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摘要:
矿物开采、煤炭燃烧等人类活动使大量的锑进入土壤，造成严重的锑污染，危害人类健康。厘清环境中锑的吸附-沉积行为对锑的环境归趋预测及污染防治具有重要意义，但土壤中典型矿物对锑的吸附沉积行为缺乏系统比较，界面吸附形态也难以表征。为了系统地比较土壤中典型矿物对锑的吸附能力差异，本文选用土壤中常见的5种金属氧化物(赤铁矿、针铁矿、水铁矿、氧化铝、斜方锰矿)和1种黏土矿物(高岭石)，探究Sb(Ⅲ)和Sb(Ⅴ)在其表面的吸附热、动力学行为，并基于原位拉曼光谱表征分析了锑的吸附形态，推测其吸附机理。结果表明：铁锰氧化物对锑的吸附容量较大，而氧化铝、高岭石对锑吸附容量较小，6种典型矿物对Sb(Ⅲ)和Sb(Ⅴ)吸附容量(mg/g)分别为水铁矿(101.4、55.9)＞斜方锰矿(16.52、7.58)＞针铁矿(13.30、5.67)＞赤铁矿(5.13、3.70)＞氧化铝(1.66、1.69)＞高岭石(0.27、0.51)；受锑存在形态及矿物表面电位的影响，酸性条件下有利于Sb(Ⅴ)的吸附，吸附量较之碱性环境有24%～78%增加，而Sb(Ⅲ)的吸附受pH值影响较小(变化范围0.3%～14%)；土壤中典型矿物对不同浓度的Sb(Ⅴ)主要为吸附作用，而Sb(Ⅲ)在较高浓度时，可能在矿物表面发生沉积，形成Sb2O3。本文通过采用拉曼光谱，基于锑的特征谱峰，可方便地对矿物表面吸附态和沉积态的锑进行原位表征。
Abstract:Human activities such as mineral mining and coal combustion cause a large amount of antimony to enter into environmental soil. Exploring the adsorption deposition behavior of antimony on typical soil minerals is important for predicting the environmental fate of antimony and preventing its pollution. Thus, six kinds of commonly found metal hydroxides and clay minerals in soil (namely hematite, goethite, ferrihydrite, aluminum oxide, ramsdellite, and kaolinite) were selected to investigate the adsorption thermodynamic and kinetic behavior of Sb(Ⅲ) and Sb(Ⅴ) on their surfaces, and speculate the adsorption mechanism. The order of adsorption capacities (mg/g) of six soil minerals for Sb(Ⅲ)/Sb(Ⅴ) were as follows: ferrihydrite (101.4, 55.9)>ramsdellite (16.52, 7.58)>goethite (13.30, 5.67)>hematite (5.13, 3.70)>aluminum oxide (1.66, 1.69)>kaolinite (0.27, 0.51). Affected by the speciation of antimony and the surface potential of minerals, acidic conditions were favorable for the adsorption of Sb(Ⅴ), while the adsorption of Sb(Ⅲ) was less affected by pH. The Sb2O3 formed after deposition was characterizedin situ by Raman spectroscopy. Sb(Ⅴ) adsorbed on the mineral by adsorption at different concentrations, while Sb(Ⅲ) deposits on the mineral surface at higher concentrations. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202404210093 .-
Key words:
- antimony /
- ferrihydrite /
- ramsdellite /
- aluminum oxide /
- adsorption /
- sedimentation /
- Raman spectroscopy
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表 1 Sb(Ⅲ)和Sb(Ⅴ)的吸附动力学拟合参数
Table 1. Fitting parameters of adsorption kinetics for Sb(Ⅲ) and Sb(Ⅴ)
矿物材料 Sb(Ⅲ)准一级动力学 Sb(Ⅲ)准二级动力学 Sb(Ⅴ)准一级动力学 Sb(Ⅴ)准二级动力学 K1
(h−1)qe
(mg/g)R2 K2
[g/(mg·h)]qe
(mg/g)R2 K1
(h−1)qe
(mg/g)R2 K2
[g/(mg·h)]qe
(mg/g)R2 赤铁矿 2.58 7.35 0.750 0.88 7.45 0.911 1.15 1.05 0.721 1.52 1.13 0.913 针铁矿 0.53 7.83 0.896 0.12 8.22 0.986 1.75 2.74 0.721 1.05 2.86 0.924 水铁矿 4.74 33.7 0.645 0.40 34.4 0.957 3.33 24.1 0.946 0.33 24.8 0.999 斜方锰矿 82.1 7.03 0.716 41.9 7.22 0.940 0.75 4.90 0.832 0.20 5.30 0.921 氧化铝 6.58 0.71 0.958 15.5 0.73 0.976 4.49 0.59 0.631 16.1 0.61 0.933 高岭石 6.45 0.08 0.927 132.8 0.08 0.973 0.34 0.09 0.894 9.17 0.06 0.939 
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表 2 Sb(Ⅲ)和Sb(Ⅴ)的吸附等温线拟合参数
Table 2. Fitting parameters of adsorption isotherms of Sb(Ⅲ) and Sb(Ⅴ)
材料 Sb(Ⅲ)-Langmuir Sb(Ⅲ)-Freundlich Sb(Ⅴ)-Langmuir Sb(Ⅴ)-Freundlich KL
(L/mg)qm
(mg/g)R2 n KF
[(mg/g)(mg/L)−1/n]R2 KL
(L/mg)qm
(mg/g)R2 n KF
[(mg/g)(mg/L)−1/n]R2 赤铁矿 0.48 5.13 0.961 2.90 1.90 0.996 0.11 3.70 0.925 2.43 0.70 0.997 针铁矿 0.21 13.30 0.834 2.22 3.05 0.997 0.14 5.67 0.987 2.79 1.30 0.994 水铁矿 1.01 101.4 0.980 2.09 45.3 0.979 1.00 55.9 0.789 4.62 31.7 0.987 斜方锰矿 0.15 16.52 0.964 2.19 3.19 0.993 0.76 7.58 0.950 4.62 3.56 0.995 氧化铝 0.08 1.66 0.961 1.84 0.20 0.993 0.10 1.69 0.871 2.75 0.36 0.983 高岭石 0.21 0.27 0.967 2.96 0.08 0.957 0.12 0.51 0.990 2.27 0.09 0.921
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表 3 Sb(Ⅲ)或Sb(Ⅴ)氧化物和相关矿物的拉曼光谱特征峰位及归属
Table 3. The characteristic Raman peaks of Sb(Ⅲ) or Sb(Ⅴ) oxides and the minerals and their assignment
材料 特征峰
(cm−1)归属 材料 特征峰
(cm−1)归属 Sb2O3［38-39］ 190 F2g振动 针铁矿［40-41］ 224 Fe—O拉伸振动 374 F2g振动 405 Fe—OH 拉伸振动 452 Ag振动 666 Fe—O拉伸振动 Sb2O5［42-43］ 495 Sb-O伸缩振动 斜方锰矿［44-45］ 575 Mn—O拉伸振动 635 Sb-O伸缩振动 645 Mn—O对称伸缩振动 赤铁矿［46-47］ 227 A1g振动 高岭石［48-49］ 189 A1g(ν1)AlO6振动 293 Eg振动 409 ν2(e)SiO4振动 413 Eg振动 460 ν2(e)SiO4振动 499 Eg振动 640 Si-O-Al伸缩振动 614 Eg振动 717 Si-O-Al伸缩振动 氧化铝［50-51］ 378 Eg振动 787 OH伸缩振动 417 A1g振动
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