污染土壤颗粒态有机质镉锌富集特征及其解吸行为研究

doi:10.16258/j.cnki.1674-5906.2022.09.020

生态环境学报 ›› 2022, Vol. 31 ›› Issue (9): 1892-1900.DOI: 10.16258/j.cnki.1674-5906.2022.09.020

污染土壤颗粒态有机质镉锌富集特征及其解吸行为研究

马闯¹^,²(), 王雨阳¹^,², 周通¹, 吴龙华¹^,^*()

1.中国科学院土壤环境与污染修复重点实验室（南京土壤研究所）,江苏南京 210008
2.中国科学院大学,北京 100049

收稿日期:2022-04-10 出版日期:2022-09-18 发布日期:2022-11-07
通讯作者: *吴龙华（1969年生）,男,研究员,博士,主要研究方向为土壤污染与修复。E-mail: lhwu@issas.ac.cn
作者简介:马闯（1996年生）,男,硕士研究生,主要从事土壤重金属污染与修复研究。E-mail: machuang19@mails.ucas.ac.cn
基金资助:
国家自然科学基金项目(42007132);国家自然科学基金项目(U2002210)

Enrichment Characteristics and Desorption Behavior of Cadmium and Zinc in Particulate Organic Matter of Polluted Soil

MA Chuang¹^,²(), WANG Yuyang¹^,², ZHOU Tong¹, WU Longhua¹^,^*()

1. CAS Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, P. R. China
2. University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Received:2022-04-10 Online:2022-09-18 Published:2022-11-07

摘要/Abstract

摘要：

颗粒态有机质（POM）不仅是土壤活性有机质的重要组分,同时也是影响土壤中污染物迁移转化的重要因子,探明其镉（Cd）锌（Zn）富集特征及解吸行为,可深入了解土壤有机质与重金属的相互作用机制,为Cd、Zn污染土壤的修复提供科学理论。以我国西南某矿区周边重金属污染农田土壤为对象,利用物理分级技术从土壤中分离出2000-250 μm和250-53 μm的POM组分,并选择乙二胺四乙酸二钠盐（EDTA）作为提取剂分析POM中Cd、Zn的解吸动力学行为,结合红外光谱分析技术探究了EDTA提取前后POM中有机官能团变化。结果表明,POM对重金属Cd、Zn具有高度富集的特征,2000-53 μm POM中Cd和Zn质量分数显著高于2000-53 μm的矿物质组分和<53 μm的有机-无机复合体,且土壤中26.61%-26.74%的Cd和13.71%-23.60%的Zn富集在2000-53 μm POM中。EDTA提取24 h后,POM中Cd和Zn的提取率分别达75.74%和58.45%以上,表明POM中Cd、Zn有效性较高,其中Cd的解吸过程用Elovich方程的拟合效果最佳,Zn的解吸过程更适于双常数方程拟合。与EDTA提取前的POM比较,EDTA提取后2000-250 μm POM和250-53 μm POM中酯基（-COO^-）等含C=O键的基团相对含量分别提高了11.81%-28.59%和5.77%-6.59%,而POM中C-H基团的相对数量未发生显著变化。综上,POM中丰富的有机功能性基团是其富集Cd、Zn的重要机制,其富集的Cd、Zn等重金属被充分提取后,可进一步改变POM中有机功能性基团的相对丰度,对深入探讨受污染土壤修复过程中有机质的转化与稳定性具有重要意义。

关键词: 土壤, 重金属污染, 颗粒态有机质, 解吸动力学, 功能性基团, 有效性

Abstract:

Particulate organic matter (POM) is not only an important active fraction of soil organic matter, but also an important factor affecting the migration and transformation of heavy metals in polluted soil. The enrichment characteristics and desorption kinetics of cadmium (Cd) and zinc (Zn) in POM were studied to understand the interaction between soil organic matter and heavy metals, and provide a scientific theory for soil remediation. The long-term metal polluted soils were collected from farmland around a mining area in southwest China, and 2000-250 μm and 250-53 μm POM fractions were physically separated from soils. The desorption kinetics of Cd and Zn in POM were studied by EDTA as an extraction agent, and the changes in organic functional groups of POM before and after the EDTA extraction were characterized by Infrared spectroscopy. According to the results, Cd and Zn mass fractions of 2000-53 μm POM were observed, higher than those of 2000-53 μm mineral fraction and <53 μm organic and inorganic composite, and 26.61%-26.74% Cd and 13.71%-23.60% Zn were enriched in 2000-53 μm POM. There were over 75.74% Cd and 58.45% Zn which could be extracted from 2000-53 μm POM fractions by the EDTA, indicating a more readily available source of Cd and Zn in polluted soils. Unlike Zn, the Cd desorption in POM can be well fitted to the Elovich equation rather than the two-constant equation. After a 24 h extraction by EDTA, the relative contents of functional groups with C=O bond were increased by 11.81%-28.59% and 5.77%-6.59% for 2000-250 μm POM and 250-53 μm POM respectively. However, there were insignificant changes in the content of C-H functional group in 2000-53 μm POM after EDTA extraction. In summary, organic functional groups that can complex heavy metals is one of the important mechanisms for Cd and Zn enrichment in POM. After the extraction of heavy metals, the abundance of organic functional groups changed in POM. This finding is significant for exploring the transformation and stability of soil organic matters during remediation.

Key words: soil, heavy metal pollution, particulate organic matter, desorption kinetic, functional group, availability

中图分类号:

X131.3

马闯, 王雨阳, 周通, 吴龙华. 污染土壤颗粒态有机质镉锌富集特征及其解吸行为研究[J]. 生态环境学报, 2022, 31(9): 1892-1900.

MA Chuang, WANG Yuyang, ZHOU Tong, WU Longhua. Enrichment Characteristics and Desorption Behavior of Cadmium and Zinc in Particulate Organic Matter of Polluted Soil[J]. Ecology and Environment, 2022, 31(9): 1892-1900.

图/表 9

参考文献 43

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供试土壤 Tested soils	有机质 Organic matter/(g∙kg^-1)	pH	砂粒 Sand/%	粉粒 Silt/%	黏粒 Clay/%	Cd质量分数 w_(Cd)/(mg∙kg^-1)	Zn质量分数 w_(Zn)/(mg∙kg^-1)
对照土壤 Control soil	77.00±1.28	5.18±0.03	56.20	36.00	7.80	0.67±0.07	77.04±4.34
高污染土壤 High polluted soil	65.10±3.79	5.55±0.03	30.20	51.00	18.80	4.03±0.27	369.87±3.69

供试土壤 Tested soils	有机质 Organic matter/(g∙kg^-1)	pH	砂粒 Sand/%	粉粒 Silt/%	黏粒 Clay/%	Cd质量分数 w_(Cd)/(mg∙kg^-1)	Zn质量分数 w_(Zn)/(mg∙kg^-1)
对照土壤 Control soil	77.00±1.28	5.18±0.03	56.20	36.00	7.80	0.67±0.07	77.04±4.34
高污染土壤 High polluted soil	65.10±3.79	5.55±0.03	30.20	51.00	18.80	4.03±0.27	369.87±3.69

动力学方程 Kinetic equations	方程式 Formula	参考文献 References
简化Elovich方程 Simple Elovich equation	Y=a+1/β lnt	Havlin et al., 1985
抛物线扩散方程 Parabolic diffusion equation	Y=a+R×t ^0.5	Dang et al., 1994
双常数方程 Two constant equation	Y=a×t^b	Havlin et al., 1985

动力学方程 Kinetic equations	方程式 Formula	参考文献 References
简化Elovich方程 Simple Elovich equation	Y=a+1/β lnt	Havlin et al., 1985
抛物线扩散方程 Parabolic diffusion equation	Y=a+R×t ^0.5	Dang et al., 1994
双常数方程 Two constant equation	Y=a×t^b	Havlin et al., 1985

土壤组分 Soil fractions	质量分数 w/%		Cd质量分数 w_(Cd)/(mg∙kg^-1)		Zn质量分数 w_(Zn)/(mg∙kg^-1)
土壤组分 Soil fractions	对照 Control	高污染 High polluted	对照 Control	高污染 High polluted	对照土壤 Control	高污染 High polluted
POM (2000-250 µm)	3.88	2.17	2.30±0.03Ab	19.33±0.49Aa	233.45±4.93Ab	868.86±2.93Aa
POM (250-53 µm)	5.44	5.04	1.65±0.02Bb	12.93±1.80Ba	226.85±6.32Ab	632.21±15.08Ba
矿物质 Mineral (2000-250 µm)	15.01	3.76	0.07±0.01Db	1.89±0.30Da	8.56±0.22Cb	265.56±19.41Da
矿物质 Mineral (250-53 µm)	33.77	18.43	0.06±0.01Db	0.88±0.20Da	8.92±1.25Cb	87.38±12.94Ea
有机-无机复合体 Organic-inorganic composite (<53 µm)	40.89	70.77	1.03±0.12Cb	3.73±0.53Ca	157.89±2.99Bb	391.76±3.31Ca

污染土壤颗粒态有机质镉锌富集特征及其解吸行为研究

Enrichment Characteristics and Desorption Behavior of Cadmium and Zinc in Particulate Organic Matter of Polluted Soil

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POM粒径 Sizes of POM/μm	污染程度 Pollution degree	Cd			Zn
POM粒径 Sizes of POM/μm	污染程度 Pollution degree	Elovich方程 Elovich equation	扩散方程 Diffusion equation	双常数方程 Two-constant equation	扩散方程 Diffusion equation	双常数方程 Two-constant equation
2000-250	对照	0.715	0.462	0.687	0.887	0.974
2000-250	高污染	0.669	0.448	0.657	0.787	0.850
250-53	对照	0.757	0.714	0.774	0.926	0.790
250-53	高污染	0.910	0.654	0.900	0.892	0.900

指标 Index	污染程度 Pollution degree	Cd		Zn
指标 Index	污染程度 Pollution degree	2000-250 μm	250-53 μm	2000-250 μm	250-53 μm
24 h EDTA提取态 Extraction by EDTA for 24 h, w/(mg∙kg^-1)	对照	2.20±0.24Ab	1.66±0.05Bb	178.93±2.39Ab	162.13±4.27Bb
24 h EDTA提取态 Extraction by EDTA for 24 h, w/(mg∙kg^-1)	高污染	16.25±0.63Aa	9.67±0.19Ba	613.84±10.35Aa	369.26±8.18Ba
24 h 提取率 Extracted rate for 24 h/%	对照	95.44±0.10Aa	100.00±0.01Aa	76.66±0.01Aa	71.47±0.01Ba
24 h 提取率 Extracted rate for 24 h/%	高污染	83.95±0.05Ab	75.74±0.13Bb	70.65±0.01Ab	58.45±0.03Bb

变量 Variables	污染程度 Pollution degree	POM (2000-250 μm)		POM (250-53 μm)
变量 Variables	污染程度 Pollution degree	提取前 Before Extraction	提取后 After extraction	提取前 Before Extraction	提取后 After extraction
C-H/石英 C-H/Quartz	对照	0.11	0.12	0.081	0.092
C-H/石英 C-H/Quartz	高污染	0.10	0.13	0.088	0.088
C=O/石英 C=O/Quartz	对照	1.17	1.31	1.04	1.10
C=O/石英 C=O/Quartz	高污染	1.09	1.40	1.08	1.15

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