Distribution and causes of selenium-rich soil in Lixiahe area of Hai 'an, Jiangsu Province
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摘要:
研究目的 近年来，天然富硒土地资源的开发利用越来越受到关注，但对于远离母岩的平原区富硒土壤成因尚不明确。以海安里下河地区为例，探讨平原区富硒土壤分布特征及其成因，进而指导富硒土地资源的开发利用。
研究方法 系统梳理了研究区1800组表层土壤样品和1000组土壤剖面样品地球化学数据，并给合以往研究资料，对数据开展了综合分析研究，采用沉积物的粒度特征反演了母质沉积环境。
研究结果 研究区农用地表层土壤中Se含量最高达0.63 mg/kg，富集区（≥ 0.3 mg/kg）面积达66 km2。土壤垂向剖面上，耕作层（0~20 cm）、犁底层（20~40 cm）、心土层（50~80 cm）、底土层（80~100 cm）和深土层（150~180 cm）Se平均含量分别为0.23 mg/kg、0.18 mg/kg、0.13 mg/kg、0.12 mg/kg、0.11 mg/kg，表聚性十分明显；表层土壤Se含量与母质层呈高度正相关，其相关系数在0.6~0.8(p＜0.01)之间。地表高程与土壤Se含量出现极显著负相关，相关系数达−0.6 (p＜0.01)，地势越高，土壤Se含量越低；土壤有机质与Se呈显著的正相关，成壤过程对硒具有重要的吸附和固定作用。
结论 研究区母质层主要受古潟湖－砂坝沉积体系的控制，富硒土壤主要为发育于古潟湖相的母质经表生富集作用形成，潟湖相沉积环境控制了土壤硒富集边界。基于多元线性回归分析技术揭示了土壤硒富集控制因素，其中土壤有机质对于研究区Se的富集起到了决定性作用，对土壤硒富集的贡献率达70%。
Abstract:Objective Recently, the development and utilization of natural selenium−rich land resources have attracted increasing attention. However, the genesis of selenium−rich soil in plain areas far from parent rocks is still unclear. This paper aims to take the Lixiahe area in Hai'an as an example to explore the distribution characteristics and genesis of selenium−rich soil in plain areas, thereby guiding the development and utilization of selenium−rich land resources.
Methods The paper systematically collated geochemical data from 1800 groups of surface soil samples and 1000 groups of soil profile samples in the study area, and combined with previous research data, conducted a comprehensive analysis and study of the data. The grain size characteristics of sediments were used to infer the depositional environment of the parent material.
Results The selenium (Se) content in the surface soil of agricultural land in the study area reaches up to 0.63 mg/kg, and the area of the enrichment zone (≥ 0.3 mg/kg) is 66 km2. In the vertical soil profile, the average Se content in plough layer ( 0~20 cm ), plough pan ( 20~40 cm ), subsoil ( 50~80 cm ), subsoil ( 80~100 cm ) and deep soil ( 150~180 cm ) were 0.23 mg/kg, 0.18 mg/kg, 0.13 mg/kg, 0.12 mg/kg, and 0.11 mg/kg, respectively, showing a very obvious surface accumulation; the selenium content in surface soil was highly positively correlated with the parent material layer, with a correlation coefficient between 0.6 and 0.8 (P<0.01). There was a highly significant negative correlation between ground elevation and soil Se content, with a correlation coefficient of −0.6 (P<0.01), indicating that the higher the terrain, the lower the soil Se content; soil organic matter (SOM) was significantly positively correlated with Se, playing an important role in the adsorption and fixation of selenium during soil formation.
Conclusions The parent material layer was mainly controlled by the ancient lagoon−sand dam sedimentary system. The selenium−rich soil in the area was mainly formed by the supergene enrichment of the parent material developed in the ancient lagoon facies. The lagoon facies sedimentary environment controls the selenium enrichment boundary of the soil. Based on multiple linear regression analysis, the controlling factors of soil selenium enrichment were revealed. Among them, SOM played a decisive role in the enrichment of Se in this area, and the contribution rate to soil Se enrichment was 70%.
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Key words:
- selenium-rich soil /
- soil organic matter (SOM) /
- lagoon /
- Lixia river /
- genesis /
- Hai 'an, Jiangsu Province
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表 1 土壤样品测试方法
Table 1. Test method of soil sample
测试指标 样品粒度 测试方法 检出限 RE RD 参照标准 pH ≤2 mm ISE 0.1 0.7~7.9% 1.6~15.8% 《土壤中pH的测定》
（NY/T 1377—2007）粒度分析 ≤2 mm 激光衍射法 0.01% 0.6~15% 2.1~19.5% 《粒度分布 激光衍射法》
（GB/T 19077—2016）有机质（SOM） ≤0.149 mm 重铬酸钾法 0.20‰ 0~4.1% 0.1~10% 《土壤检测 第6部分：土壤有机质的测定》（NY/T 1121.6—2006） 全Se ≤0.149 mm 原子荧光光谱法 0.01
mg/kg0.2~4.8% 3.0~12.8% 《土壤中全硒的测定》
（NY/T1104—2006)
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表 2 土壤Se及主要理化指标特征统计结果
Table 2. Characteristics of soil selenium and its main physicochemical indicators
土壤层位 耕作层(0~20 cm) 犁底层(20~40 cm) 心土层(50~80 cm) 底土层(80~100 cm) 深土层(150~180 cm) 样本数 n=1800 n=200 n=200 n=200 n=200 Se/(mg·kg−1) 范围 0.07~0.63 0.05~0.37 0.04~0.32 0.04~0.28 0.05~0.23 均值 0.23 0.18 0.13 0.12 0.11 SOM/‰ 范围 6.2~64.5 3.6~28.4 3.2~23.1 1.3~25.2 0.3~25.4 均值 26.9 13.2 8.7 6.7 6.5 pH 范围 4.90~8.48 6.80~8.50 6.89~8.74 7.19~9.07 7.11~9.25 中值 7.24 7.89 8.01 8.23 8.41 平均粒径/Ф 范围 4.97~8.04 5.00~8.71 4.67~8.72 4.91~9.05 4.49~9.23 均值 5.91 6.18 6.27 6.43 6.47
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表 3 土壤Se分级标准
Table 3. Soil selenium classification standard
指标 缺乏 边缘 足硒 富集区 过剩 Se/（mg·kg−1） ≤0.125 0.125~0.175 0.175~0.3 0.3~3 ＞3
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表 4 研究区各沉积单元粒度参数特征
Table 4. Characteristics of particle size parameters of each sedimentary unit in the study area
地貌分区 沉积单元 参数 平均粒径/Ф 粘粒/% 粉粒/% 砂粒/% SOM/‰ Se/（mg·kg−1） 里下河
浅洼区潟湖 范围 6.88~9.23 20~51.5 30~51.29 9.28~39.13 1.26~25.36 0.06~0.23 平均值 8.14 34.5 44.04 21.45 10.08 0.14 砂坝 范围 4.56~7.36 0.34~4.22 17.5~79.05 18.29~82.17 1.2~16.76 0.05~0.16 平均值 5.84 2.14 50.89 46.94 5.79 0.1 高沙平原 砂坝 范围 4.49~6.53 0.42~3.48 15.87~71.55 24.97~83.71 1.26~10.36 0.04~0.11 平均值 5.61 1.83 45.66 52.48 3.11 0.06 滨海平原 砂坝 范围 4.93~6.32 0.6~3.16 28.44~64.57 32.27~70.96 1.2~7.26 0.04~0.11 平均值 5.48 1.34 41.59 57.07 3.07 0.06
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表 5 表层土壤Se含量与下部各土壤Se含量相关系数（n=200）
Table 5. Relationship between Se content in surface soil and Se content in lower soil
土层/cm 犁底层（20~40） 心土层（50~80） 底土层（80~100） 深土层（150~180） 表层（0～20） 0.79** 0.71** 0.65** 0.60** 注：**表示在0.01水平（双侧）上显著相关
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表 6 地表高程与各层位Se、SOM、粘粒、Mz相关系数（n=200）
Table 6. Correlation coefficient between surface elevation and Se, SOM, Clay, Mz of each layer
项目 土层/cm 0~20 20~40 50~80 80~100 150~180 地表高程-Se −0.600** −0.646** −0.590** −0.621** −0.577** 地表高程-SOM −0.401** −0.519** −0.488** −0.492** −0.539** 地表高程-Clay −0.116 −0.101 −0.247** −0.246** −0.318** 地表高程-Mz −0.178* −0.164* −0.296** −0.281** −0.405** 注：**表示在0.01 水平（双侧）上显著相关；*表示在 0.05 水平（双侧）上显著相关（下同）
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表 7 各土层Se全量与土壤主要理化性质的相关系数
Table 7. Correlation coefficient between total soil Se content and main physicochemical properties
土层/cm 有机质 pH 粘粒 粉粒 砂粒 平均粒径 0~20 0.46** −0.04 0.20** 0.23** −0.23** 0.15* 20~40 0.82** −0.64** 0.16* 0.31** −0.39** 0.28** 50~80 0.83** −0.55** 0.26** 0.34** −0.52** 0.39** 80~100 0.86** −0.65** 0.47** 0.15* −0.62** 0.54** 150~180 0.87** −0.64** 0.55** 0.27** −0.67** 0.65** 0~180 0.86** −0.70** 0.36** 0.30** −0.29** 0.11*
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表 8 全土层（0 ～ 180 cm）Se含量多元回归线性模型
Table 8. Multiple regression linear model for Se content in the entire soil layer (0~180 cm)
因子 预测方程 (n=1000) R2 p 德宾-沃森值 F 单因子 SOM lg Sesoil＝ 0.480 lg SOM – 1.298 0.747 ＜0.01 1.225 322.52 pH lg Sesoil＝ - 3.96 lg pH + 2.703 0.456 ＜0.01 1.075 84.22 Mz lg Sesoil＝ 0.682 lg Mz – 1.391 0.046 ＜0.01 0.477 17.53 双因子 SOM+pH lg Sesoil＝ 0.449 lg SOM – 0.443 lg pH – 0.873 0.764 ＜0.01 1.203 163.50 SOM+Mz lg Sesoil＝ 0.476 lg SOM + 0.157 lg Mz – 1.419 0.765 ＜0.01 1.238 162.79 三因子 SOM+Mz+pH lg Sesoil＝ 0.436 lg SOM + 0.213 lg Mz
– 0.561 lg pH – 0.9220.779 ＜0.01 1.220 110.87 注：式中，Sesoil为土壤Se含量（单位为mg/kg）；SOM为土壤有机质含量（单位：‰）；Mz为平均粒径（单位：Ф）。R2为回归分析中自变量变异对因变量的解释度，即相对控制程度，范围为0~1；p为显著性水平，p < 0.05为有显著性，p < 0.01为极显著性，p＞0.05为没有显著性；德宾-沃森值为检验变量自相关性的指标，若在0~4之间，符合数据独立性；F值为组间和组内的离差平方和与自由度的比值，在p < 0.01下其值越大表明模型越具统计学意义
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表 9 土壤Se实测值与模型预测值偏差统计
Table 9. Deviation between measured soil Se values and model predictions
项目 含量偏差/
（mg·kg−1）实测值/
（mg·kg−1）预测值/
（mg·kg−1）相对偏差/% 最大正偏差 0.07 0.22 0.29 31.8 最大负偏差 −0.13 0.44 0.31 −29.5 均值 −0.001 0.24 0.23 −1.1 绝对值均值 0.035 0.24 0.23 17.2 注：含量偏差=预测值−实测值；相对偏差=含量偏差/实测值
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