王祎(1997—),女,山东淄博人,硕士研究生,主要从事土壤发生与地球化学研究。E-mail:
铁锰结核是土壤演化过程中形成的一种特殊新生体,其内部同心圆环带构造可用于反演古气候条件和成土环境,其组分可为微生物代谢提供营养元素和能量,进而影响土壤中养分和重金属的转化、固定与释放。本文综述了近几十年来国内外学者对土壤中铁锰结核研究所取得的进展,包括铁锰结核形成机制、演变过程与影响因素,不同地区铁锰结核微结构与组分差异,以及铁锰结核对养分转化与重金属吸附的影响。未来需进一步研究不同成土阶段铁锰结核形成速率与环境阈值,构建不同成土环境中铁锰结核演化模型,阐明铁锰结核对土壤中养分和重金属的固释机理,以期更好地理解地表关键带土壤发生过程与元素生物地球化学循环,为定量评价变化环境下土壤质量和功能提供依据。
Ferromanganese concretions (or Fe-Mn nodules), as a specific type of soil neoformations, are formed during pedogenic processes. The structure of concentric rings in soil Fe-Mn nodules can be used to reconstruct paleoclimatic conditions and soil-forming environments. The constituents of soil Fe-Mn nodules can provide nutrients and energy for microbial metabolism that in turn affect the transformation, fixation and mobilization of soil nutrients and heavy metals. This article reviewed the research progresses on soil Fe-Mn nodules during the past several decades, including(i) the formation mechanism and process of Fe-Mn nodules and the associated influencing factors; (ii)differences in the microstructure and constituents of Fe-Mn nodules in different regions; and(iii) effects of Fe-Mn nodules on nutrient transformation and heavy metal sorption. Future research priorities include(a) study of the formation rates and environmental thresholds of Fe-Mn nodules during different stages of soil development; (b) establishment of the evolution models of Fe-Mn nodules in different soil-forming environments; and(c) elucidation of the mechanisms of stabilization and release of soil nutrients and heavy metals by Fe-Mn nodules. This will facilitate understanding of the pedogenic processes and elemental biogeochemical cycling in the Earth's Critical Zone and provide a basis for quantitative evaluation of soil quality and function under changing environments.
土壤形成与演化过程、速率及环境阈值是地球关键带研究的核心问题之一[
铁锰结核是成土过程的产物,其同心圆环带构造可用于反演古气候条件和成土环境[
铁锰结核是土壤长期演化的产物,是铁、锰元素在氧化还原作用下经过一系列的溶解—沉淀反应,并与土体中其他物质聚集而形成的[
铁锰结核形成机制示意图
Schematic diagram of the formation mechanism of Fe-Mn nodules
铁锰结核中主要存在3种环带:铁富集环带、锰富集环带和铁锰共生环带(
铁锰结核的形成过程包括成核和“生长”两个阶段,不同阶段成土环境具有很大差异,从而导致铁锰结核环带构造(例如环带数量、厚度、孔隙度和元素空间分布)不断发生变化。然而,由于常规技术手段(显微镜、扫描电镜、X-射线衍射仪等)所限,过去的研究无法揭示铁锰结核形成过程以及不同发育阶段铁锰结核环带构造动态演变特征。最近,Yu等[
直径为5~6.5 mm的铁锰结核形成过程及不同形成阶段所对应的成土环境(据Yu等[
Reconstruction of the geologic climate corresponding to the forming process of the 5~6.5 mm Fe-Mn nodule(modified from Yu et al., 2020)
不同pH-Eh条件下铁、锰氧化物溶解度(据刘英俊等[
Solubility of iron oxides and manganese oxides under different pH-Eh conditions(modified from Liu et al., 1984)
综上所述,铁锰结核的环带构造(环带数量、厚度、孔隙度、元素组成和分布特征等)作为“指纹信息”可以有效记录成土古气候环境变化过程和不同阶段干湿交替频率(相对值)[
铁锰结核的形成受不同因素共同影响,可分为内因和外因(
影响铁锰结核形成过程的因素
Factors influencing the forming process of Fe-Mn nodules
外部环境条件变化可以改变土壤性质或成土过程,从而间接影响铁锰结核环带构造和组分。例如,地下水位周期性波动影响土壤干湿状况和Eh值,进而影响铁锰结核形态与构造[
铁锰结核的形成与成土作用同步进行,不同地区成土因素和成土过程具有很大差异,因此不同地区土壤中铁锰结核形态构造、元素含量及矿物组成也具有很大差异,本文将从这三方面来阐述不同地区或不同类型土壤中铁锰结核特征及其异同点。
铁锰结核主要由铁锰氧化物、矿物颗粒和养分元素富集区域组成[
铁锰结核颜色受铁、锰氧化物含量及二者之间比值的影响,铁氧化物含量高的结核以红色、黄棕色为主,锰氧化物含量高的以黑色、深灰色为主[
铁锰结核中化学元素以Si、Al、Fe、Mn为主,其中铁、锰元素含量远高于周围土壤(约为周围土壤的10~100倍)。结核中Mn的含量一般低于Si、Al和Fe,而Fe/Mn比值与其矿物组成和丰度有关[
铁锰结核还能够富集微量元素,主要存在3种富集方式:继承土壤母质中微量元素、铁细菌等微生物参与氧化还原反应释放微量元素、结核表面发生络合反应或吸附微量元素[
铁锰结核广泛存在于不同类型土壤中(
不同地区或不同类型土壤中铁锰结核研究文献汇总
Summary of published literature on Fe-Mn nodules in different areas or different types of soils
中国土壤系统分类名称[ |
研究地点 |
气候类型 |
植被类型 |
成土母质 |
原生矿物 |
次生矿物Secondary minerals | 参考文献 |
||
黏土矿物 |
铁氧化物 |
锰氧化物 |
|||||||
雏形土 |
西班牙韦斯卡省 | 半干旱地中海气候 | -b | 全新世沉积物 | 石英、方解石 | 伊利石 | 针铁矿 | 水钠锰矿、 |
[ |
雏形土 |
俄罗斯远 |
温带季风 |
原始针叶林和落叶林 | 晚白垩纪火山岩 | - | - | - | - | [ |
变性土 |
法国艾居 |
温带海洋性气候 | - | 角闪岩、 |
- | - | - | - | [ |
变性土 |
玻利维亚圣克鲁斯 | 热带草原 |
- | 中新世泥岩和砂岩 | 石英 | - | 针铁矿、磁赤铁矿、赤铁矿 | - | [ |
变性土 |
波兰 | 温带阔叶林气候 | 角树、青柠、橡树 | 第四纪黄土 | 云母、长石 | 蒙脱石、高岭石、绿泥石 | 针铁矿、 |
水锰矿、钡镁锰矿 | [ |
变性土 |
美国德克萨斯州 | 亚热带季风气候 | - | - | 石英、云母 | 蒙脱石、高岭石 | - | - | [ |
淋溶土 |
美国密苏里州 | 大陆性湿润气候 | 农作物 | 第四纪冲积物、沉积物 | 石英 | - | 针铁矿、 |
- | [ |
淋溶土 |
中国湖北 | 亚热带季风气候 | - | 第四纪冲积物 | 石英 | 伊利石、高岭石 | 针铁矿、 |
锂硬锰矿、羟锰矿 | [ |
淋溶土 |
希腊中部 | 地中海气候 | - | 第四纪冲积物 | 石英、长石 | 伊利石 | 针铁矿、 |
- | [ |
淋溶土 |
美国密西西比州 | 温带大陆季风气候 | - | - | [ |
||||
淋溶土 |
美国肯德基州 | 亚热带湿润气候 | - | - | 云母、石英 | 高岭石 | 针铁矿 | - | [ |
淋溶土 |
意大利西西里 | 地中海气候 | - | 更新世碳酸岩 | 石英 | 高岭石、伊利石 | 针铁矿、赤铁矿 | - | [ |
淋溶土 |
美国印第安纳州 | 热带季风气候 | 玉米 | - | - | - | - | - | [ |
淋溶土 |
中国河南 | 大陆性季风气候 | - | 第四纪红黏土 | - | - | - | - | [ |
淋溶土 |
中国湖北 | 亚热带季风气候 | - | 第四纪红黏土 | - | - | - | - | |
淋溶土 |
日本冲绳 | 亚热带海洋性气候 | 柠檬树、 |
石灰岩 | - | 高岭石 | - | 水钠锰矿、锂硬锰矿 | [ |
均腐土 |
美国伊利诺伊州 | 温带季风 |
- | - | - | - | - | - | [ |
铁铝土 |
中国湖南 | 亚热带季风气候 | - | 第四纪红黏土 | - | 高岭石、伊利石、蛭石 | 针铁矿、 |
锂硬锰矿 | [ |
富铁土 |
中国台湾 | 亚热带季风气候 | 水稻 | 第四纪冲积物 | - | - | - | - | [ |
富铁土 |
美国密苏里州东 |
亚热带湿润气候 | 白橡树、红橡树 |
前寒武纪花岗岩 | - | - | - | - | [ |
富铁土 |
中国浙江 | 亚热带季风气候 | 柑橘树 | 第四纪红黏土 | 石英 | - | - | 锰钾矿、 |
[ |
- | 中国浙江 | 亚热带季风气候 | 水稻 | 第四纪红黏土 | - | - | - | - | [ |
雏形土、 |
印度 |
热带季 |
- | - | 石英、长石 | 伊利石 | - | - | [ |
不同类型土壤(雏形土、均腐土、淋溶土) |
中国北方 | 温带湿润 |
- | 第四纪黄土 | - | - | - | - | [ |
不同地区、同一类型土壤中铁锰结核的矿物组成也存在差异(
铁锰结核形成过程中不仅能够耦合土壤中碳、氮、磷等养分转化[
铁锰结核中富含比表面积大的铁、锰氧化物,由于Fe和Mn是活性较高的变价元素,因此在滞水还原条件下结核中铁、锰氧化物发生溶解反应,并向土壤中释放Fe2+、Mn2+和养分元素;而在氧化环境中Fe2+和Mn2+会迅速沉淀形成铁、锰氧化物,并吸附和固定土壤中碳、氮、磷等养分元素[
铁锰结核形成过程中会吸附和固定
前人研究结果显示铁锰结核具有吸附重金属和净化土壤的能力[
潘根兴[
前人通过化学分析、扫描电镜和同步辐射等技术手段对土壤中铁锰结核的形态、结构和组分进行了大量研究,揭示了铁锰结核形成机制、演变过程和影响因素,阐明了不同地区铁锰结核微结构和组分差异,探讨了铁锰结核对养分转化和重金属吸附的影响,为解译土壤发生过程、重建古气候环境和拓展元素循环路径提供了重要信息。基于对土壤中铁锰结核研究现状的分析,提出了未来铁锰结核研究的方向和需进一步解决的关键科学问题(
铁锰结核形成过程及其与元素循环之间的关系示意图
Schematic diagram of the formation process of Fe-Mn nodules and its relationship with element cycling
(1)揭示不同成土阶段铁锰结核形成速率与环境阈值。过去往往选取不同地区土壤中的铁锰结核进行静态对比研究,为分析和阐释不同成土条件下铁锰结核元素含量、同心圆环带构造及矿物组成差异奠定了基础,但这些研究难以量化不同成土阶段铁锰结核的形成速率与环境阈值,使得进一步理解铁锰结核与成土微环境之间的相互作用与反馈机理陷入困境。土壤时间序列为研究土壤演变速率、方向及关键土壤属性动态变化特征和环境阈值提供了有效手段[
(2)构建不同成土环境中铁锰结核演化模型。铁锰结核是在特定的成土环境中经过物理、化学和生物作用而逐渐“成核”并不断“消长”,这些过程受到自然成土因素和人为作用的共同影响。在漫长的成土过程中,不仅自然成土因素发生改变,人为作用的方式和强度也会发生变化[
(3)阐明铁锰结核对土壤中养分和重金属的固释机理。过去的研究表明,铁锰结核不仅能够耦合土壤中碳、氮、磷等养分转化[
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