Characteristics and influencing factors of environmental persistent free radicals of humic acid extracts from different types of soil

doi:10.16085/j.issn.1000-6613.2020-1272

Abstract

Abstract:

Environmentally persistent free radicals (EPFRs) are widespread in soil organic matter. There is still insufficient research about the relationship between its characteristics (signal strength, g-value and line width) and the structure of organic matter composition. In this study, humic acids (HAs) extracted from Heilongjiang black soil, Yunnan red soil and Shandong yellow soil were used as experimental samples. The signal characteristics of EPFRs in HAs were determined by electron paramagnetic resonance spectroscopy (EPR). Elemental analysis, ultraviolet spectrophotometry,¹³C NMR nuclear magnetic, high performance liquid phase and other methods were used to determine the structure, composition and molecular weight distribution of HAs. The results showed that the amount of EPFRs (0.84×10¹⁶—7.42×10¹⁶spin/g) in HAs decreases with the increase of molecular weight. There were a significant positive correlation with the aromaticity of HAs (r=0.813, p<0.01), which is due to the fact that free electrons of aromatic compounds can partially separate domains to form EPFRs. The g values of EPFRs (2.0034—2.0041) decrease with the increase of aromaticity (r=-0.752, p<0.01). It was indicated that aromatic components have a major contribution to the carbon-centered free radicals. Compared with the soil in the other two regions, the EPFRs signal in Yunnan red soil with the rich Fe³⁺ content is the most stable. Under strong ultraviolet radiation in Yungui Plateau, it is more conducive to the formation of stable EPFRs. The present study is of great significance for understanding the environmental behavior of widely distributed EPFRs in soil.

Key words: natural organic matter, humic acid, molecular structure, environmental persistent free radical, aromaticity

摘要：

土壤有机质中存在环境持久性自由基（EPFRs），其特征（信号强度、g值和线宽）与天然有机质组分及其结构之间关联的研究还存在不足。本文采用黑龙江黑土、云南红土和山东黄土提取的胡敏酸（HAs）作为实验样品，通过电子顺磁共振波谱技术（EPR）分析测定HAs中自由基的信号特征，利用元素分析、紫外分光光度法、¹³C NMR核磁、高效液相等方法测定HAs提取物的结构、组分和分子量分布等。结果表明，HAs中EPFRs的量（0.84×10¹⁶~7.42×10¹⁶spin/g）随着分子量的增加而减少，且与HAs的芳香性有显著的正相关关系（r=0.813， p<0.01），这归因于芳香族化合物自由电子能够部分离域形成EPFRs。EPFRs的g值（2.0034~2.0041）随芳香性的增加而减少（r=-0.752，p<0.01），表明芳香性组分对碳中心自由基有主要的贡献。相比于其他两个地区的土壤，红土HAs中EPFRs信号最稳定，主要归因于云南土壤中Fe³⁺含量丰富，在强紫外线的辐射下更有利于形成稳定的EPFRs。

关键词: 天然有机质, 胡敏酸, 分子结构, 环境持久性自由基, 芳香性

CLC Number:

LU Yao, WANG Peng, YIN Mengnan, YANG Mingyi, ZHANG Huang. Characteristics and influencing factors of environmental persistent free radicals of humic acid extracts from different types of soil[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2917-2927.

鲁遥, 王朋, 尹梦楠, 杨名毅, 张凰. 不同类型土壤胡敏酸提取物环境持久性自由基特征及影响因素[J]. 化工进展, 2021, 40(5): 2917-2927.

Figures/Tables 9

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样品	g值	线宽ΔH	自旋密度/spin·g^-1
B-HA-1	2.0034	4.36	7.42×10¹⁶
B-HA-2	2.0035	4.52	4.37×10¹⁶
B-HA-3	2.0036	4.58	2.99×10¹⁶
B-HA-4	2.0039	4.66	2.13×10¹⁶
R-HA-1	2.0041	4.66	3.66××10¹⁶
R-HA-2	2.0040	4.35	4.91××10¹⁶
R-HA-3	2.0039	4.38	2.94××10¹⁶
R-HA-4	2.0038	4.66	2.43××10¹⁶
Y-HA-1	2.0040	4.36	3.03×10¹⁶
Y-HA-2	2.0039	4.51	1.11×10¹⁶
Y-HA-3	2.0040	4.58	1.14×10¹⁶
Y-HA-4	2.0039	4.66	0.84×10¹⁶

样品	g值	线宽ΔH	自旋密度/spin·g^-1
B-HA-1	2.0034	4.36	7.42×10¹⁶
B-HA-2	2.0035	4.52	4.37×10¹⁶
B-HA-3	2.0036	4.58	2.99×10¹⁶
B-HA-4	2.0039	4.66	2.13×10¹⁶
R-HA-1	2.0041	4.66	3.66××10¹⁶
R-HA-2	2.0040	4.35	4.91××10¹⁶
R-HA-3	2.0039	4.38	2.94××10¹⁶
R-HA-4	2.0038	4.66	2.43××10¹⁶
Y-HA-1	2.0040	4.36	3.03×10¹⁶
Y-HA-2	2.0039	4.51	1.11×10¹⁶
Y-HA-3	2.0040	4.58	1.14×10¹⁶
Y-HA-4	2.0039	4.66	0.84×10¹⁶

样品	元素分析（质量分数）						灰分 /%	E₂₈₅	E₄/E₆
样品	C/%	H/%	O/%	N/%	C/H比	(N+O)/C比	灰分 /%	E₂₈₅	E₄/E₆
B-HA-1	54.39	4.26	37.36	3.06	1.04	0.57	0.9	0.95	4.23
B-HA-2	54.63	4.53	36.99	3.24	1.00	0.56	1.1	0.87	4.33
B-HA-3	54.70	4.87	36.40	3.59	0.94	0.55	1.1	0.83	4.35
B-HA-4	54.81	5.24	35.72	3.82	0.87	0.54	1.2	0.64	4.38
R-HA-1	53.75	5.03	37.44	3.20	0.89	0.57	2.6	0.89	3.71
R-HA-2	53.88	5.22	37.12	3.22	0.86	0.56	1.4	0.75	3.93
R-HA-3	54.57	5.39	36.23	3.27	0.84	0.54	2.2	0.73	4.05
R-HA-4	55.34	5.79	34.93	3.32	0.80	0.52	2.0	0.68	4.16
Y-HA-1	51.13	5.14	39.83	3.57	0.83	0.64	2.7	0.74	4.15
Y-HA-2	51.30	5.34	38.31	4.42	0.80	0.63	1.7	0.62	4.23
Y-HA-3	51.59	5.70	37.82	4.26	0.75	0.62	2.6	0.51	4.27
Y-HA-4	51.72	5.86	36.87	4.92	0.73	0.61	2.4	0.41	4.30

样品	元素分析（质量分数）						灰分 /%	E₂₈₅	E₄/E₆
样品	C/%	H/%	O/%	N/%	C/H比	(N+O)/C比	灰分 /%	E₂₈₅	E₄/E₆
B-HA-1	54.39	4.26	37.36	3.06	1.04	0.57	0.9	0.95	4.23
B-HA-2	54.63	4.53	36.99	3.24	1.00	0.56	1.1	0.87	4.33
B-HA-3	54.70	4.87	36.40	3.59	0.94	0.55	1.1	0.83	4.35
B-HA-4	54.81	5.24	35.72	3.82	0.87	0.54	1.2	0.64	4.38
R-HA-1	53.75	5.03	37.44	3.20	0.89	0.57	2.6	0.89	3.71
R-HA-2	53.88	5.22	37.12	3.22	0.86	0.56	1.4	0.75	3.93
R-HA-3	54.57	5.39	36.23	3.27	0.84	0.54	2.2	0.73	4.05
R-HA-4	55.34	5.79	34.93	3.32	0.80	0.52	2.0	0.68	4.16
Y-HA-1	51.13	5.14	39.83	3.57	0.83	0.64	2.7	0.74	4.15
Y-HA-2	51.30	5.34	38.31	4.42	0.80	0.63	1.7	0.62	4.23
Y-HA-3	51.59	5.70	37.82	4.26	0.75	0.62	2.6	0.51	4.27
Y-HA-4	51.72	5.86	36.87	4.92	0.73	0.61	2.4	0.41	4.30

样品	脂肪碳（δ0~45）	烷氧基碳（δ45~110）	芳香碳（δ110~165）	羧基碳（δ165~190）	羰基碳（δ190~220）	芳香性/%	脂肪性/%
B-HA-1	19.95	13.05	45.02	13.08	8.90	57.69	42.31
B-HA-2	21.14	13.86	42.95	16.18	5.87	55.13	44.87
B-HA-3	22.45	15.55	40.96	17.08	3.96	51.89	48.10
B-HA-4	24.66	17.34	39.96	11.09	6.95	48.78	51.22
R-HA-1	24.75	16.83	37.62	12.87	7.93	47.50	52.50
R-HA-2	27.27	15.15	37.37	16.16	4.05	46.83	53.16
R-HA-3	31.63	12.24	36.73	17.35	2.05	45.57	54.43
R-HA-4	30.00	19.00	36.36	11.11	3.53	41.86	58.14
Y-HA-1	26.26	17.17	36.63	11.98	7.98	45.68	54.32
Y-HA-2	24.63	18.81	35.35	12.12	9.09	44.87	55.13
Y-HA-3	21.11	28.29	32.35	9.43	8.82	39.76	60.24
Y-HA-4	27.35	23.65	30.50	14.50	4.00	37.04	62.96