Variation patterns of boron and lithium isotopes in salt lakes on the Qinghai–Tibetan Plateau and their application in evaluating resources in the Damxung Co salt lake
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摘要: 近年，硼、锂同位素地球化学理论和分馏机理的深入，为盐湖体系硼、锂同位素示踪奠定了基础。基于现有大量研究数据，文章系统归纳盐湖体系硼、锂同位素分馏变化特征，总结盐湖演化过程硼、锂同位素组成的变化规律，建立它们的示踪方法。并以此为基础，对西藏典型富硼、锂盐湖−当雄错开展了硼同位素示踪，解决了当雄错与其物源硼同位素特征不符的难题，提出当雄错湖底蕴含大型硼、锂矿床的新认识，并预测了湖底的硼、锂资源量。根据盐湖体系硼、锂同位素地球化学特征，揭示了溶蚀湖的盐湖资源评价意义，为盐湖体系硼、锂同位素示踪和盐湖资源评价奠定理论基础。此外，借助硼同位素地球化学手段建立的当雄错“围岩−地热水−盐湖”的物源补给模式在西藏和全球具有普遍性。Abstract:
Objective The Qinghai–Tibet Plateau is rich in salt lake resources, known particularly for the concentration of elements such as boron and lithium, forming many distinctive resource-type salt lakes. Compared with ordinary salt lakes, a notable characteristic of resource-type salt lakes is the abundant supply of elements such as boron and lithium. Consequently, these elements' sources and accumulation patterns are key scientific issues for understanding the genesis and mineralization patterns of resource-type salt lakes. Boron and lithium isotopes, characterized by significant mass differences and variations in natural isotope ratios, serve as effective tracers for studying the material sources of boron and lithium in salt lakes. However, the application of boron and lithium isotopes in salt lake systems faces the following three challenges: (1) There is insufficient understanding of how boron and lithium isotopes respond to the fundamental geochemical processes of salt lakes. The salt dissolution process that occurs when supply water flows into lake basins is the main reason for drastic changes in geochemical parameters. Inadequate recognition of salt dissolution processes can lead to an overinterpretation of boron and lithium isotope fractionation changes, weakening their tracking capabilities. (2) Isotope fractionation degree is conflated with changes in isotope composition. In salt lake research, discussions of the solid phase's influence on boron and brine's lithium isotopes are often based solely on fractionation factors between the solid and liquid phases, without considering the ratios of boron and lithium amounts involved in the fractionation process. (3) Discrepancies still exist in understanding the fractionation patterns of boron and lithium isotopes during salt crystallization. Methods In light of these problems, our study systematically reviews and analyzes the mechanisms of boron and lithium isotopic fractionation in salt lake systems and summarizes some essential understandings. Conclusion (1) Only salt crystallizations have specific impacts on B and Li isotopes in salt lakes. Since there is a genetic association between salt assemblages and specific salt lake hydrochemical types, the salt lakes with the same hydrochemical type exhibit consistent patterns of B and Li isotope changes during their evolutionary processes. Until halite precipitation, the B and Li isotopic compositions in sulfate- and chloride-type salt lakes are in accord with δ11B and δ7Li values of their sources instead of being controlled by their salt deposits. In contrast, the paths of B and Li isotopic changes of carbonate-type salt lakes are complex and are divided into two branches: calcite subtype and hydromagnesite subtype. After calcite precipitation, the δ11B value of the salt lake increases, and its δ7Li value is marginally above source characteristics (less than 2‰). After hydromagnesite precipitation, the δ11B value of the salt lake is also marginally above source characteristics (less than 2‰). After the stage of halite precipitation, the B and Li isotopic compositions of salt lakes in all types show an increasing trend. (2) Based on the evolutionary processes of B, Li, and K during seawater evaporation, the amounts of B, Li, and K in the current salt lake represent most of the corresponding resources in the lake if the salt lake never experienced complete dryness such as playa. For the salt-dissolving lake, most of the B, Li, and K resources are preserved in salt deposits and interstitial brine at the bottom of the lake. It is optimal for the resource potential of a carbonate-type salt lake in the salt-dissolving lake. (3) The B sources of the current Damxung Co salt lake located in the Tibetan Plateau are from clay carbonates exposed to the lake shore and highly soluble salts and interstitial brine at the bottom of the lake. The geothermal waters produced during early hydrothermal activity are the original B source of the Damxung Co salt lake. Based on mass balance equations, it is estimated that the B resource at the bottom of the Damxung Co salt lake is at least 9.1×106t (B2O3), and the lithium resource is at least 8.6 ×106t (LiCl). -
Key words:
- Qinghai–Tibet Plateau /
- salt lake /
- boron /
- lithium /
- isotopic tracing /
- dissolving lake /
- resource evaluation
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图 1 当雄错构造地质背景与泉华群概况
DX—当雄错盐湖；DR—当若雍措；XR—许如错a—当雄错构造地质背景；b—当雄错泉华分布概况（红线区域指示新、老泉华的分布，影像呈现白色的区域为出露地表的碳酸盐）；c—当雄错泉华群野外概况（拍摄位置位于南泉华群一个泉华体顶部）
Figure 1. Tectonic setting of Damxung Co salt lake and overview of the travertine group
(a) Tectonic setting of the Damxung Co salt lake; (b) Overview of travertine distribution in the Damxung Co salt lake (The red lines indicate the distribution of new and old travertines, and the white areas in the image represent exposed carbonate on the surface); (c) Field photo of the travertine outcrops near the Damxung Co lake (taken at one of the travertine top of the southern outcrops) DX−Damxung Co salt lake; DR−Tangra Yumco lake; XR−Xuru Co lake
图 2 当雄错硼同位素地球化学行为与硼矿形成过程.
a—湖水蒸发浓缩至碳酸盐析出阶段；b—干盐滩阶段；c—溶蚀湖阶段
Figure 2. Geochemical behavior of boron isotope and the formation process of boron minerals in the Damxung Co salt lake
(a) Evaporative concentration and carbonate precipitation of the Damxung Co salt lake; (b) Total desiccation of the Damxung Co salt lake; (c) Formation of a salt dissolving lake in the Damxung basin
图 3 当雄错湖岸碳酸盐沉积剖面及光释光年代序列
Figure 3. Lacustrine carbonate sections in the Damxung Co salt lake and their OSL dating results
图 4 随着总碳酸盐沉积的硼矿占比（n）和现今湖水来自碳酸盐的硼占比（m）变化，当雄错未剥蚀碳酸盐的硼矿资源量情况
Figure 4. Boron resource of residual carbonate on lakeshore as a function of proportion of boron in total boron resource derived from carbonate (n), proportion of boron from carbonate erosion in lake water (m) and the degree of carbonate erosion (s)
图 5 随着总碳酸盐沉积的硼矿占比（n）和现今湖水来自碳酸盐的硼占比（m）变化，当雄错总硼矿资源量情况
Figure 5. Total boron resource as a function of proportion of boron in total boron resource derived from carbonate (n), proportion of boron from carbonate erosion in lake water (m) and the degree of carbonate erosion (s)
图 6 随着总碳酸盐沉积的硼矿占比（n）和现今湖水来自碳酸盐的硼占比（m）变化，当雄错湖底未溶蚀的盐沉积和晶间卤水的硼矿资源量情况
Figure 6. Boron resource buried in the bottom of the Damxung Co salt lake as a function of proportion of boron in total boron resource derived from carbonate (n), proportion of boron from carbonate erosion in lake water (m) and the degree of carbonate erosion (s)
表 1 海水和盐湖卤水中黏土矿物吸附的硼同位素分馏系数
Table 1. Boron isotopic fractionation factor (α) during adsorption of boron on clay in seawater and salt lake brine
编号 研究对象 分馏系数α 文献出处 1 海水与沉积物 0.975，0.976 Spivack et al.，1987；Palmer et al.，1987 2 柴达木盐湖−咸水湖与对应沉积物 0.987~0.998 Shirodkar and Xiao，1997；肖应凯等，1999 3 大柴旦卤水与沉积物 0.987~0.992 Xiao et al.，1992 4 卤水与沉积物模拟吸附实验 0.982~0.999 Xiao and Wang，2001（不包括负分馏） 5 尕海盐湖（青海湖旁边）与湖底淤泥 0.985 孙大鹏等，1993 
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表 2 石盐蒸发实验硼含量和硼同位素组成（据Liu et al.，2000修改）
Table 2. Boron concentrations and isotopic compositions in rock salt evaporation experiments (revised after Liu et al., 2000)
卤水 石盐 α B/ (μg/g) δ11B/ ‰ B/ (μg/g) δ11B/ ‰ 实验-1（纯石盐） 677 10.9 4.4 10.8 0.9999 710 11.2 8.0 10.7 0.9995 1120 11.0 12.2 10.8 0.9999 2871 10.8 39.7 10.9 1.0000 实验-2（含石膏石盐） 585 11.1 6.9 10.8 0.99996 712 10.6 12.4 9.2 0.9987 1038 10.5 17.7 7.1 0.9966 2303 11.0 48.0 7.8 0.9965
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表 3 不同水化学类型盐湖的硼、锂同位素变化特征
Table 3. The characteristics of boron and lithium isotopes in salt lakes of different hydrochemical types
水化学类型 主要盐沉积 硼、锂同位素特征 代表盐湖 硫酸盐型 芒硝+石盐 δl=δi 大柴旦，一里坪，东台，西台等 氯化物型 芒硝+石盐 δl=δi 察尔汗，钾湖，巴仑马海等 碳酸盐型 碳酸钙+芒硝+石盐 δ11Bl>δ11Bi；δ7Lil-δ7Lii<2‰ 扎布耶，当雄错 碳酸盐型 碳酸镁+芒硝+石盐 δ11Bl-δ11Bi<2‰；δ7Lil与δ7Lii关系待定 班戈错
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表 4 当雄错各类样品硼含量和硼同位素组成
Table 4. Boron concentrations and isotopic compositions of samples from the Damxung Co salt lake
样品类型 B/×10−6 δ11B /‰ 数据来源 地热水 0.40~6.20 −9.8~−8.5 Lü et al.，2013 冷泉水 0.12~0.61 −14.5~-14.1 Lü et al.，2013 河水 0.02~0.15 −4.9~−1.2 Lü et al.，2013 盐湖卤水（0.1~14.6 m) 208.10~1760.80 −18.5~−17.4 北京绵平盐湖研究院，2006；Lü et al.，2013 钙华 90.40~236.00 −29.5~−24.9 Lü et al.，2013 碳酸盐 47.50~264.00 −37.2~−35.3 Lü et al.，2013
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表 5 当雄错泉华铀系年龄
Table 5. U-Th results of travertine samples near the Damxung Co salt lake
样品编号 样品类型 238U/×10−9 232Th/×10−9 230Th/232Th/×10−6 δ234U 230Th /238U 230Th年龄/a（未校正） 231Th年龄/a（校正） DXC003-1 泉华 670±2 10076±203 43.4±0.9 452.9±3.2 0.0395±0.0003 3003±23 2702±214 DXC003-15 泉华 302±1 14692±295 13.1±0.3 500.3±3.0 0.0386±0.0006 2836±44 1890±671 DXC003-8 泉华 454±1 8601±173 97.6±2.0 421.4±2.4 0.1122±0.0004 8935±36 8549±275 DXC009-2 泉华 125064±383 59295±1198 1227.8±25.1 521.4±2.5 0.0353±0.0002 2557±12 2548±14 DXC009-14 泉华 46742±165 496200±10093 72.2±1.5 592.3±3.9 0.0465±0.0003 3225±22 3032±139
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