authigenic carbonates were used to investigate control calcium isotope fractionation. The δ44/40Ca ratios of the southwestern Dongsha area samples ranged from 1.21‰ to 1.52‰ and the ratio of the Baiyun Sag sample was 1.55‰ of the SRM915a isotope standard. X-ray diffraction analysis showed that the carbonate samples consisted of dolomite, calcite and aragonite, with small amounts of high-Mg calcite and siderite. The δ13C values of the carbonates of the southwestern Dongsha area varied between δ49.21‰ and δ16.86‰ of the Vienna PeeDee Belemnite (VPDB) standard and the δ18O values ranged from 2.25‰ to 3.72‰ VPDB. The δ13C value of the Baiyun Sag sample was 2.36‰ VPDB and the δ18O value was 0.44‰ VPDB. The δ13C values of the carbonates of the southwestern Dongsha area revealed there is methane seeping into this area, with a variable contribution of methane-derived carbon. The sampled carbonates covered a range of δ13C values suggesting a dominant methane carbon source for the light samples and mixtures of δ13C values for the heavier samples, with possibly an organic or seawater carbon source. The δ18O values indicated that there is enrichment in 18O, which is related to the larger oxygen isotope fractionation in dolomite compared to calcite. The results of the Baiyun Sag sample exhibited normal seawater carbon and oxygen isotopic values, indicating that this sample is not related to methane seepage but instead to precipitation from seawater. The relatively high δ44/40Ca values indicated either precipitation at comparatively high rates in pore-water regimes with high alkalinity, or precipitation from an evolved heavy fluid with high degrees of Ca consumption (Raleigh type fractionation). The dolomite samples from the Dongsha area revealed a clear correlation between the carbon and calcium isotope composition, indicating a link between the amount and/or rate of carbonate precipitation and methane contribution to the bicarbonate source. The results of the three stable isotope systems, mineralogy and petrography, show that mineral composition, the geochemical environment of authigenic carbonates and carbon source can control the calcium isotope fractionation.     

Boron and oxygen isotope evidence for recycling of subducted components over the past 2.5 Gyr

Evidence for the deep recycling of surficial materials through the Earth's mantle and their antiquity has long been sought to understand the role of subducting plates and plumes in mantle convection. Radiogenic isotope evidence for such recycling remains equivocal because the age and location of parent-daughter fractionation are not known. Conversely, while stable isotopes can provide irrefutable evidence for low-temperature fractionation, their range in most unaltered oceanic basalts is limited and the age of any variation is unconstrained. Here we show that delta(18)O ratios in basalts from the Azores are often lower than in pristine mantle. This, combined with increased Nb/B ratios and a large range in delta(11)B ratios, provides compelling evidence for the recycling of materials that had undergone fractionation near the Earth's surface. Moreover, delta(11)B is negatively correlated with (187)Os/(188)Os ratios, which extend to subchondritic values, constraining the age of the high Nb/B, (11)B-enriched endmember to be more than 2.5 billion years (Gyr) old. We infer this component to be melt- and fluid-depleted lithospheric mantle from a subducted oceanic plate, whereas other Azores basalts contain a contribution from approximately 3-Gyr-old melt-enriched basalt. We conclude that both components are most probably derived from an Archaean oceanic plate that was subducted, arguably into the deep mantle, where it was stored until thermal buoyancy caused it to rise beneath the Azores islands approximately 3 Gyr later.     

Applications of stable isotopes to study plant-animal relationships in terrestrial ecosystems

As natural tracers, stable isotopes have been extensively used in plant physiological, ecological and environmental research. Recently, animal physiological ecologists have also applied stable isotope techniques to study plantanimal relationships. The isotopic compositions of animal body generally reflect and integrate their diets over a time period ranging from hours to years to the lifetime of an individual. When animal living habitat changes or animals move to a new environment, the animal isotopic compositions will shift accordingly. Thus, stable isotope signatures of an animal can truly reflect its food sources, habitat, distribution and movement patterns during a given time period. Moreover, by analyzing animal-tissue isotopic compositions at different temporal scales, we can improve our understanding of animal adaptation to environmental changes. Stable isotope technique also provides an ideal tool to study animal foodweb relationship and community structure because of isotopic fractionation during the processes of nutrient assimilation by animals. Stable isotope technique can continuously measure animal trophic position in a foodweb, which can eventually reveal the predator-prey relationship and its role in determining matter balance and energy flow in the entire ecosystem. Stable isotope technique has been one of the most important and efficient tools in studying plant-animal relationship. In this paper, we first review recent advances in the application of stable isotope techniques to plant-animal relationship research then evaluate their advantages and disadvantages, and finally discuss some future directions associated with stable isotope applications to plant-animal relationship research.     

Continental warming preceding the Palaeocene-Eocene thermal maximum

Marine and continental records show an abrupt negative shift in carbon isotope values at ～55.8?Myr ago. This carbon isotope excursion (CIE) is consistent with the release of a massive amount of isotopically light carbon into the atmosphere and was associated with a dramatic rise in global temperatures termed the Palaeocene-Eocene thermal maximum (PETM). Greenhouse gases released during the CIE, probably including methane, have often been considered the main cause of PETM warming. However, some evidence from the marine record suggests that warming directly preceded the CIE, raising the possibility that the CIE and PETM may have been linked to earlier warming with different origins. Yet pre-CIE warming is still uncertain. Disentangling the sequence of events before and during the CIE and PETM is important for understanding the causes of, and Earth system responses to, abrupt climate change. Here we show that continental warming of about 5?°C preceded the CIE in the Bighorn Basin, Wyoming. Our evidence, based on oxygen isotopes in mammal teeth (which reflect temperature-sensitive fractionation processes) and other proxies, reveals a marked temperature increase directly below the CIE, and again in the CIE. Pre-CIE warming is also supported by a negative amplification of δ(13)C values in soil carbonates below the CIE. Our results suggest that at least two sources of warming-the earlier of which is unlikely to have been methane-contributed to the PETM.     

碳酸盐岩碳、氧同位素分析激光微取样技术

碳酸盐岩碳、氧同位素分析激光微取样技术是利用高能聚焦激光束与碳酸盐岩样品作用,热分解产生CO₂气体,经真空提纯净化后送质谱仪分析测定其C、O同位素值。其空间分辨率优于20μm,能有效地对碳酸盐岩各细微组分结构分别取样,以满足同位素地质学研究的需要。经标样测定,δ¹³C和δ¹⁸O的最好分析精度可达±0.22‰(σ),与常规磷酸分解法分析精度相;δ¹³C无明显分馏现象,δ¹⁸O分馏明显,但对同种矿物是一个常量(方解石偏负1.72‰;白云石偏负1.59‰)易于校正。激光微取样主要应用于碳酸盐储集岩样品碳、氧同位素分析,能较好地解释油气储层孔隙演化和成岩过程。     

High-precision measurement of mercury isotope ratios of atmospheric deposition over the past 150 years recorded in a peat core taken from Hongyuan,Sichuan Province,China

High-precision 210Pb dating technology was applied to a peat core with a time span of about 150 years that was taken from Hongyuan, Sichuan Province, China. The concentrations of total mercury (Hg) and stable isotope compositions of mercury in the peat core were measured using a LUMEX 915 instrument and multi-collector inductively coupled plasma mass spectrometer, respectively. Total mercury (Hg) concentrations in the peat core had a clearly increasing trend from the bottom to top of the core while δ 202Hg ...