大陆风化过程的锂同位素地球化学研究进展

锂同位素在地质学、地球化学研究中有着广阔的应用前景,大陆风化过程的锂同位素地球化学研究已经成为近年来国际上研究的热点,在过去十多年发展快速,并取得一批优异研究成果。系统综述了本领域国内外近年来的主要研究思路,各研究方向的主要进展,并在此基础上提出现阶段存在的问题。主要研究方向包括流域尺度大空间范围的总体研究、风化壳剖面的精细研究以及实验室内的模拟研究,均涉及水/岩作用过程的锂同位素分馏机理研究。现有研究结果有的需要进一步论证,有的相互之间存在矛盾,还有部分结论不能自圆其说,因此还需要进一步开展深入细致的研究工作。     

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.     

长江流域河水和悬浮物的锂同位素地球化学研究

深入理解流域侵蚀过程中的锂同位素分馏对于运用锂同位素来示踪化学循环和气候变化是十分必要的。研究集中在长江干流和主要支流的水体和悬浮物的锂及锂同位素组成。长江流域水体的锂及锂同位素组成（δ⁷Li）分别为150~4 570 nmol/L和+7.6‰~+28.1‰,两者沿上游至下游的变化趋势相反。悬浮物锂同位素组成（δ⁷Li）变化比较稳定,分别为41~92 μg/g和-4.7‰~+0.7‰,而且总是低于相应水体的锂同位素组成。悬浮物和流体之间的锂同位素分馏系数在0.977和0.992之间,与悬浮物的量及组成存在明显相关性,反映了粘土矿物的吸附和化学风化的程度。锂含量与锂同位素组成之间良好的负相关性表明流域水体的锂来自2个端元混合：其一可能是蒸发盐岩,并伴有深部热泉水;其二可能是硅酸岩。     

离子交换过程中锂同位素分馏对锂同位素测试准确度的影响

锂同位素被广泛应用于地球与行星科学各个领域,准确测定锂同位素比值是示踪各种自然过程的前提,但目前国际实验室报道的锂同位素标准物质测定值存在较大偏差,例如已报道的海水δ7Li测试值相差5‰。针对这一现状,本文基于离子交换理论基础,使用正态分布函数拟合淋出曲线,通过理论计算得到离子交换纯化过程造成的锂同位素分馏的理论值,该数值与MC-ICP-MS检测无关,但对锂同位素测试准确度有直接的影响。在此基础上,定义相对回收率(Rc)用于监测锂同位素分馏。基于本实验室分离纯化流程,通过理论计算得出,当Rc 99. 8%时,可认为离子交换纯化过程中没有引起可观察到的锂同位素分馏,进而不影响MC-ICP-MS检测准确度。目前世界上各实验室主要通过绝对回收率或Rc来判断分离过程中是否发生同位素分馏。由于测试的空间电荷效应,绝对回收率易被高估,而 99%的Rc并未全部达到理论计算得到的Rc,表明各实验室对同种标准物质测试结果的偏差极可能是由于离子交换纯化过程中锂同位素分馏导致的。本文提出,对于每一样品,只需要分别测量离子交换过程中接收区间及其前后一定区间溶液中锂含量,将得到的Rc值与其理论值比较,即可判断分离纯化过程中是否引起可观察到的锂同位素分馏。     

锂同位素分馏机制讨论

作为一种新兴的稳定同位素示踪工具, 锂同位素地球化学的研究近年来受到了国际地学界日益广泛的关注.其应用领域涵盖了从地表到地幔的流体与矿物之间的相互作用.在地表风化作用过程中, 轻锂同位素(6Li) 优先进入固体相, 而7Li则进入流体相, 因而地表风化作用淋滤出了岩石中的重锂, 致使河水具有重的锂同位素组成, 河水又将重锂同位素组分补给海洋, 洋壳的低温蚀变作用使得海水的锂同位素组成进一步变重.在俯冲带, 由于俯冲板片释放的流体具有重锂同位素组成的特征, 它们上升并交代上覆的地幔楔和相邻的地幔, 使得地幔楔的锂同位素组成变重.同时, 深俯冲的板片由于脱水而具有较轻的锂同位素组成, 它们在地幔中可能形成一个局部轻锂的地幔储源.影响地幔橄榄岩锂同位素分馏的因素主要有3个方面: 温度、扩散机制以及外来熔体的反应.由于高温下地幔矿物之间的锂同位素分馏很小, 而单纯的扩散分馏机制不能够很好的解释我国华北汉诺坝地区地幔橄榄岩中矿物之间的锂同位素分馏.因此, 具有轻锂同位素组成的熔体与橄榄岩之间的反应是上述现象的一个合理解释.需要指出的是, 在橄榄岩-熔体反应的过程中, 锂同位素的扩散作用也对地幔矿物之间的同位素分馏有一定的贡献.      

2.5Ma以来大陆风化强度的演变

本次研究得出了２．５ＭａＢＰ以来洛川剖面黄土－古土壤序列的酸不深物＾８７Ｓｒ／＾８６Ｓｒ、Ｒｂ／Ｓｒ、磁化率和沉积速率的变化曲线。黄土和古土壤酸不深物＾８７Ｓｒ／８６Ｓｒ、Ｒｂ／Ｓｒ和磁化率的变化具有类似的阶段性和周期性,这与晚新生代以来古气候的主要变化以及行星轨道参数相一致。研究证明,黄土和古土壤酸不深物＾８７Ｓｒ／＾８６Ｓｒ值得化学风化强度的替代指标,沉积速率是物理风化强度的替代指标。自２．５     

大陆风化与全球气候变化

:“构造隆升驱动气候变化”的假说是当前解释新生代以来全球气候变冷的主流观点。该假说把新生代以来发生的几个主要现象 ,即全球气候总体上趋冷 ,大气 CO2 浓度下降 ,海洋 87Sr/ 86Sr比值上升 ,以及构造作用引起的大面积隆升等加以有机的联系 ,给以了合理的解释。近几年围绕大陆风化和全球气候变化问题取得了一些新的进展 ,主要是对发源于喜马拉雅山的河流进行研究 ,探讨青藏高原隆起对于大陆风化速率的影响。这些争论主要是有关硅酸盐风化还是碳酸盐风化 ,有机碳的风化与埋藏 ,大陆风化与大气温度 ,大气 CO2 浓度与大气温度等问题。最后介绍了我国研究人员在黄土高原的黄土沉积地层所作的研究工作和取得的成果。     

锂同位素在环境地球化学研究中的新进展

锂的两个稳定同位素(6Li和7Li)相对质量差较大,因此易产生明显的同位素分馏。业已查明,自然界中δ7Li值的变化在-40‰和 50‰之间。其中较小的δ7Li值见于海相生物碳酸盐样品,较大的δ7Li值见于某些盐湖卤水以及有孔虫的样品。由于明显的同位素分馏和不同地质体中截然不同的δ7Li值,锂同位素应用十分广泛,且在壳-幔演化、陆壳风化、卤水和污染水体示踪等研究领域取得显著成效。     

锂同位素在伟晶岩矿床成因研究中的应用

稀有金属矿产对现代工业和科技的发展极其重要,伟晶岩矿床作为稀有金属的主要来源,其成因与成矿作用有待深入研究,普遍争论的成因模式包括:花岗岩结晶分异、地壳部分熔融以及岩浆液态不混溶。研究表明地壳深熔过程中锂同位素不发生有意义的分馏,因此在解决花岗岩和伟晶岩的岩浆源区性质方面提供了强有力的证据。文章主要从花岗伟晶岩的成因、锂同位素分馏机制以及锂同位素在伟晶岩矿床中的应用三个方面系统综述了国内外近年来取得的一些研究进展。国内外学者以锂同位素分馏机制详细论述了花岗伟晶岩的Li同位素组成,认为伟晶岩矿床的成因主要为花岗岩结晶分异或地壳部分熔融。但是锂同位素应用于伟晶岩矿床成因方面的研究还不够成熟,需要开展更多的工作。     

大兴安岭地区花岗岩风化过程中锂同位素地球化学行为

锂(Li)同位素具有示踪大陆风化的潜力,但风化体系中Li同位素组成(δ⁷Li)对风化强度的指示关系仍不明确。本文以大兴安岭地区花岗岩风化剖面为研究对象,采集了剖面不同风化层位的样品,测定了原岩及其风化产物样品的元素含量和δ⁷Li值。结果表明,风化剖面上部的δ⁷Li值为-0.08‰～+1.8‰,中下部的δ⁷Li值为-2.6‰～+0.25‰并低于原岩的值(+0.75‰)。δ⁷Li值在剖面上部的变化主要是黄土输入及其再风化的结果,而中部主要是受次生矿物溶解和再沉淀过程的影响,下部主要是受控于次生矿物形成过程。岩石风化产物的Li同位素组成可以作为风化强度的替代指标,但次生矿物溶解和再沉淀过程可能会影响风化剖面的δ⁷Li值对风化强度的指示关系。     

200 ka以来澳大利亚西北岸外沉积物源区风化的Mg同位素记录及其对澳洲古季风的响应

本文通过对IODP 363航次于澳大利亚西北岸外陆架上钻取的U1483站岩芯进行沉积物粒度、镁同位素以及主量元素成分等分析,重建200 ka以来帝汶海西南部沉积物输入演化及其指示的源区风化和侵蚀历史,探讨海洋沉积物中细粒硅质碎屑组分镁同位素的古环境指示意义。U1483站陆源碎屑组分主要由黏土质粉砂组成,其δ²⁶Mg变化范围超过0.25‰。通过计算化学蚀变指数(chemical index of alteration, CIA)和两种物理侵蚀指标(包括陆源物质堆积速率和Ti/Ca比值),结果显示200 ka以来δ²⁶Mg指标与CIA具有非常一致的曲线形态。本文推测陆源碎屑组分的Mg同位素组成主要反映物源区大陆硅酸盐风化强度的变化,而受矿物学分选、岩性和早期成岩作用的影响较小。结合区域古气候记录,我们发现本研究中的风化和侵蚀记录与同一个站位已发表的澳洲夏季风降水和表层海水温度变化具有较好的耦合关系,而与赤道太平洋海平面变化的相关程度较低,反映了轨道时间尺度上沉积物所记录的物源区风化和侵蚀演化主要受控于澳洲古季风系统,表现为气候驱动型风化模式。本研...     

Chemical processes affecting alkalis and alkaline earths during continental weathering

The alkali and alkaline earth concentrations in the Toorongo Granodiorite weathering profile are controlled by two competing processes; leaching of cations from primary minerals during their degradation to clays; fixation, by exchange and adsorption, of the same cations onto the secondary clay minerals. Degradation and leaching dominate the early weathering stages whereas during the advanced stages, exchange and adsorption onto clays are of most influence.The alkali and alkaline earth compositional changes in the Toorongo Granodiorite weathering profile are typical of changes occurring during weathering of the continents, consequently the following generalizations apply to continental weathering. Ca, Sr and Na are most rapidly and most strongly removed (as dissolved species) during weathering of fresh continental rocks. Although large quantities of Mg are transported to the marine environment as dissolved species, appreciable amounts remain (fixed in secondary clay minerals) at the weathering site to be removed during mass wasting of continental weathering profiles. Large quantities of Rb, Cs and Ba, fixed in continental weathering profiles by exchange and adsorption onto secondary clays, are transported from the continents only during mass wasting of the continents.     

The effect of weathering on the distribution of strontium isotopes in weathering profiles

The strontium isotope ratio in sea water has varied through geologic time owing to the input of strontium from rock weathering. To evaluate the possibility that $\text{Sr}{}^{87}\text{Sr}{}^{86}$ ratios might be altered during weathering, seven weathering profiles developed on Mesozoic arkoses located along the length of New Zealand were investigated. The rubidium-strontium-strontium isotope relations in these profiles give ‘isochron’ ages less than the ages of deposition of the arkoses. These ages appear to result from the weathering of a homogeneous source rock. The age calculated from the rubidium-strontium system (t′) is related to the original age (t) by the equation t′/t = (n ? 1)/n, where n is the ratio of the amounts of common and radiogenic strontium leached from the rock. Shales formed by the accumulation of these residual solids may inherit misleading isochron relationships which may not be erased during deposition or early diagenesis. The strontium which goes into solution and is transported to the sea is slightly less radiogenic than the strontium in the unweathered rock, while the residual clays may be much more radiogenic.     

Lithium isotopes in global mid-ocean ridge basalts

The lithium isotope compositions of 30 well-characterized samples of glassy lavas from the three major mid-ocean ridge segments of the world, spanning a wide range in radiogenic isotope and elemental content and sea floor physical parameters, have been measured. The overall data set shows a significant range in δ⁷Li (+1.6 to +5.6), with no global correlation between Li isotopes and other geochemical or tectonic parameters. The samples with the greatest lithophile element depletion (N-MORB: K₂O/TiO₂ < 0.09) display an isotopic range consistent with the extant database. Samples with greater trace element enrichment display a greater degree of isotopic variability and trend toward heavier compositions (δ⁷Li = +2.4 to +5.6), but are not distinct on average from N-MORB. Together with published data, N-MORB is estimated to have mean δ⁷Li = +3.4 ± 1.4‰ (2σ), consistent with the estimate for an uncontaminated MORB source based on pristine peridotite xenoliths. Locally, where sampling density permits, sources of Li isotope heterogeneity may be evaluated. Sample sets from the East Pacific Rise show correlation of δ⁷Li with halogen concentration ratios. This is interpreted at 15.5°N latitude to represent incorporation of <5 weight percent recycled subduction-modified mantle in the MORB source. At 9.5°N latitude the data are more consistent with shallow level magma chamber contamination by seawater-derived components (<0.5 wt.%).     

Lithium isotopic composition and concentration of the upper continental crust

The Li isotopic composition of the upper continental crust is estimated from the analyses of well-characterized shales, loess, granites and upper crustal composites (51 samples in total) from North America, China, Europe, Australia and New Zealand. Correlations between Li, δ⁷Li, and chemical weathering (as measured by the Chemical Index of Alteration (CIA)), and δ⁷Li and the clay content of shales (as measured by Al₂O₃/SiO₂), reflect uptake of heavy Li from the hydrosphere by clays. S-type granites from the Lachlan fold belt (-1.1 to -1.4‰) have δ⁷Li indistinguishable from their associated sedimentary rocks (-0.7 to 1.2‰), and show no variation in δ⁷Li throughout the differentiation sequence, suggesting that isotopic fractionation during crustal anatexis and subsequent differentiation is less than analytical uncertainty (±1‰, 2σ). The isotopically light compositions for both I- and S-type granites from the Lachlan fold belt (-2.5 to + 2.7 ‰) and loess from around the world (-3.1 to + 4.5‰) reflect the influence of weathering in their source regions. Collectively, these lithologies possess a limited range of Li isotopic compositions (δ⁷Li of −5‰ to + 5‰), with an average (δ⁷Li of 0 ± 2‰ at 1σ) that is representative of the average upper continental crust. Thus, the Li isotopic composition of the upper continental crust is lighter than the average upper mantle (δ⁷Li of + 4 ± 2‰), reflecting the influence of weathering on the upper crustal composition. The concentration of Li in the upper continental crust is estimated to be 35 ± 11 ppm (2σ), based on the average loess composition and correlations between insoluble elements (Ti, Nb, Ta, Ga and Al₂O₃, Th and HREE) and Li in shales. This value is somewhat higher than previous estimates (∼20 ppm), but is probably indistinguishable when uncertainties in the latter are accounted for.     

Redistribution of uranium and thorium series isotopes during isovolumetric weathering of granite

Previous studies of the distribution of U and Th in parent versus weathered granites have shown both depletion and enrichment of these elements during weathering. In this study, the distribution of U and Th decay series isotopes was determined in a weathering profile of a granitic saprolite, which showed textural preservation indicating isovolumetric weathering. Two types of dissolution methods were used: a whole-rock dissolution and a sodium-citrate dithionite leach to preferentially attack noncrystalline phases of weathering products. Using volume-based activities, 45–70 percent of the total ²³²Th was gradually removed during weathering. Although the whole-rock ${}^{228}\text{Th}{}^{232}\text{Th}$ activity ratios were in equilibrium, there were large excesses of ²²⁸Th in the leachable fraction of both parent rock (${}^{228}\text{Th}{}^{232}\text{Th}\text{= 2.06}$) and partially weathered saprolite (${}^{228}\text{Th}{}^{232}\text{Th}\text{= 3–6.5}$), due to alpha recoil and release of daughter ²²⁸Th to the weathering rind of the mineral grain. For the most weathered sample, 81 percent of the thorium was in the teachable fraction and ${}^{228}\text{Th}{}^{232}\text{Th}\text{= 1}$, indicating that even the more resistant minerals were attacked.The total U activities showed as much variation in the six parent rock samples as in the weathered profile, and ${}^{234}\text{U}{}^{238}\text{U}$ were in equilibrium in both the whole-rock and leachable fractions. ²³⁰Th was deficient relative to ²³⁴U and ²²⁶Ra in both fractions, suggesting recent addition of U and Ra to the entire profile. The large variation in U was not from absorption onto the intermediate weathering products, because only 11–23 percent of the U was in the leachable fraction.     

Tourmaline composition and boron isotopes record lateritic weathering during the Great Oxidation Event

Identifying evidence of oxidative weathering in the geological record is essential to trace the evolution of Earth's atmosphere oxygenation. Metamorphosed residues of lateritic weathering have been identified as two rock types in the 2.1‐Ga‐old Cercadinho Formation, Piracicaba Group, Quadrilátero Ferrífero of Minas Gerais. One is tourmaline–hematite–sillimanite–kyanite quartzite; the other is rutile–tourmaline–hematite–muscovite phyllite. Both rocks have abundant tourmaline with δ¹¹B values between about ?17‰ and ?13‰. The Cercadinho tourmaline is roughly parallel to the povondraite–“oxy‐dravite” join of meta‐evaporitic tourmaline, in its more aluminous segment, offset to higher contents of iron. These compositional and isotopic characteristics of the Cercadinho tourmaline indicate that continental evaporitic brines interacted with aluminium‐ and iron‐rich residues of lateritic weathering. The abundance of disseminated tourmaline, a mineral poorly reported from palaeosols worldwide, implies a boron‐rich brine overprint on the lateritic profile before the onset of metamorphism, reflecting a climatic change from humid to arid conditions in a continental setting. The recognition of lateritic weathering in the Cercadinho Formation contributes to the amount of evidence for increased levels of atmospheric oxygen between 2.22 and 2.06 Ga ago.     

Evolution of continental crust and mantle heterogeneity: Evidence from Hf isotopes

We present initial ¹⁷⁶Hf/¹⁷⁷ Hf ratios for many samples of continental crust 3.7-0.3 Gy old. Results are based chiefly on zircons (1% Hf) and whole rocks: zircons are shown to be reliable carriers of essentially the initial Hf itself when properly chosen on the basis of U-Pb studies. Pre-3.0 Gy gneisses were apparently derived from an unfractionated mantle, but both depleted and undepleted mantle are evident as magma sources from 2.9 Gy to present. This mantle was sampled mainly from major crustal growth episodes 2.8, 1.8 and 0.7 Gy ago, all of which show gross heterogeneity of ¹⁷⁶Hf/¹⁷⁷Hf in magma sources from _Hf=0 to +14, or about 60% of the variability of the present mantle.The approximate _Hf=2_Nd relationship in ancient and modern igneous rocks shows that ¹⁷⁶Lu/¹⁷⁷Hf fractionates in general twice as much as ¹⁴⁷Sm/¹⁴⁴Nd in mantle melting processes. This allows an estimation of the relative value of the unknown bulk solid/liquid distribution coefficient for Hf. D_Lu/D_Hf= 2.3 holds for most mantle source regions. For garnet to be an important residual mantle phase, it must hold Hf strongly in order to preserve Hf-Nd isotopic relationships.The ancient Hf initials are consistent with only a small proportion of recycled older cratons in new continental crust, and with quasi-continuous, episodic growth of the continental crust with time. However, recycling of crust less than 150 My old cannot realistically be detected using Hf initials. The mantle shows clearly the general positive _Hf resulting from a residual geochemical state at least back to 2.9 Gy ago, and seems to have repeatedly possessed a similar degree of heterogeneity, rather than a continuously-developing depletion. This is consistent with a complex dynamic disequilibrium model for the creation, maintenance and destruction of heterogeneity in the mantle.     

Calcium isotopes in a proglacial weathering environment: Damma glacier, Switzerland

The biogeochemical cycling and isotopic fractionation of calcium during the initial stages of weathering were investigated in an alpine soil chronosequence (Damma glacier, Switzerland). This site has a homogeneous silicate lithology and minimal biological impacts due to sparse vegetation cover. Calcium isotopic compositions, obtained by TIMS using a ⁴³Ca-⁴⁶Ca double spike, were measured in the main Ca pools. During this very early stage of weathering, the young soils which have formed (δ^44/42Ca=+0.44‰) were indistinguishable to the rocks from which they were derived (δ^44/42Ca=+0.44‰) and stream water (δ^44/42Ca=+0.48‰) was also within error of the average rock. This lack of variation indicates that the dissolution of the bulk silicate rock does not strongly fractionate Ca isotopes. The only Ca pool which was strongly fractionated from bulk rock was vegetation, which exhibited an enrichment of light Ca isotopes. Significant Ca isotope fractionation between bulk rock and the dissolved flux of Ca is likely to only occur where the Ca biogeochemical cycle is dominated by secondary processes such as biological cycling, adsorption and secondary mineral precipitation.     

Lithium and boron isotopes in illite-smectite: The importance of crystal size

Clay minerals record chemical data about the past, acting like natural computer memory chips. To retrieve the data we must understand how they are stored. To achieve this we have examined the isotopic information revealed by two trace elements, lithium and boron, that are incorporated into the common clay minerals illite-smectite (I-S) during diagenesis. We used hydrothermal experiments at 300°C, 100 MPa, to speed up the reaction of smectite to illite that normally occurs during slow (10-100 Ma) sediment burial. During illitization, Li substitutes into the octahedral sites and B enters the tetrahedral sites of the silicate framework. Both Li and B are also adsorbed in the interlayer of smectite, but Li is preferred over B in the exchange sites. To determine the equilibrium isotope fractionation of the two trace elements it is important to remove these adsorbed interlayer species. By measuring the isotopic composition of Li and B in the silicate framework during reaction, we can address the relative timing of element exchange in the different crystallographic sites. Furthermore, because illitization of smectite is a crystal growth process (not an isomorphous replacement) we have examined the effect of crystal size on the isotope fractionation.The results show that Li and B approach an isotopic steady state when R1 ordering occurs, long before oxygen isotopes equilibrate with the fluid. The isotopic fractionation (α_{mineral-water}) for Li (0.989) is similar to that for B (0.984) at 300°C. However, when separated into <0.2, 0.2-2.0, and >2.0 μm fractions, there are significant differences in measured isotope ratios by as much as 9‰. Crystal growth mechanisms and surface energy effects of nanoscale crystals may explain the observed isotopic differences. The fact that different crystals equilibrate at different rates (based on size) may be applied to natural samples to reveal the changing paleofluid history, provided we understand the conditions of equilibrium. This has very important implications for the interpretation of diagenetic environments, fluid flow, and surficial geochemical cycling.