Research progress of stable isotopic geochemistry of cadmium and zinc and its harm and control in soil and other geological bodies
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摘要:研究目的
镉、锌既是重要的矿产资源，也是有害的重金属元素。随着多接收电感耦合等离子体质谱仪（MC–ICP–MS）的发展，镉、锌等非传统稳定同位素体系的建立与应用使镉、锌地球化学研究水平迈上新的高度，镉、锌同位素体系建立与应用成为国际研究热点。
研究方法本文通过查阅大量镉、锌同位素的相关文献，从镉、锌同位素的分析方法、分馏机制、自然界储库组成及应用领域进行了综述。
研究结果（1）随着镉、锌同位素分析技术的不断改进，其同位素体系正在逐步建立；（2）地球各储库中的锌同位素组成已基本查明，镉同位素组成正处于数据积累阶段；（3）镉、锌同位素分馏机制主要包括吸附沉淀、生物作用、化学作用等，目前已逐渐被应用到指示行星分异、探明成矿机制、重建古环境、示踪污染源等多种领域中；（4）在解析重金属污染源时，多种同位素的联用有助于减小不确定性。
结论在新型同位素分析仪器和技术的开发下，镉、锌同位素的研究拥有更大的发展空间。未来的研究重点主要包括对镉、锌同位素分馏机制、部分储库含量、应用领域进行完善。
创新点:（1）本文将具有相似地球化学性质的镉元素和锌元素放在一起进行论述，有利于该领域学者对其进行对比分析；（2）本文较全面地总结了近年来镉、锌同位素的分析方法、研究成果、污染现状及修复技术，并提出了未来的主要研究方向，旨在推动镉、锌同位素的研究进程。
Abstract:This paper is the result of environmental geological survey engineering.
ObjectiveCadmium(Cd) and zinc(Zn) are both important mineral resources and harmful heavy metal elements. The recent development of multi–collector inductively coupled plasma mass spectrometry (MC–ICP–MS) has improved the precision of Zn isotope composition analysis in different environments. The establishment and application of non–traditional stable isotope systems such as cadmium and zinc have raised the geochemical research of cadmium and zinc to a new level, which also have become hot topics in isotope geochemistry.
MethodsThis paper reviews recent research progress on the analytical methods, fractionation mechanisms, isotopic compositions in different reservoirs, and application fields of Zn and Cd isotopes investigated in many studies.
Results(1) The improvement of Zn and Cd isotope analysis technology has promoted the establishment of their isotope systems. (2) The compositions of Zn isotopes in various reservoirs have been basically identified. The data for Cd isotope compositions in reservoirs and anthropogenic sources is in the period of accumulation. (3) The isotopic fractionation mechanisms of Cd and Zn mainly include mineral adsorption, biological processes, and chemical reactions, which have been applied in the indication of planetary evolution, the exploration of metallogenic mechanisms, paleoenvironmental reconstruction, and pollution source tracer. (4) The combination of multiple isotopes helps to reduce uncertainty in the analysis of heavy metal pollution sources.
ConclusionsThe development of new isotope analysis instruments and technologies has made the research of Zn and Cd isotopes more promising. It is expected that more work should be carried out in the near future to improve the fractionation mechanisms, compositions in partial reservoirs, and application fields.
Highlights:(1) This paper reviews Cd and Zn with similar geochemical properties together, which is conducive to similar research; (2) This paper summarizes the analysis methods, research results, pollution status, and remediation technology of Cd and Zn isotopes. The authors propose the main research directions for the future with the aim of promoting the research process for Cd and Zn isotopes.
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1. 研究目的（Objective）
湘中坳陷作为南方复杂构造区页岩气勘探的热点地区之一，也是中国油气勘探久攻未克的地区。前期在湘中地区北部的涟源凹陷泥盆系和石炭系获得了页岩气突破和发现，证实了湘中地区上古生界页岩气资源丰富。但对湘中地区南部的邵阳凹陷调查程度较为薄弱，针对邵阳凹陷二叠系仅开展了少量基础地质调查工作，页岩气资源潜力评价方面的工作尤为欠缺。本次研究依托邵阳湘邵地1井（XSD1井）钻探工程建立了邵阳凹陷二叠系地层层序序列，揭示了主要含气页岩层系的分布特征，获取了含气性评价参数，对湘中地区二叠系页岩气勘探开发和重新评价湘中坳陷页岩气资源潜力具有重要的现实意义。
2. 研究方法（Methods）
中国地质调查局武汉地质调查中心在收集分析区域地质相关资料的基础上，结合邵阳凹陷短陂桥向斜的煤田浅钻、非震物探等资料开展页岩气地质综合评价，采用页岩埋深500~4500 m，页岩有机碳含量≥1.0%，页岩厚度≥15 m，页岩有机质热演化程度1.0%~3.5%的评价参数在短陂桥向斜区优选页岩气远景区，论证部署了1口小口径页岩气地质调查井—XSD1井，湖南煤田地质勘查有限公司组织实施钻探（图 1a）。该井采样全井段取心钻井工艺，测井选取PSJ-2数字测井系统，录井采用SK-2000G气测录井，钻获二叠系大隆组156.05 m（暗色硅质页岩、钙质泥岩94.48 m），龙潭组349.95 m（暗色泥岩216.93 m，粉砂质泥岩36.9 m），对这两套层系共采集暗色泥岩样品33件，进行解析气含量测定分析，落实了含气性评价参数。
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图 1 湘邵地1井构造位置图（a）、主要含气层段岩性和含气性参数柱状图（b）、以及富集模式图（c）Figure 1. Structural location of Xiangshaodi 1 well (a), lithology and gas-bearing parameters of main gas bearing zones (b), and enrichment mode (c)3. 结果（Results）
本次样品分析工作由武汉地质调查中心古生物与生命-环境协同演化重点实验室完成，采用YSQ-IIIA岩石解析气测定仪（燃烧法）对含气段岩心共计33件样品进行分析。该井钻获二叠系大隆组厚度156.05 m，为一套硅质岩、硅质页岩、炭质钙质泥岩地层。其中在井深842~930.2 m硅质页岩、钙质泥岩段，气测全烃值从1.06%上升至16.54%，甲烷值从1.01%上升至14.04%，13件大隆组硅质页岩现场解析总含气量为1.29~9.97 m3/t，平均4.85 m3/t。实现了湘中坳陷二叠系页岩气新发现，有效拓展了华南地区大隆组勘探范围。
钻获龙潭组厚度349.95 m，上段为一套细砂岩、粉砂岩夹泥岩潮坪相沉积地层，下段为一套炭质泥岩、粉砂质泥岩夹薄层细砂岩泻湖相沉积地层。在井深1013.4~1048 m泥岩与粉砂岩互层段气测全烃值最高可达19.87%，甲烷值最高为16.94%，7件泥岩与粉砂岩样品现场解析总含气量0.57~3.42 m3/t，平均1.78 m3/t；井深1088.10~1199.75 m泥岩夹泥质粉砂岩含气层111.6 m，气测全烃值最高可达28.2%，甲烷值最高为23.6%，13件泥岩、粉砂质泥岩样品现场解析总含气量0.90~4.55 m3/t，平均2.01 m3/t（图 1b），首次查明了湘中坳陷二叠系龙潭组非常规油气分布特点。
通过区域地质背景分析，并结合煤田区域地质资料，本研究认为滑脱断裂（F9）上下盘具有不同的页岩气聚集条件。滑脱断裂之上由一系列的同向逆断层形成的逆冲推覆体，地层变形强烈，且裂缝发育，导致页岩气保存条件变差。滑脱断裂下盘是页岩气主要富集区，地层平缓，不发育次级通天断裂，与下盘地层形成反向遮挡，易形成封闭，保存条件良好（图 1c）。
4. 结论（Conclusions）
（1）二叠系大隆组岩性以硅质岩、硅质页岩为主，夹少量灰岩。主要含气段存在于上段硅质页岩段，厚88.2 m，含气量平均为4.85 m3/t，含气性优越，资源潜力大。
（2）二叠系龙潭组上段以致密砂岩气为主，含气量平均为1.78 m3/t；下段以页岩气为主，泥岩厚达177.47 m，含气量平均为2.01 m3/t，具有泥岩厚度大，含气性好等特征。
（3）保存条件是页岩气富集关键，构造改造弱的封闭演化环境有利于页岩气保存，研究区滑脱断裂下盘是页岩气主要富集区，易形成封闭，保存条件良好。
（4）湘邵地1井在二叠系大隆组和龙潭组获得良好的页岩气显示，证实了湘中地区二叠系具有良好的页岩气资源潜力，对湘中地区页岩气资源潜力评价具有重要意义。
5. 基金项目（Fund support）
本文为中国地质调查局项目“中扬子地区油气页岩气调查评价”（DD20221659）资助的成果。
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图 1 阴离子交换树脂法洗脱过程中的Zn同位素分馏（据Maréchal and Albaréde, 2002）
Figure 1. Zn isotope fractionation during anionexchange chromatography (after Maréchal and Albaréde, 2002)
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图 2 不同高等植物在培养液中的Zn同位素分馏（据Weiss et al., 2005）
Figure 2. Zn isotope fractionation of different higher plantsin nutrient solutions (after Weiss et al., 2005)
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图 3 不同矿物吸附过程中的Zn同位素分馏（据Pokrovsky et al., 2005）
Figure 3. Zn isotope fractionation during adsorption on different minerals (after Pokrovsky et al., 2005)
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图 4 氧化铝吸附过程中的Zn同位素分馏（据Gou et al., 2018修改）
Figure 4. Zn isotope fractionation during adsorption on aluminum oxide (modified from Gou et al., 2018)
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图 5 氧化还原反应电位变化过程中的Zn同位素分馏（据Kavner et al., 2008）
Figure 5. Zn isotope fractionation duringthe potential change process of redox reaction (after Kavner et al., 2008)
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图 6 加拿大不列颠哥伦比亚省一冶炼厂样品中的Cd同位素分馏（据Shiel et al., 2010）
Figure 6. Cd isotope fractionation in samples from a smelter in British Columbia, Canada (after Shiel et al., 2010)
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图 7 小麦不同部位的Cd同位素组成（据钟松雄等, 2021）
Figure 7. Isotope composition of the cadmium in the root, straw and grain of wheat (after Zhong Songxiong et al., 2021)
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图 8 δ114/110Cdsolid–solution值与针铁矿（a）、赤铁矿（b）和水铁矿（c）表面Cd吸附率的函数关系（图形内部线条代表误差棒；据Yan et al., 2021）
Figure 8. Cd isotope compositions between solution and solid phases as the function of Cd–adsorbed fraction during adsorption onto goethite (a), hematite (b), and 2L ferrihydrite (c) (the lines inside the graphs represent error bars; after Yan et al., 2021)
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图 9 铁氧化物和羟基氧化物吸附和共沉淀过程中的Cd同位素分馏（据Yan et al., 2021）
Figure 9. Cd isotope fractionation during adsorption and coprecipitation of iron (oxyhydr) oxides (after Yan et al., 2021)
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图 10 陨石中的Zn同位素组成（据Brugier et al., 2019）
Figure 10. Zn isotopic composition of meteorites (after Brugier et al., 2019)
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图 11 东北太平洋SAFe站（30°N 140°W）海水中的Zn浓度和δ66Zn值（据Conway and John, 2015）
Figure 11. Dissolved Zn concentrations and stable isotope ratio (δ66Zn) profiles from the SAFe station in the Northeast Pacific (30°N 140°W) (after Conway and John, 2015)
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图 12 不同类型土壤的Zn同位素组成（据Liang et al., 2022）
Figure 12. δ66Zn variations in the different types of soils (after Liang et al., 2022)
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图 13 热带地区土壤（a）和非热带地区土壤（b）中的δ66Zn值频率分布（据Liang et al., 2022）
Figure 13. Frequency distribution of δ66Zn in the tropical soils (a) and non–tropical soils (b) (after Liang et al., 2022)
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图 14 不同地区双壳类的Cd同位素组成（据Zhong et al., 2020）
Figure 14. Cadmium isotopic compositions of bivalves in the different areas (after Zhong et al., 2020)
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图 15 杨堤剖面F–F 之交δ114Cd演化图（据王伟中等, 2020）
Figure 15. Variations of δ114Cd of carbonates in the Yangdi profile across the FFB (after Wang Weizhong et al., 2020)
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图 16 中国沘江河流沉积物和河岸土壤Cd浓度及同位素组成（据Zhang et al., 2016）
Figure 16. Cd concentrations and Cd isotopic compositions in the soil and stream sediment samples of the Bijiang River, China (after Zhang et al., 2016)
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图 17 橄辉无球粒陨石中δ66Zn与锌同位素丰度的关系（据Moynier et al., 2010）
Figure 17. δ66Zn vs. abundance of Zn in ureilites. The ureilite samples are designatedwith their degree of shock (after Moynier et al., 2010)
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图 18 月海玄武岩中δ66Zn与锌元素丰度的数据（据Dhaliwal et al., 2018）
Figure 18. Zinc isotope vs. abundance data in the lunar samples (after Dhaliwal et al., 2018)
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图 19 金顶矿床和乌斯河矿床中δ66Zn值与Zn/Cd值的关系（据Li et al., 2019）
Figure 19. Correlation between Zn/Cd ratios and δ66Zn of sphalerites in the Jinding and Wusihe Zn–Pb deposits (after Li et al., 2019)
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图 20 金顶矿床中δ66Zn值与δ34S值的关系（据Li et al., 2019）
注：除第2组闪锌矿外，第1组闪锌矿的δ66Zn值与δ34S值呈负相关。灰色框代表硫细菌的δ34S值范围，灰色箭头指向细菌代谢更强的方向。文献数据来源于Pašava et al. (2014)
Figure 20. Variation of zinc isotope ratios of sphalerites as a function of sulfur isotopic compositions (after Li et al., 2019)
The gray box represents δ34S ranges of bacteriogenic sulfur and the gray arrow points to the larger degree of bacterial metabolism (Li et al., 2019). Literature data in the figure are from Pašava et al. (2014)
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图 21 雪球事件后海洋和盖层白云岩的Zn同位素演化示意图（据Kunzmann et al., 2013）
①—66Zn亏损；②—运输66Zn贫化的锌同位素；③—66Zn贫化的表层海水；④—66Zn富集；⑤—初级生产者优先摄取64Zn；⑥—66Zn富集的表层海水
Figure 21. Schematic portrayal of the Zn isotope evolution of the post–snowball ocean and cap dolostones (after Kunzmann et al., 2013)
①−66Zn depleted caps; ②−Delivering of 66Zn–depleted zinc; ③−Surface ocean depleted in 66Zn; ④−66Zn enriched caps; ⑤−Preferential 64Zn−uptake by primary producers; ⑥−Surface ocean enriched in 66Zn
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图 22 Hietajärvi、Outokumpu和Harjavalta三地泥炭样品的锌浓度和δ66ZnJMC值（据Weiss et al., 2007）
Figure 22. δ66ZnJMC and zinc concentrations measured in the peat samples at Hietajärvi Outokumpu and Harjavalta (after Weiss et al., 2007)
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图 23 Hietajärvi、Outokumpu和Harjavalta三地泥炭样品δ66ZnJMC值变化过程及机制（据Weiss et al., 2007）
Figure 23. Processes and mechanisms of the observed isotopic variability of zinc in the peat samples at Hietajärvi Outokumpu and Harjavalta (after Weiss et al., 2007)
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图 24 全国不同地区土壤Cd污染指数（据王静等, 2023）
Figure 24. Soil Cd pollution index in different regions of China (after Wang Jing et al., 2023)
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图 25 植物修复原理（据Shen et al., 2021）
Figure 25. Principles of phytoremediation (after Shen et al., 2021)
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图 26 微生物修复原理（据常海伟等, 2018）
Figure 26. Principles of microbial remediation (after Chang Haiwei et al., 2018)
表 2 不同样品中Zn的分离纯化方法
Table 2 Separation and purification methods of zinc in the different samples
样品类型 树脂类型 淋洗酸种类 Zn回收率 文献来源 黄铜矿和闪锌矿 AG MP–1 HCl 100%±6% Maréchal et al. (1999) 玄武岩 AG MP–1
EichromTRUSpecHCl 100% Archer and Vance (2004) 硅酸盐、金属硫化物等 AG MP–1 HCl+HNO3 100%±5% Zhu et al. (2015) 海水 Chelex100 HNO3 100.8%±0.7% Bermin et al. (2006) 溪水 AG MP–1 HCl 100% Borrok et al. (2007) 雨水和河水 Chelex100
AG1–X4HNO3 100%±1% Chen et al. (2009b) 
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表 3 固体样品中Cd的消解方法
Table 3 Digestion method of cadmium in the solid samples
样品类型 消解方法 酸的种类 Cd回收率 文献来源 土壤、污泥和沉积物 微波消解法 HCl+ HNO3+HF 94%~102% Pallavicini et al. (2014) 富含有机物的基质 高温高压密闭消解法 HNO3 高温灰化法 HCl 植物 酸提取法 HF+HNO3+HClO4 >95% Wei et al. (2015) 煤灰、受污染的土壤、生活污泥、工业污泥 酸提取法 HNO3、HClO4、HCl和HF的不同组合 2.6%~89.1% Park et al. (2019) 全消解法 21.6%~88.7% 沉积物、大米 干法灰化法 HNO3 72.8%~97.0% 苗鑫等(2021) 酸提取法 HNO3+HCl 90.2%~98.0% 微波消解法 HNO3+HF 96.6%~99.8% 高温高压密闭消解法 HNO3+HF 97.6%~102%
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表 4 不同样品中Cd的分离纯化方法
Table 4 Separation and purification methods of cadmium in the different samples
样品类型 分离方法 树脂类型 淋洗酸种类 Cd回收率 文献来源 陆源矿物 两步阴离子树脂分离 DowexAGI–X8 HCl 50% Rosman and De Laeter (1975) 岩石
陨石离子交换树脂双柱法 Biorad AG 1–X8
Eichrom TRU SpecHNO3+HCl+HBr 98% Wombacher et al. (2003) 土壤、
铁锰结核等离子交换树脂单柱法 AG MP–1 HCl >95% Cloquet et al. (2005) 河流沉积物 离子交换树脂单柱法 AG MP–1 HCl >90% Gao et al. (2008) 铅锌矿床矿物 离子交换树脂单柱法 AGMP–1M HCl 99.82% 朱传威等(2013, 2015) 海水 离子交换树脂双柱法 Chelex+AG MP–1 HCl+ HNO3+HBr 93% Lacan et al. (2006) 海水 离子交换树脂三柱法 Biorad AG 1–X8
Eichrom TRU SpecHCl >90% Ripperger and Rehkämper (2007) 海水 离子交换树脂三柱法 Biorad AG 1–X8+TRU HCl+H2O2+HNO3 >99% Gault–Ringold et al. (2012) 海水 离子交换树脂三柱法 Biorad AG 1–X8+TRU HCl+ HNO3+HBr >90% Yang et al. (2012) 低Cd含量
海水离子交换树脂三柱法 Biorad AG 1–X8
Eichrom TRU SpecHCl >85% Xue et al. (2012)
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表 5 Zn、Cd同位素的质量歧视校正及测试精度
Table 5 Precision of Zn and Cd isotopic determination and instrument mass fractionation correction in literatures
目标元素 校正方法 ±2SD 资料来源 Zn Cu 0.04 Maréchal et al. (1999) SSB 0.07 Mason et al. (2005) 0.09 Archer and Vance(2004) DS 0.04~0.08 Bermin et al. (2006) Cd Ag、Sb 0.2~0.8 Wombacher et al. (2003) Ag 0.8 Lacan et al. (2006) 0.2~1 Pallavicini et al. (2014) SSB 1.0~1.5 Wombacher et al. (2004) 0.1~0.5 Cloquet et al. (2005) Cd106–Cd108DS 0.04 Abouchami et al. (2011) Cd111–Cd113 DS 0.13~0.2 Xue et al. (2012) 0.15 Martinková et al. (2016) 注：Ag、Sb分别表示Ag、Sb外标法；SSB表示标样–样品交叉法；DS表示双稀释剂法；2SD表示多次测定标准溶液所得数值的重现性（魏荣菲等, 2014），对于Zn和Cd分别代表δZn/amu和εCd/amu。
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表 6 沘江河流沉积物和河岸土壤Cd同位素组成（据Zhang et al., 2016修改）
Table 6 Cd concentrations and Cd isotopic compositions of stream sediment and soil samples in the Bijiang River (modified from Zhang et al., 2016)
河流沉积物 左岸土壤 右岸土壤 距离/km 样品编号 δ114/110Cd/‰ 样品编号 δ114/110Cd/‰ 样品编号 δ114/110Cd/‰ SSD–1 0.29±0.04 LS–1 –0.23±0.02 RS–1 –0.19±0.06 0 SSD–2 0.10±0.02 LS–2 –0.23±0.04 RS–2 –0.22±0.01 1 SSD–3 0.13±0.05 LS–3 –0.23±0.02 RS–3 –0.14±0.05 2 SSD–4 0.08±0.02 LS–4 –0.24±0.01 RS–4 –0.13±0.02 3 SSD–5 0.05±0.04 LS–5 –0.25±0.04 RS–5 –0.10±0.02 4 SSD–6 0.02±0.04 LS–6 –0.29±0.05 RS–6 –0.15±0.04 5 SSD–7 0.03±0.05 LS–7 –0.24±0.02 RS–7 –0.17±0.03 6 SSD–8 –0.08±0.04 LS–8 –0.20±0.04 RS–8 –0.31±0.03 7 SSD–9 –0.09±0.03 LS–9 –0.32±0.04 RS–9 –0.31±0.01 8 SSD–10 –0.09±0.04 LS–10 –0.21±0.01 RS–10 –0.27±0.01 8.8 SSD–11 –0.10±0.05 LS–11 –0.24±0.01 RS–11 –0.31±0.04 9 SSD–12 –0.11±0.02 LS–12 –0.24±0.06 RS–12 –0.26±0.02 9.5 SSD–13 –0.17±0.02 LS–13 –0.20±0.04 10 SSD–14 –0.11±0.03 LS–14 –0.27±0.04 RS–14 –0.29±0.02 10.5 SSD–15 –0.18±0.02 LS–15 –0.20±0.04 RS–15 –0.13±0.02 11 SSD–16 –0.14±0.02 LS–16 –0.27±0.04 RS–16 –0.20±0.06 11.5
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表 7 自然界不同储库中的Zn同位素的组成
Table 7 Isotopic compositions of Zn in the different reservoirs
地质体 δ66Zn值 资料来源 变化范围 均值 天体
陨石碳质球粒陨石 +0.16‰~+0.52‰ +0.37‰ Luck et al. (2006) 普通球粒陨石 –1.30‰~+0.76‰ +0.10‰ 铁陨石 –0.59‰~+3.68‰ +1.34‰ 顽火辉石球粒陨石 +0.01‰~+7.35‰ — Moynier et al. (2017) 橄辉无球粒陨石 +0.40‰~+2.71‰ +0.85‰ Brugier et al. (2019) 月壤 +2.18‰~+6.39‰ +0.46‰ Moynier et al. (2006) 月海玄武岩 +0.17‰~+0.75‰ +3.89‰ 地幔 火山岩 +0.28‰±0.05‰ +0.28‰ Chen et al. (2013) 橄榄岩 +0.18‰±0.06‰ +0.18‰ Wang et al. (2016) 橄榄岩、科马提岩 +0.16‰±0.06‰ +0.16‰ Sossi et al. (2017) 苦橄岩 +0.20‰±0.03‰ +0.20‰ Mccoy–West et al. (2018) 上地壳 黑山页岩 +0.20‰~+0.32‰ +0.26‰ Maréchal et al. (2000) 地中海腐泥 +0.26‰~+0.29‰ +0.28‰ 海相碳酸盐岩 +0.32‰~+1.34‰ +0.91‰ Pichat et al. (2003) 黄土 +0.17‰±0.30‰ +0.24‰ Zhang et al. (2022a) 下地壳 麻粒岩、下地壳捕虏体 +0.28‰±0.04‰ +0.28‰ Zhang et al. (2020) 水圈 巴黎市区雨水 — +0.17‰ Chen et al. (2008, 2009a) 巴黎市区屋顶径流 –0.07‰~–0.02‰ –0.04‰ 巴黎市区污水 –0.03‰~+0.28‰ +0.11‰ 塞纳河流域 +0.07‰~+0.58‰ — 河流 –0.12‰~+0.88‰ +0.38‰ Little et al. (2014) 中欧雪样 –0.60‰~+0.68‰ — Voldrichova et al. (2014) 中欧冰样 –0.67‰~+0.14‰ — 生物圈 喀麦隆南部植物、枯枝落叶 –0.91‰~+0.75‰ +0.31‰ Viers et al. (2007) 绵羊骨骼 +0.36‰~+0.53‰ +0.45‰ Balter et al. (2010) 绵羊红细胞 –0.13‰~–0.01‰ –0.06‰ 绵羊血清 +0.41‰~+0.57‰ +0.49‰ 绵羊肝脏 –0.67‰~–0.34‰ –0.45‰ 绵羊肾脏 –0.36‰~+0.03‰ –0.11‰ 绵羊肌肉 +0.26‰~+0.59‰ +0.46‰ 绵羊粪便 +0.15‰~+0.19‰ +0.17‰ 绵羊尿液 +0.17‰~+0.47‰ +0.37‰ 杂食者血液 +0.12‰±0.07‰ +0.12‰ Costas–Rodriguez et al. (2013) 素食者血液 +0.26‰±0.04‰ +0.26‰
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表 8 自然界不同储库中的Cd同位素的组成
Table 8 Isotopic compositions of Cd in the different reservoirs
地质体 δ114/110Cd值 资料来源 变化范围 均值 天体
陨石普通球粒陨石 –9.2‰~+15.0‰ +3.1‰ Wombacher et al. (2008) 碳质球粒陨石 –3.9‰~+4.5‰ –0.1‰ 顽火辉石球粒陨石 –0.7‰~+16.0‰ +3.3‰ 辉石无球粒陨石 –0.8‰~–0.3‰ –0.6‰ 月球样品 +1.1‰~+11.3‰ +7.6‰ 海水 南海北部深水层 +0.34‰±0.05‰ +0.34‰ Yang et al. (2012) 双壳类 英吉利海峡 –0.88‰~–0.20‰ –0.54‰ Shiel et al. (2013) 大西洋 –1.08‰~–0.62‰ –0.88‰ 地中海 –0.51‰~–0.27‰ –0.43‰
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表 9 部分陨石及月球样品中的Cd同位素组成（据Wombacher et al., 2008修改）
Table 9 Cd isotope composition of some meteorites and lunar samples (modified from Wombacher et al., 2008)
陨石类型 δ114/110Cd值/‰ 碳质球粒陨石 Orgueil C1 regolith breccia –0.1 –0.3 Murchison CM2 breccia 0.4 Acfer 209 CR2 breccia 0.3 0.5 Acfer 094 C2 ungrouped breccia –0.3 –0.4 Leoville CV3 reduced 1.8 Dar al Gani 005 CO3 4.5 Watson 002 CK3–anomalous 0.4 Dar al Gani 275 CK4/5 –1.0 Dar al Gani 412 CK5 –0.3 辉石球粒陨石 Sahara 97166 EH3 3.4 Qingzhen EH3 16.0 Indarch EH 4 0.0 –0.4 Abee EH4 impact melt breccia –0.1 –0.7 Hvittis EL6 breccia 7.6 Ilafegh 009 EL7 with impact melt 4.3 月球样品 Dar al Gani 400 anorthositic breccia 1.1 Dar al Gani 262 polym anorth breccia 10.0 Pristine ferroan anorthosite (60025,771) 7.8 Soil (14163,910) 11.3
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表 10 不同铅锌矿床样品的Cd含量和同位素组成（据Zhu et al., 2013）
Table 10 Cadmium concentrations and isotopic compositions of samples in the different lead−zinc deposits (modified from Zhu et al., 2013)
名称 样品编号 样品类型 颜色 Cd/ (µg/g) δ114/110Cd /‰ 会泽 HZP5–11–2 闪锌矿 黑色 913 0.12 ± 0.08 会泽 HZP5–11–2 闪锌矿 黑色 923 0.07 ± 0.04 会泽 HZP9–2–1–① 闪锌矿 红棕色 770 0.16 ± 0.23 会泽 HZP9–2–1–② 闪锌矿 红棕色 1410 0.31 ± 0.28 会泽 HZP9–6–1 闪锌矿 黑色 623 0.24 ± 0.21 会泽 HZP9–7–1 闪锌矿 黑色 673 0.15 ± 0.11 会泽 HZP10–7 闪锌矿 黑色 725 −0.08 ± 0.20 会泽 HZP5–11–2 方铅矿 8 −1.53 ± 0.18 会泽 HZP9–2–2 方铅矿 24 −0.60 ± 0.10 会泽 HZP9–8–2 方铅矿 21 −0.63 ± 0.12 会泽 HZP9–8–2 方铅矿 15 −0.58±0.08 杉树林 SS01 闪锌矿 黑色 590 −0.13 ± 0.24 杉树林 SS13 闪锌矿 黑色 571 0.12 ± 0.03 杉树林 SS14–1 闪锌矿 黑色 930 −0.07 ± 0.21 杉树林 SS14–3 闪锌矿 红棕色 884 0.02 ± 0.34 杉树林 SS16 闪锌矿 黑色 608 −0.34 ± 0.24 杉树林 SS16 闪锌矿 黑色 510 −0.28 ± 0.28 富乐 FL128–① 闪锌矿 黑色 5430 0.32 ± 0.16 富乐 FL128–② 闪锌矿 浅黄褐色 11477 0.32 ± 0.13 富乐 FL43–① 闪锌矿 红棕色 9263 0.34 ± 0.21 富乐 FL43–② 闪锌矿 黑色 19714 0.03 ± 0.07 富乐 FL48 闪锌矿 黑色 6953 −0.20 ± 0.13 富乐 FL46 闪锌矿 黑色 10799 −0.30 ± 0.11 富乐 FL86 闪锌矿 红棕色 7116 0.02 ± 0.03 牛角塘 LJP3–3 闪锌矿 浅黄褐色 5330 −0.48 ± 0.01 牛角塘 LJP4–3 闪锌矿 浅黄褐色 7128 −0.34 ± 0.16 牛角塘 LJP2–2 闪锌矿 浅黄褐色 2177 0.18 ± 0.07 牛角塘 LJP2–8 闪锌矿 浅黄褐色 5207 −0.59 ± 0.01 牛角塘 LJP 3–1 闪锌矿 浅黄褐色 2075 −0.41 ± 0.07 金顶 Z–3 氧化物 −0.58 ± 0.09 金顶 Z–4 氧化物 −0.74 ± 0.09 金顶 Z–5 原生矿物 −0.35 ± 0.13 金顶 Z–6 原生矿物 −0.39 ± 0.07 金顶 Z–7 原生矿物 −0.50 ± 0.10
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表 11 巴西中元古代晚期Paranoá群穹隆状叠层石和共生型叠层石的部分元素含量及Cd同位素组成（据Viehmann et al., 2018修改）
Table 11 Partial element concentrations and Cd isotopic compositions of the Paranoá Group stromatolites (modified from Viehmann et al., 2018)
样品类型 样品编号 ε112/ 110Cd Cd/(µg/g) U/(µg/g) Ce/(µg/g) MnO/% 穹隆状叠层石 BR_SG_10a –0.58 0.1201 0.0721 1.48 20.2 BR_SG_10c –0.17 0.0383 0.0846 1.43 21.0 共生型叠层石 BR_FF_20b 1.72 0.0195 0.24 3.04 0.05 BR_FF_30b –0.74 0.0177 0.357 2.14 0.05 BR_FF_30cI 0.32 0.0121 0.483 2.60 0.05 BR_FF_30cII (duplicate) 0.67 0.0149 BR_FF_STR40aI –3.06 0.024 0.639 2.77 0.04 BR_FF_STR40aII (duplicate) –3.52 0.0203 BR_FF_STR40b –2.78 0.0249 0.565 2.61 0.04 BR_FF_STR40c –1.00 0.0160 0.456 2.59 0.05 BR_FF_STR40d –1.19 0.0145 0.537 2.55 0.04 BR_FF_STR50b 3.46 0.0057 0.28 1.85 0.06
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表 12 锌镉污染环境的修复技术
Table 12 Remediation technology of cadmium and zinc contaminated environment
修复技术 修复方法 优点 缺点 资料来源 物理修复 客土法 在受污染的土壤之上覆盖非当地原生的、由其他地区移来的非污染优质土壤 修复效果好，能隔离污染土壤、提高土壤的养分含量 施行代价高，对大面积污染的土壤治理难以推广，容易降低土壤肥力 侯李云等, 2015; Aoshima, 2016 换土法 将部分或全部受污染的土壤替换成非污染土壤 黄益宗等, 2013 深耕翻土 通过机械方式翻出深层的非污染土壤，从而置换表层的污染土壤 提高土壤肥力，改善土壤的理化性质 未从根源上解决污染问题，存在二次污染 黄益宗等, 2013 电动力学修复法 在污染环境的两侧施加直流电压，驱动重金属活化，并通过电泳、电渗流、电迁移使环境中重金属离子迁移到电极两端 设备简单、不易发生二次污染、去除效
率高具有局限性，适用于小范围的污染，修复成本高 Acar et al., 1995; 魏树和等, 2019 化学修复 化学淋洗法 使用淋洗液淋洗，使得吸附在土壤颗粒上的重金属离子发生溶解从而被清除 效率高、操作简单、修复范围广、时间短 成本高，容易造成二次污染和降低土壤肥力或水体质量 Poclecha and Lestan, 2010; 姚振楠等, 2021 化学固定法 加入固化剂，降低重金属的有效性 操作简单、成本低 只改变了元素的存在形式 徐慧婷等, 2019 生物修复 植物修复 通过植物稳定与吸收进行转运、修复重金属污染 环保性能高、成本低 修复周期长，不适用于多种重金属元素污染的环境；微生物活性易受温度等其他条件的影响 Rubin and Ramaswami, 1998; 俞文钰等, 2023 微生物修复 通过吸附、矿化、沉淀、溶解等方式来改变元素的生物有效性 Singh et al., 2004 动物修复 通过动物直接吸收或通过动物活动降低元素含量 田伟莉等,2013
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