Determination of Various Forms of Iron and Manganese Oxides and the Main Controlling Factors of Absorption of Sb(Ⅲ) in Soil
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摘要:
研究影响土壤吸附Sb(Ⅲ)的主控因子对土壤锑污染的评价、预警及修复具有重要意义。本文采用化学法、电感耦合等离子体发射光谱法和原子荧光光谱法测定了10个不同地区土壤的理化性质和机械组成、主要化学组成，采用原子吸收光谱法测定了土壤铁锰氧化物的不同形态以及土壤对Sb(Ⅲ)的饱和吸附容量, 并开展了土壤对Sb(Ⅲ)的饱和吸附容量和土壤理化性质、机械组成、铁锰氧化物及其形态的相关性分析、主成分分析和因子分析。在研究土壤吸附Sb(Ⅲ)的影响因素基础上，进一步研究其主控因子。结果表明，10个不同性质的土壤对Sb(Ⅲ)饱和吸附容量介于0.63~3.98mg/g之间，与土壤类型有关，其大小顺序为：红壤＞棕壤＞黄壤＞褐土＞沙土。土壤对Sb(Ⅲ)饱和吸附容量与阳离子交换容量(CEC)、氧化铁总量、无定形铁含量呈极显著正相关，与游离铁含量、无定形锰含量以及游离锰含量呈显著正相关。主成分分析和因子分析结果表明土壤中6个因子是影响土壤吸附Sb(Ⅲ)的主控因子，影响力大小为：氧化铁总量＞CEC＞无定形铁含量＞游离铁含量＞无定形锰含量＞游离锰含量。铁锰氧化物及其形态显著影响土壤吸附Sb(Ⅲ)。
Abstract:BACKGROUND It is of great significance for evaluation, early warning and remediation of antimony contaminated soil to study the sorption factors affecting Sb(Ⅲ) adsorption in soil.
OBJECTIVES To investigate the forms of Fe and Mn oxides and controlling factors of Sb(Ⅲ) adsorption in soil.
METHODS The physicochemical properties, mechanical composition, and main chemical composition of soils from 10 different areas were determined by chemical method, inductively coupled plasma-optical emission spectrometry and atomic fluorescence spectrometry. The contents of different forms of iron and manganese and the saturated adsorption capacity of soils to Sb(Ⅲ) were determined by atomic absorption spectrometry. The correlation analysis, principal component analysis and factor analysis of soil saturated adsorption capacity to Sb(Ⅲ), soil physicochemical properties, mechanical composition, iron and manganese oxides and their forms were carried out by SPSS 21.0.
RESULTS On the basis of studying the influencing factors of soil adsorption of Sb(Ⅲ), the main controlling factors were further studied. The saturated adsorption capacity of soil to Sb(Ⅲ) was between 0.63mg/g and 3.98mg/g, and was related to soil type with the order of red soil>brown soil>yellow soil>cinnamon soil>sandy soil. According to the correlation analysis results, the saturated adsorption capacity of soil to Sb(Ⅲ) was significantly positively correlated with cation exchange capacity, total iron oxide, amorphous iron content, and was positively correlated with free iron content, amorphous manganese content and free manganese content. The principal component analysis and factor analysis showed that these six factors were the main controlling factors affecting the adsorption of Sb(Ⅲ) in soil, and the influence degree was: total iron oxide>cation exchange capacity>amorphous iron content>free iron content>amorphous manganese content>free manganese content.
CONCLUSIONS The adsorption capacity of soil to Sb(Ⅲ) is significantly affected by the total amount of iron and manganese oxides and their forms.
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Key words:
- soil /
- Sb(Ⅲ) /
- absorption /
- main controlling factors /
- iron manganese oxide forms /
- atomic absorption spectrometry
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表 1 土壤信息
Table 1. Soil information
样品编号 土壤类型 采集地 土壤利用类型 1# 褐土 天津市和平区蒙古路滨府里小区 城市绿地 2# 棕壤 河北省邯郸市磁县贾壁乡中贾壁村 菜地 3# 棕壤 广东省肇庆市金利镇梓里一工业区 绿地 4# 黄壤 湖南省株洲市渌口区渌湘大道 城市绿地 5# 褐土 甘肃省兰州市城关区骆驼滩村 绿地 6# 褐土 山东省德州市德新区新华街道 城市绿地 7# 棕壤 四川省眉山市丹棱县扬场镇 水稻土 8# 黄壤 江西省萍乡市芦溪镇温埠村 菜地 9# 沙土 四川省阿坝州诺尔盖 裸沙地 10# 红壤 四川省攀枝花市二滩水电站 果园地 
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表 2 土壤的理化性质
Table 2. Physical and chemical properties of soils
样品编号 pH SOM
(mg/g)CEC
(cmol/kg)机械组成(%) 黏粒(mm) 粉粒(mm) 砂粒(mm) < 0.005 0.005~0.01 0.01~0.05 0.05~0.075 0.075~0.25 0.25~0.5 0.5~1.0 1# 7.76 8.59 22.2 20.3 11.3 51.2 7.90 6.50 1.70 1.10 2# 8.12 6.44 29.5 18.3 9.30 56.9 6.20 5.00 1.60 2.70 3# 6.81 7.81 22.6 23.7 14.2 53.4 5.10 2.40 0.70 0.50 4# 6.53 1.33 17.4 37.3 10.9 26.0 5.20 12.80 2.90 4.90 5# 7.72 2.33 13.6 20.3 2.50 66.5 8.40 1.70 0.30 0.30 6# 8.57 2.67 19.8 16.1 10.0 40.1 24.9 5.40 1.40 2.10 7# 6.59 14.5 15.1 34.4 10.9 34.9 1.00 13.5 3.60 1.70 8# 5.04 5.09 12.9 43.1 11.1 28.8 5.60 9.40 0.90 1.10 9# 7.67 1.43 7.10 — — — 2.20 97.8 — — 10# 7.09 4.76 32.5 36.2 3.90 10.1 2.10 22.6 10.6 14.5
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表 3 土壤的主要化学成分及锑的含量
Table 3. Main chemical composition and Sb content of soils
样品编号 SiO2
(%)Al2O3
(%)Fe2O3
(%)MnO2
(%)CaO
(%)MgO
(%)K2O
(%)Na2O
(%)Sb
(mg/kg)1# 71.5 11.6 2.75 0.086 5.99 2.60 3.67 0.72 1.52 2# 70.6 13.9 5.12 0.093 3.31 1.25 4.21 0.77 1.46 3# 77.1 13.0 5.47 0.066 0.22 0.40 3.15 0.16 2.94 4# 58.2 20.4 3.34 0.062 0.46 0.64 4.47 0.30 2.91 5# 44.3 12.1 2.69 0.094 6.78 2.38 2.38 0.88 1.24 6# 59.4 6.63 1.95 0.101 5.73 1.98 2.05 0.51 1.28 7# 73.2 10.2 3.60 0.048 0.53 0.83 2.14 0.25 1.85 8# 50.3 14.2 2.71 0.020 0.14 0.47 16.65 0.19 1.26 9# 85.8 6.76 2.09 0.036 1.43 0.28 1.72 0.68 0.94 10# 53.5 22.2 12.3 0.048 0.37 0.39 0.80 0.18 1.97
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表 4 土壤中不同形态铁锰氧化物的含量
Table 4. Content of iron and manganese oxide forms in soils
样品编号 游离铁
(mg/g)无定形铁
(mg/g)络合铁
(mg/kg)游离锰
(mg/kg)无定形锰
(mg/kg)络合锰
(mg/kg)1# 5.00 3.19 89.0 315 277 27.1 2# 4.99 2.12 38.0 261 192 14.5 3# 12.7 2.50 127 328 249 112 4# 23.8 1.98 58.5 99.0 65.5 8.70 5# 2.56 1.61 32.5 171 82.0 9.40 6# 3.64 1.80 38.5 256 115 9.30 7# 9.97 5.91 479 193 187 94.0 8# 15.8 2.87 229 189 27.0 4.60 9# 3.06 0.82 29.5 54.0 94.0 12.4 10# 36.5 8.24 53.5 285 212 19.0
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表 5 土壤对Sb(Ⅲ)饱和吸附容量与土壤理化性质及各形态铁锰含量的相关性
Table 5. Correlation between soil with saturated adsorption capacity for Sb(Ⅲ) and soil physical and chemical properties, various forms of iron and manganese content
参数 氧化铁 氧化锰 游离铁 无定形铁 络合铁 游离锰 无定形锰 土壤对Sb(Ⅲ)饱和吸附容量 0.828** -0.052 0.685* 0.833** 0.052 0.645* 0.643* 参数 pH 络合锰 SOM CEC 黏粒 粉粒 砂粒 土壤对Sb(Ⅲ)饱和吸附容量 -0.08 0.131 0.363 0.815** 0.234 -0.114 -0.101 注：“*”表示在0.05水平上显著相关; “**”表示在0.01水平上显著相关。
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表 6 主成分分析特征值及其贡献率
Table 6. Eigenvalues and proportion of principal component analysis
成分 解释的总方差(初始特征值) 解释的总方差
(提取平方和载入)合计 方差
(%)累积
(%)合计 方差
(%)累积
(%)1 5.28 35.17 35.17 5.28 35.17 35.17 2 3.30 21.96 57.13 3.29 21.96 57.14 3 2.59 17.23 74.36 2.59 17.23 74.37 4 1.81 12.07 86.43 1.81 12.07 86.44 5 0.98 6.54 92.98 6 0.46 3.10 96.07 7 0.25 1.68 97.76 8 0.19 1.30 99.05 9 0.14 0.95 100 10 1×10-13 1×10-13 100 11 1×10-13 1×10-13 100 12 1×10-13 1×10-13 100 13 -1×10-13 -1×10-13 100 14 -1×10-13 -1×10-13 100 15 -1×10-13 -1×10-13 100
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表 7 最大方差法旋转成分矩阵
Table 7. Component matrix with maximum variance rotation method
因子 F1
(主成分1)F2
(主成分2)F3
(主成分3)F4
(主成分4)饱和吸附容量 0.959 0.074 -0.015 0.168 氧化铁总量 0.933 -0.158 -0.095 -0.035 CEC 0.866 0.375 0.156 -0.150 无定形铁含量 0.790 -0.146 -0.209 0.447 游离铁含量 0.751 -0.265 -0.549 -0.081 砂粒 -0.014 -0.959 0.171 -0.148 粉粒 -0.172 0.947 0.213 0.043 游离锰含量 0.626 0.603 0.010 0.229 氧化锰总量 0.017 0.468 0.428 -0.235 pH -0.029 0.149 0.888 -0.177 黏粒 0.386 0.240 -0.827 0.249 无定形锰含量 0.694 0.198 0.596 0.425 络合铁含量 -0.111 0.006 -0.378 0.882 SOM含量 0.112 0.240 -0.121 0.865 络合锰含量 0.416 -0.125 0.443 0.604
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