Formation Mechanism and Characterization of Mn(Ⅲ)-Humic Ligands Colloids in Ground Water Environment
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摘要: Mn（Ⅲ）是锰氧化还原循环中电子传递的中间体，广泛参与陆地和海洋生态系统中的碳、铁和硫的地球化学循环. 近年来在厌氧、微氧和有氧水环境中陆续发现了Mn（Ⅲ）有机络合物存在，研究地下水环境中Mn（Ⅲ）-腐殖质胶体的形成机制与行为特征对于认识锰的地球化学循环及其影响的营养物和污染物的迁移转化机制具有重要意义. 通过开展批实验，探讨氧气条件、腐殖质浓度和有机质种类对Mn（Ⅲ）-腐殖质胶体形成的影响，并结合FTIR、XRD、XPS、TEM多种手段表征其理化性质与稳定性.研究发现：厌氧或有氧-厌氧环境有利于Mn（Ⅲ）-腐殖质胶体形成，Mn（Ⅲ）-腐殖质的络合程度随着腐殖质浓度的升高而增强，富里酸更容易与Mn（Ⅲ）络合，但形成的胶体稳定性较Mn（Ⅲ）-胡敏酸胶体差. Mn（Ⅲ）-腐殖质胶体呈无定形形态，腐殖质上的羧基等含氧官能团与Mn（Ⅲ）形成内球络合物，可减缓Mn（Ⅲ）歧化程度. Mn（Ⅲ）-腐殖质胶体具有氧化和吸附能力，对地下水中污染物的迁移转化具有重要的环境意义.Abstract: Mn(Ⅲ) is the intermediate electron transport of manganese cycling, widely involved in the terrestrial and marine ecosystems in the geochemical cycle of carbon, iron and sulfur. Recently, Mn(Ⅲ)-humic ligands colloids are found in oxide, suboxic and anoxic zone.It is of great significance to study the formation mechanism and behavior characteristics of Mn(Ⅲ)-humic colloid in groundwater environment for understanding the geochemical cycle of manganese and the migration and transformation mechanism of nutrients and pollutants affected by it. In this study, batch experiments were conducted to explore the effects of oxygen conditions, humus concentration and organic matter species on the formation of Mn(Ⅲ)-humic ligands colloids andcombined with FTIR, XRD, XPS, TEM and other means to characterize the physicochemical properties and stability. Resultsshow that suboxic and anoxic environments favor Mn(Ⅲ)-humiccolloid formation. The degree of complexation of Mn(Ⅲ)-humic colloid increases with the increase of humic ligands concentration. FA is more easily complexed with Mn(Ⅲ), but the colloidal stability is worse than that of Mn(Ⅲ)-HA colloid.Furthermore, Mn(Ⅲ)-humic colloid is in an amorphous form, and oxygen-containing functional groups such as carboxyl groups on humus form an internal sphere complex with Mn(Ⅲ), which can stabilize Mn(Ⅲ) and slow down the degree of disproportionation.Mn(Ⅲ)-humic colloid has oxidation and adsorption capacity, which has important environmental significance for the migration and transformation of pollutants in groundwater.
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Key words:
- Mn(Ⅲ) /
- umic ligands /
- olloid stability /
- omplexation mechanism /
- groundwater
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图 1 不同环境条件下悬浮液中Mn形态随腐殖质浓度的变化
a，b，c，d分别对应HA厌氧条件、有氧-厌氧条件、有氧条件和FA有氧条件
Fig. 1. Formation of manganese colloids under different environmental conditions
图 2 Mn(Ⅲ)-腐殖质的(a) Zeta电位；(b)平均稳定常数KMn-Sol.DOM/Mn-Col.DOM
Fig. 2. Zeta(a) potential and KMn-Sol.DOM/Mn-Col.DOM(b) of Mn(Ⅲ)-humic colloids
图 3 络合Mn(Ⅲ)后腐殖质的性质变化
a为特征值SUVA254；b为特征值E2/E3
Fig. 3. Spectral properties of humus after complexation Mn(Ⅲ)
图 5 Mn(Ⅲ)与腐殖质络合作用前后的XRD图谱
Fig. 5. Comparisonof XRD patterns between Mn(Ⅲ)-humic colloids and humic alone
图 6 Mn(Ⅲ)-腐殖质络合物的XPS谱图
a, b. 为Mn(Ⅲ)-HA的Mn2p3/2谱图和C1s谱图；c, d. 为Mn(Ⅲ)-FA的Mn2p3/2谱图和C1s谱图
Fig. 6. XPS spectra of Mn(Ⅲ)-HA and Mn(Ⅲ)-FA colloids (A, B) XPS spectra of Mn(Ⅲ)-HA(C, D) XPS spectra of Mn(Ⅲ)-FA
图 7 TEM表征下Mn(Ⅲ)-腐殖质胶体的形貌结构以及相应的EDS元素映射
Fig. 7. Morphology and microscopic structure of Mn(Ⅲ)-humic colloids
表 1 标准腐殖质元素组成
Table 1. Elemental composition of standard humicligands
标准腐殖质 C H O N S P TOC (%) (mg/L) PPHA 56.37 3.82 37.34 3.69 0.71 0.03 408.65±3 PPFA 51.31 3.53 43.32 2.34 0.76 < 0.01 371.97±5 
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