镁同位素地球化学研究新进展及其应用

作为一种新兴的地质示踪剂,Mg同位素正受到国际地学界日益广泛的关注。Mg同位素地球化学研究已取得了巨大的进展,近期研究工作主要包括两个方面。首先,调查了地球各主要储库和陨石的Mg同位素组成特征,结果表明陨石和地球地幔具有均一并且相似的Mg同位素组成,平均δ²⁶Mg值分别为-0.28±0.06‰和-0.25±0.07‰;相反,上地壳和水圈的Mg同位素组成很不均一,δ²⁶Mg值变化范围分别为-4.84‰~+0.92‰和-2.93‰~+1.13‰。其次,对一些地质和物理化学过程中Mg同位素的分馏行为进行研究,结果表明:(1)地表风化作用可以造成大的Mg同位素分馏,导致重Mg同位素残留在风化产物中而轻Mg同位素进入水圈;(2)岩浆分异过程中Mg同位素平衡分馏很小;(3)高温化学扩散和热扩散过程中Mg同位素会发生显著的动力学分馏。基于这些研究成果,Mg同位素体系已经被初步应用于示踪早期地球形成和壳内物质再循环等过程,并有望在不久的将来应用于示踪大陆地壳的化学演化和地质温度计等研究领域。     

镁同位素地球化学研究进展

镁有3个稳定同位素:24Mg、25Mg和26Mg.已有数据表明,自然界Mg同位素组成的变化在陨石中较大.δ26Mg值在-0.71‰～11.92‰之间(相对于DSM3标准),而地球岩石中Mg同位素组成的变化较小,如地幔橄榄岩的δ26Mg变化范围为-3.01‰-1.03‰,沉积碳酸盐岩的δ26Mg变化范围为-4.84‰～-1.09‰,黄土的δ26Mg为-0.60‰.目前,大多数实验室均采用MC-ICP-MS方法来获得高精度的Mg同位素数据.原有Mg同位素国际标准SRM980由于具有不均一性应该废弃,应使用新的DSM3标准.Mg同位素地球化学的研究主要集中在太阳系星云形成过程、记录亏损地幔和地幔交代作用、揭示地质历史时期海水的Mg同位素组成演化、估算大陆风化通量等方面.我国开展的Mg同位素研究还非常少,且尚处于建立Mg同位素分析方法的研究阶段.随着技术的不断发展以及Mg同位素分馏机理的深入研究,Mg同位素的地质应用前景将日趋广泛.     

镁同位素地球化学研究新进展及其在碳酸岩研究中的应用

镁（Mg）同位素有3个,24Mg、25Mg和26Mg,其中24Mg和26Mg的相对质量差较大,高达8.33%,这种大的相对质量差使地壳活动或其他地质过程中Mg同位素因化学物理条件的变化而发生明显的同位素质量分馏.目前,自然界可观测到的δ26Mg变化范围为-5.60‰~0.92‰,约6.5‰.镁在低温地球化学过程中分馏显著,而在高温环境下分馏不明显,因而Mg同位素是地质过程的潜在地球化学指标和示踪剂,在低温风化作用、高温部分熔融与岩浆结晶分异、变质作用、板片俯冲及壳幔物质循环、热液蚀变和矿床成因等方面取得重要进展.为此,简要介绍了镁同位素分析方法,系统总结了Mg同位素在地球各储库中的组成与分布特征以及地质作用过程中的镁同位素分馏机理;其次重点介绍了镁同位素近年来在碳酸岩研究中的应用;最后对有关问题进行了探讨,包括幔源岩石低δ26Mg成因解释（与俯冲再循环的碳酸盐岩、洋壳物质有关或与矿物分离结晶有关）和Li-Mg-Ca同位素联合示踪岩浆碳酸岩岩石成因.并对碰撞反应池多接收器电感耦合等离子体质谱仪（Nu Sapphire MC-ICP-MS）分析优势和Li-Mg-Ca等金属同位素联合示踪在稀土元素富集机制的应用进行了展望.      

镁同位素示踪碳酸盐岩沉积—成岩过程

镁（Mg）作为主要的造岩元素及生物营养元素,是连接大陆、海洋和地球内部循环的重要纽带。碳酸盐岩作为Mg的主要储库,是全球Mg循环的重要组成环节,利用Mg同位素示踪碳酸盐岩沉积—成岩过程是有效反演深时海水Mg同位素组成（δ26Mg_海水）、恢复全球Mg循环的基本前提。近二十年来,Mg同位素在示踪碳酸盐岩沉积—成岩过程研究中取得了较大进展:1）不同类型碳酸盐矿物形成过程中的Mg同位素分馏及其影响因素的研究得到完善;2）建立了Mg同位素地球化学模型,对不同白云石化过程进行半定量—定量模拟;3）初步探索了利用Mg同位素反演早期成岩流体体系的方法。以上研究进展为利用碳酸盐岩恢复δ26Mg_海水奠定了理论基础,在选择有效的碳酸盐岩载体恢复δ26Mg_海水时,需充分考虑碳酸盐岩的沉积—成岩过程及其对Mg同位素组成的影响,并适当结合地球化学模型,消除沉积—成岩因素的影响,进而恢复δ26Mg_海水。     

碳酸盐岩Mg同位素分析方法及研究进展

Mg是中等挥发和流体活动性元素，也是生物所必需的元素，几乎参与了地球上所有的地球化学过程，包括物理、化学和生物循环。近20年来，随着多接收电感耦合等离子体质谱仪（MC-ICP-MS）高精度测定Mg同位素技术的快速发展，Mg同位素在碳酸盐岩研究中显示出非常广阔的应用前景，其中低Mg碳酸盐岩的研究对了解大陆地壳的化学演化具有非常重要的作用。然而，由于现有高Ca低Mg碳酸盐岩的分析方法并不能很好地将Ca完全去除，因此利用低Mg碳酸盐岩的Mg同位素特征进行地质研究仍然存在很大的局限性。通过对已有碳酸盐岩的Mg同位素分析方法进行归纳总结，认为可采取下列措施提高低Mg碳酸盐岩样品的Mg同位素分析精度，即上柱前完全溶解样品；化学分离过程中确保Mg与其他基质元素完全分离；淋洗基质过程中采用HF与HNO3混合酸进行淋洗，同时提高Mg的进样量；采用新鲜的测试样品和标准溶液进行测试等。上述措施可为该分析方法的改进及其在碳酸盐岩类Mg同位素研究中的应用提供参考。     

钛同位素地球化学综述

随着分析技术的进步,非传统稳定同位素体系在地球化学、天体化学和生物地球化学等研究领域的应用日益广泛。钛(Ti)是一个非常重要的过渡族金属元素,在地球和其他类地球行星中广泛存在。但是由于Ti是一种难熔的、流体不活动性元素,高温地质过程中Ti同位素分馏很小。人们对Ti同位素体系的地球化学应用的关注相对其他非传统稳定同位非常有限。而近年来,随着化学纯化方案的优化以及双稀释剂方法的改进和仪器质谱性能的提高,Ti同位素组成的高精度测试已经能够实现。天然样品中Ti同位素组成的变化随之得以发现,使得学者们能够利用这一新的稳定同位素体系来解决与高温和低温地球化学相关的问题。很快Ti同位素体系地球化学研究成为当前国际地质学界的前沿研究课题和新的发展方向之一。本文首先在简要介绍Ti元素和Ti同位素体地球化学性质的基础上,介绍了Ti元素化学分离和Ti同位素分析方法。随后笔者总结了已有的不同类型球粒陨石和地球样品的质量相关Ti同位素组成研究结果,对硅酸盐地球的Ti同位素组成做了初步评估。前人对高温地质样品的Ti同位素组成研究初步探明Ti同位素在岩浆演化过程,例如部分熔融和结晶分异等重要地质过程中的分馏行为。笔者在此基础上探讨了结晶分异过程中引起Ti同位素分馏的主要控制因素,指出Ti同位素是潜在的研究岩浆演化过程的新工具。最后笔者探讨了Ti同位素地球化学未来的发展方向,以加速我国在Ti同位素地球化学方面的应用研究。     

Re-Os同位素体系及其地质应用

Re-Os同位素体系是近年来地球化学研究的热点,也是发展较快的同位素地球化学方法,被广泛应用于同位素地质年代学、矿床成因、陨石定年、岩浆成因以及壳-幔演化、大陆岩石圈地幔定年等领域,尤其在地幔地球化学动力学等前缘领域,Re-Os同位素体系成为一种新的强有力的研究工具.     

地表及海洋环境的镁同位素地球化学研究进展

镁(Mg)是主要造岩元素,其地球丰度仅次于铁和氧。Mg几乎参与了地表所有圈层间的物理、化学和生物作用。随着多接收器等离子质谱等分析方法的改进和完善,Mg同位素显示出更加广阔的应用前景。同时,Mg独特的地球化学特征,使其在地表及海洋地球化学领域的应用日益广泛。本文主要就近几十年来Mg同位素在地表及海洋地球化学领域的研究现状、存在的问题以及发展趋势进行系统的总结与探讨。虽然,目前对Mg同位素的研究还处于早期阶段,但许多研究成果显示,Mg同位素具有很大潜力成为环境变化的新的指示工具。     

大陆硅酸盐岩石风化过程中镁同位素地球化学研究进展

Mg同位素体系被证明在示踪硅酸盐矿物风化方面颇具优势.通过总结近年来大陆硅酸盐风化过程中Mg同位素地球化学的研究,归纳出以下认识:①化学风化方面,原生矿物溶解使得液相的Mg同位素组成变轻,而固相残留的Mg同位素组成变重;次生矿物中含有两种形态的Mg(交换态Mg和结构态Mg),二者δ26Mg不同,次生矿物形成过程中Mg同位素分馏方向与矿物种类、结构和形成机制等因素有关;黏土矿物吸附和解吸Mg2+引起Mg同位素分馏,但方向尚不确定;土壤可交换复合物倾向于优先吸附和解吸26Mg.②物理风化方面,水流、风等造成的矿物分选会引起风化产物Mg同位素组成发生变化.③植物—土壤体系Mg同位素的分馏很小.目前,大陆硅酸盐风化中一些重要过程的Mg同位素地球化学行为还存在争议,亟待通过室内试验、模拟计算,以及与其他同位素联用等途径完善理论基础,推动Mg同位素在示踪大陆风化中的广泛应用.     

陨石中锆石对地球总体Lu-Hf同位素组成和早期壳幔分异演化的制约

<正>176Lu-176Hf同位素衰变体系是研究硅酸盐固体行星分异演化的一个重要工具,也能为认识地球最早期地壳的起源提供有利手段。然而,对于Lu-Hf同位素体系数据的解释,需要首先建立完好的地球总体Hf同位素的生长曲线。Lu和Hf均是难熔(highly refractory)的中等-强不相容元素。陨石中的Lu-Hf同位素组成是研究地球全球或硅酸盐地球Lu-Hf同位素组成的重要参考。然而,现代地球的176Hf/177Hf值和球粒陨石中的176Hf/177Hf值(即CHUR化学储库)相比有很大的变化范围,也     

Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios (²⁶Mg/²⁴Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant ²⁶Mg/²⁴Mg ratio (expressed as δ²⁶Mg) at −0.79 ± 0.05‰, identical to seawater δ²⁶Mg. Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ²⁶Mg value of 0.11‰, potentially enriched in ²⁶Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ²⁶Mg, ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ²⁶Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain (δ²⁶Mg_grass-δ²⁶Mg_rain) of 0.21‰. The deep pore-waters (1-15 m deep) have δ²⁶Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of ²⁴Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.     

Experimental determination of magnesium isotope fractionation during higher plant growth

Two higher plant species (rye grass and clover) were cultivated under laboratory conditions on two substrates (solution, phlogopite) in order to constrain the corresponding Mg isotope fractionations during plant growth and Mg uptake. We show that bulk plants are systematically enriched in heavy isotopes relative to their nutrient source. The Δ²⁶Mg_plant-source range from 0.72‰ to 0.26‰ for rye grass and from 1.05‰ to 0.41‰ for clover. Plants grown on phlogopite display Mg isotope signatures (relative to the Mg source) ∼0.3‰ lower than hydroponic plants. For a given substrate, rye grass display lower δ²⁶Mg (by ∼0.3‰) relative to clover. Magnesium desorbed from rye grass roots display a δ²⁶Mg greater than the nutrient solution. Adsorption experiments on dead and living rye grass roots also indicate a significant enrichment in heavy isotopes of the Mg adsorbed on the root surface. Our results indicate that the key processes responsible for heavy isotope enrichment in plants are located at the root level. Both species also exhibit an enrichment in light isotopes from roots to shoots (Δ²⁶Mg_leaf-root = −0.65‰ and −0.34‰ for rye grass and clover grown on phlogopite respectively, and Δ²⁶Mg_leaf-root of −0.06‰ and −0.22‰ for the same species grown hydroponically). This heavy isotope depletion in leaves can be explained by biological processes that affect leaves and roots differently: (1) organo-Mg complex (including chlorophyll) formation, and (2) Mg transport within plant. For both species, a positive correlation between δ²⁶Mg and K/Mg was observed among the various organs. This correlation is consistent with the link between K and Mg internal cycles, as well as with formation of organo-magnesium compounds associated with enrichment in heavy isotopes. Considering our results together with the published range for δ²⁶Mg of natural plants and rivers, we estimate that a significant change in continental vegetation would induce a change of the mean river δ²⁶Mg that is comparable to analytical uncertainties.     

Heterogeneous magnesium isotopic composition of the upper continental crust

High-precision Mg isotopic data are reported for ∼100 well-characterized samples (granites, loess, shales and upper crustal composites) that were previously used to estimate the upper continental crust composition. Magnesium isotopic compositions display limited variation in eight I-type granites from southeastern Australia (δ²⁶Mg = −0.25 to −0.15) and in 15 granitoid composites from eastern China (δ²⁶Mg = −0.35 to −0.16) and do not correlate with SiO₂ contents, indicating the absence of significant Mg isotope fractionation during differentiation of granitic magma. Similarly, the two S-type granites, which represent the two end-members of the S-type granite spectrum from southeastern Australia, have Mg isotopic composition (δ²⁶Mg = −0.23 and −0.14) within the range of their potential source rocks (δ²⁶Mg = −0.20 and +0.15) and I-type granites, suggesting that Mg isotope fractionation during crustal anatexis is also insignificant. By contrast, δ²⁶Mg varies significantly in 19 A-type granites from northeastern China (−0.28 to +0.34) and may reflect source heterogeneity.Compared to I-type and S-type granites, sedimentary rocks have highly heterogeneous and, in most cases, heavier Mg isotopic compositions, with δ²⁶Mg ranging from −0.32 to +0.05 in nine loess from New Zealand and the USA, from −0.27 to +0.49 in 20 post-Archean Australian shales (PAAS), and from −0.52 to +0.92 in 20 sedimentary composites from eastern China. With increasing chemical weathering, as measured by the chemical index of alternation (CIA), δ²⁶Mg values show a larger dispersion in shales than loess. Furthermore, δ²⁶Mg correlates negatively with δ⁷Li in loess. These characteristics suggest that chemical weathering significantly fractionates Mg isotopes and plays an important role in producing the highly variable Mg isotopic composition of sedimentary rocks.Based on the estimated proportions of major rock units within the upper continental crust and their average MgO contents, a weighted average δ²⁶Mg value of −0.22 is derived for the average upper continental crust. Our studies indicate that Mg isotopic composition of the upper crust is, on average, mantle-like but highly heterogeneous, with δ²⁶Mg ranging from −0.52 to +0.92. Such large isotopic variation mainly results from chemical weathering, during which light Mg isotopes are lost to the hydrosphere, leaving weathered products (e.g., sedimentary rocks) with heavy Mg isotopes.     

Mg Isotope Interlaboratory Comparison of Reference Materials from Earth‐Surface Low‐Temperature Environments

To enable quality control of measurement procedures for determinations of Mg isotope amount ratios, expressed as δ²⁶Mg and δ²⁵Mg values, in Earth‐surface studies, the δ²⁶Mg and δ²⁵Mg values of eight reference materials (RMs) were determined by interlaboratory comparison between five laboratories and considering published data, if available. These matrix RMs, including river water SLRS‐5, spring water NIST SRM 1640a, Dead Sea brine DSW‐1, dolomites JDo‐1 and BCS‐CRM 512, limestone BCS‐CRM 513, soil NIST SRM 2709a and vegetation NIST SRM 1515, are representative of a wide range of Earth‐surface materials from low‐temperature environments. The interlaboratory variability, 2s (twice the standard deviation), of all eight RMs ranges from 0.05 to 0.17‰ in δ²⁶Mg. Thus, it is suggested that all these materials are suitable for validation of δ²⁶Mg and δ²⁵Mg determinations in Earth‐surface geochemical studies.     

Magnesium isotopic composition of the Earth and chondrites

To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ²⁵Mg and ±0.07‰ on δ²⁶Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL).Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ²⁵Mg = −0.13 ± 0.05 (2SD) and δ²⁶Mg = −0.26 ± 0.07 (2SD) for global oceanic basalts (n = 110) and δ²⁵Mg = −0.13 ± 0.03 (2SD) and δ²⁶Mg = −0.25 ± 0.04 (2SD) for global peridotite xenoliths (n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ²⁵Mg = −0.15 ± 0.04 (2SD) and δ²⁶Mg = −0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes.Collectively, the Mg isotopic composition of the Earth’s mantle, based on oceanic basalts and peridotites, is estimated to be −0.13 ± 0.04 for δ²⁵Mg and −0.25 ± 0.07 for δ²⁶Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites. The chondritic composition of the Earth implies that Mg isotopes were well mixed during accretion of the inner solar system.     

Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive

Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater. Mg isotopes are significantly (up to 5‰) fractionated during carbonate precipitation by preferential incorporation of ²⁴Mg, while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of ²⁶Mg. Thus, the marine Mg cycle could be reflected by seawater Mg isotopic composition (δ²⁶Mg_sw), which might be recorded in marine carbonate. However, carbonates are both texturally and compositionally heterogeneous, and it is unclear which carbonate component is the most reliable for reconstructing δ²⁶Mg_sw. In this study, we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China. Based on petrographic studies, four carbonate components were recognized: micrite, marine cement, brachiopod shell, and mixture. The four components had distinct δ²⁶Mg: (1) micrite samples ranged from ?2.86‰ to ?2.97‰; (2) pure marine cements varied from ?3.40‰ to ?3.54‰, while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range (?3.27‰ to ?3.75‰); (3) values for the mixture component were ?3.17‰ and ?3.49‰; and (4) brachiopod shells ranged from ?2.20‰ to ?3.07‰, with the thickened hinge area enriched in ²⁴Mg. Due to having multiple carbonate sources, neither the micrite nor the mixture component could be used to reconstruct δ²⁶Mg_sw. In addition, the marine cement was homogenous in Mg isotopes, but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ²⁶Mg_sw. Furthermore, brachiopod shells had heterogeneous C and Mg isotopes, suggesting a significant vital effect during growth. Overall, the heterogeneous δ²⁶Mg of the Huangjin limestone makes it difficult to reconstruct δ²⁶Mg_sw using bulk carbonate/calcareous sediments. Finally, δ²⁶Mg_sw was only slightly affected by the faunal composition of carbonate-secreting organisms, even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range (0.2‰–4.8‰) of fractionation during biogenic carbonate formation.     

Magnesium isotopic composition of igneous rock standards measured by MC-ICP-MS

To provide inter-lab comparison for high-precision Mg isotope analysis, Mg isotope compositions (expressed as δ²⁶Mg relative to DSM-3) for commercially accessible peridotite, basalt, andesite, and granite geo-standards have been measured by multi-collector inductively coupled mass-spectrometry (Nu-Plasma) using sample-standard bracketing method. There is a large tolerance of matrix cations during the measurement of Mg isotopes, as intensity ratios of ²³Na/²⁴Mg and ²⁷Al/²⁴Mg of about 20% only change the δ²⁶Mg by less than 0.1‰, and low ⁵⁵Mn/²⁴Mg (<0.1) and ⁵⁸Ni/²⁴Mg (<0.01) do not cause significant mass bias either. Concentration match between samples and standards within 90% is adequate to obtain accurate isotope analysis, which also mitigates the isobaric interference of ¹²C¹⁴N⁺ on ²⁶Mg. Organic matrix from chemical purification can cause significant analytical errors when the mass of Mg processed is small. The long-term reproducibility of δ²⁶Mg_DSM-3 for samples with relatively higher MgO content is about 0.11‰ (2SD), and granites with lower MgO content is about 0.2‰ (2SD). Although the standards in this study have wide ranges of major element compositions with SiO₂ from 40 to 70 wt.% and MgO from 0.75 to 49.6 wt.%, they exhibit a variation of Mg isotopic compositions with δ²⁶Mg from −0.07 to −0.40‰. δ²⁶Mg do not correlate with SiO₂ or MgO contents, suggesting homogenous Mg isotope compositions in igneous rocks at the level of current precision, relative to low temperature samples including sediments and riverine and sea waters. Our data do not support a non-chondritic Mg isotope composition of the Earth.     

Constraining magnesium cycling in marine sediments using magnesium isotopes

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid δ²⁶Mg values increase with depth by as much as 2‰. Because carbonates preferentially incorporate ²⁴Mg (low δ²⁶Mg), the increase in pore-fluid δ²⁶Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid δ²⁶Mg values decrease with depth by up to 2‰. The decline in pore-fluid δ²⁶Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured δ²⁶Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7‰ depleted in δ²⁶Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in δ²⁶Mg by 0‰ to +1.25‰ relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.     

表生环境中镁同位素的地球化学循环

近些年表生环境中镁同位素分馏取得了一系列重要研究进展,这些新认识为深入理解表生环境中镁同位素地球化学循环奠定了基础。表生环境中镁同位素的地球化学循环主要涉及风化、河流搬运、碳酸盐沉淀、水岩反应等重要地质过程。风化过程中镁同位素发生显著分馏,硅酸盐风化产物中富集重的镁同位素,轻的镁同位素易进入水体。河流搬运过程中,镁同位素不发生分馏,但外源输入可能影响水体的镁同位素组成。河水汇入海洋后,碳酸盐沉淀过程可导致轻的镁同位素以碳酸盐的形式从海水中移出。在海底高温水岩反应过程中,海水中绝大多数的镁(80%~87%)都进入岩石,循环后的热液可能富集轻的镁同位素。海底低温水岩反应过程中海水的镁可以进入岩石并形成次生矿物,此过程的镁同位素分馏主要与次生矿物的形成有关。此外,海水中的镁易与黏土矿物发生交换反应,此过程黏土矿物倾向于吸附轻的镁同位素。总之,在表生环境中上地壳的镁(δ26Mg约为-0.22‰)经历风化作用、河流搬运、海洋贮存,最终以碳酸盐岩(δ26Mg一般小于-1‰)或与玄武岩发生反应的形式重新回到岩石圈。