锰对土壤砷形态转化及水稻吸收砷的影响

doi:10.16258/j.cnki.1674-5906.2022.04.019

生态环境学报 ›› 2022, Vol. 31 ›› Issue (4): 802-813.DOI: 10.16258/j.cnki.1674-5906.2022.04.019

锰对土壤砷形态转化及水稻吸收砷的影响

徐梅华¹(), 顾明华¹, 王骋臻¹, 雷静²^,^*(), 韦燕燕¹, 沈方科¹

1.广西大学农学院,广西南宁 530004
2.广西大学农牧产业发展研究院,广西南宁 530004

收稿日期:2021-11-08 出版日期:2022-04-18 发布日期:2022-06-22
通讯作者: *雷静（1973年生）,女,讲师,硕士,研究方向为环境生态。E-mail: ljfy1173@126.com
作者简介:徐梅华（1997年生）,女,硕士研究生,研究方向为土壤学。E-mail: xu_meihua02@163.com
基金资助:
国家自然科学基金项目(41967045)

Effect of Manganese on Arsenic Speciation in Soil and Arsenic Migration to Rice

XU Meihua¹(), GU Minghua¹, WANG Chengzhen¹, LEI Jing²^,^*(), WEI Yanyan¹, SHEN Fangke¹

1. College of Agriculture, Guangxi University, Nanning 530004, P. R. China
2. Institute of Agricultural and Animal Husbandry Industry Development, Nanning 530004, P. R. China

Received:2021-11-08 Online:2022-04-18 Published:2022-06-22

摘要/Abstract

摘要：

土壤中铁锰氧化物是影响土壤砷形态及其生物有效性的重要因素。通过盆栽试验法,利用土壤理化性质相近而锰质量分数相差大的两种自然土壤混合得到土壤锰质量分数（mg·kg^-1）分别为580（Mn1）、980（Mn2）、1900（Mn3）、3030（Mn4）、4230（Mn5）的5个土壤,种植水稻（Oryza sativa L.）后,分别在水稻分蘖期、抽穗期和成熟期采集土壤孔隙水、水稻和土壤样品进行分析,探讨锰质量分数对土壤中铁、锰氧化物形态和砷形态转变及其对水稻吸收砷的影响和作用机制。结果表明,随着土壤锰质量分数增加,土壤Eh呈升高趋势;土壤中无定形铁氧化物、锰氧化物和游离态锰氧化物质量分数增加,成熟期Mn1和Mn5处理土壤无定形态铁氧化物、锰氧化物分别比分蘖期增加11.9%、40.5%和3.6%、35.7%;随着土壤锰质量分数增加,土壤中非专性吸附砷和专性吸附砷比例呈下降趋势,土壤砷更大比例以无定形铁氧化物结合态、晶质铁氧化物结合态和残渣态存在,从水稻分蘖期到成熟期处理Mn1土壤晶质铁氧化物结合态砷和残渣态砷的质量分数共减少了2.7%,Mn2至Mn5处理晶质铁氧化物结合砷和残渣砷的质量分数共增加了6.3%—14.0%,土壤孔隙水Fe(Ⅱ)、As(Ⅲ) 质量浓度降低;随着土壤锰质量分数增加,水稻根、茎、叶和籽粒砷质量分数减少,各部位的砷富集系数减小,水稻各部位砷质量分数与土壤非专性吸附态砷质量分数呈现极显著正相关,与无定形铁氧化物结合态砷质量分数显著负相关。综上所述,土壤中高质量分数锰可以延缓Eh下降,促进土壤中无定形态铁氧化物、锰氧化物和游离态锰氧化物的形成及对砷的氧化和吸附固定,降低土壤砷的有效性,从而减少水稻对砷的吸收。

关键词: 铁锰氧化物, 砷形态, 土壤, 水稻, 砷, 吸收

Abstract:

Iron (Fe) and manganese (Mn) oxides are important factors affecting the speciation and bioavailability of arsenic (As) in soil. In this study, a pot experiment was conducted to investigate the effects of manganese content on the speciation of iron, manganese oxides, and arsenic in soils. Five soils with manganese contents of 580 mg∙kg^-1 (Mn1), 980 mg∙kg^-1 (Mn2), 1900 mg·kg^-1 (Mn3), 3030 mg∙kg^-1 (Mn4), and 4230 mg∙kg^-1 (Mn5) were obtained by mixing two natural soils with similar soil physical and chemical properties and different manganese contents. After planting rice (Oryza sativa L), pore water, rice, and soil samples were collected at the tillering, heading, and maturity stages of rice, respectively. The results showed that Eh, mass fraction of amorphous Fe oxides, amorphous Mn oxides, and free Mn oxides in soil were increased with the increase of Mn mass fraction in the soil at each growth stage of rice. These results indicated that a higher mass fraction Mn in soil can delay the decrease of Eh and further promote the formation of amorphous Fe oxides, amorphous Mn oxides, and free Mn oxides in soil. With the increase of soil manganese content, the proportion of non-obligate adsorbed As and obligate adsorbed As in soil decreased, and the dominant As in soil was amorphous iron oxide bound As, crystalline iron oxide bound As, and residual As. The mass fraction of crystalline iron oxide bound As and residual As in Mn1 soil decreased by 2.7% from the tillering stage to the maturity stage, and the mass fraction of crystalline iron oxide bound arsenic and residual As in Mn2-Mn5 soil increased by 6.3%-14.0%. Meanwhile, the mass concentrations of Fe (II) and As (III) in soil pore water decreased. These observations reflected that an increase of Mn content can promote the transformation of dissolved and adsorbed As to iron oxide bound or residual As, leading to a decrease of the availability of As in soil. As a result, with the increase of soil Mn contents, the As concentrations in roots, stems, leaves, and grains of rice decreased and the As enrichment coefficient in each part decreased. In summary, findings suggested a new insight on As inactivation in soil: a higher Mn concentration in soil can promote the formation of amorphous Fe oxides, amorphous Mn oxides, and free Mn oxides in soil and further increase the immobilization of As in soil.

Key words: iron-manganese oxide, arsenic speciation, soil, rice, arsenic, uptake

中图分类号:

徐梅华, 顾明华, 王骋臻, 雷静, 韦燕燕, 沈方科. 锰对土壤砷形态转化及水稻吸收砷的影响[J]. 生态环境学报, 2022, 31(4): 802-813.

XU Meihua, GU Minghua, WANG Chengzhen, LEI Jing, WEI Yanyan, SHEN Fangke. Effect of Manganese on Arsenic Speciation in Soil and Arsenic Migration to Rice[J]. Ecology and Environment, 2022, 31(4): 802-813.

图/表 18

表1 供试土壤相关性质

Table 1 Related properties of tested soils

土壤类型 Soil types	土壤基本性质 Basic properties of soils
土壤类型 Soil types	w_{(总铁 Total Fe)}/ %	w_{(总锰 Total Mn)}/ (mg∙kg^-1)	w_{(总砷 Total As)}/ (mg∙kg^-1)	pH	w_{(有机质 Organic matter)}/ (mg∙kg^-1)	w_{(总氮 Total nitrogen)}/ (g∙kg^-1)	w_{(有效磷 Effective phosphorus)}/ (g∙kg^-1)	w_{(有效钾 Effective potassium)}/ (mg∙kg^-1)
低锰土 Soil with low Mn mass fraction	6.56	582.67	57.54	6	24	1.82	0.55	410.25
高锰土 Soil with high Mn mass fraction	6.85	4232.66	69.75	6.6	26.4	2.03	1.14	398.47

图1 不同处理对土壤pH的影响不同字母表示同一时期处理之间有,下同

Figure 1 Effects of different treatments on soil pH Different letters indicate significant differences between treatments during the same period (P<0.05), n=4, the same as below

图2 不同处理对土壤Eh的影响

Figure 2 Effects of different treatments on soil Eh

图3 不同处理对土壤中无定形态铁、锰氧化物质量分数的影响

Figure 3 Effects of different treatments on the mass fraction of amorphous Fe and Mn oxides in the soil

图4 不同处理对土壤中游离态铁、锰氧化物质量分数的影响

Figure 4 Effects of different treatments on the mass fraction of free Fe and Mn oxides in the soil

图5 不同处理对分蘖期土壤各砷形态质量分数的影响 S2、S3、S4、S5分别为专性吸附态砷,无定形态铁氧化物结合态砷,晶质铁氧化物结合态砷和残渣态砷,n=4,下同

Figure 5 Effects of different treatments on mass fractions of As speciation in soils at tillering stage S2, S3, S4, S5 denote obligate adsorbed As, amorphous Fe oxides bound As, crystalline Fes oxide bound As and residual As, respectively, n=4, The same as below

图6 不同处理对抽穗期土壤各砷形态质量分数的影响

Figure 6 Effects of different treatments on mass fractions of As speciation in soils at the heading stage

图7 不同处理对成熟期土壤各砷形态质量分数的影响

Figure 7 Effects of different treatments on mass fractions of As speciation in soils at maturity

表2 不同处理对土壤中非专性吸附态砷质量分数占总砷质量分数比例的影响

Table 2 Effects of different treatments on the mass fraction ratio of non-obligate adsorbed As to total As in soils

处理 Treatment	非专性吸附态砷质量分数的比例 Proportion of non-obligate adsorbed As mass fraction in soils/%
处理 Treatment	分蘖期 Tillering	抽穗期 Heading	成熟期 Maturity
Mn1	0.06	0.09	0.13
Mn2	0.05	0.04	0.09
Mn3	0.02	0.05	0.08
Mn4	0.01	0.04	0.06
Mn5	0.02	0.03	0.06

图8 不同处理对土壤各砷形态质量分数随时间变化的影响

Figure 8 Effects of different treatments on the variation of As speciation mass fraction with time in soils

表3 土壤砷形态质量分数与土壤铁锰氧化物质量分数相关性分析

Table 3 Correlation analysis between As speciation and Fe/Mn oxides in soils

土壤砷形态 Speciation of As in soil	土壤铁锰氧化物形态 Speciation of Fe oxides and Mn oxides in soils
土壤砷形态 Speciation of As in soil	无定形铁氧化物 Amorphous Fe oxides	无定形锰氧化物 Amorphous Mn oxides	游离铁氧化物 Free Fe oxides	游离锰氧化物 Free Mn oxides
S1	0.035	-0.409**	-0.071	-0.438**
S2	-0.137	0.114	0.429**	0.182
S3	0.278*	0.652**	-0.258*	0.747**
S4	0.370**	0.365**	-0.282*	0.387**
S5	0.238	0.302*	-0.0816	0.272*

图9 不同处理对土壤孔隙水中Fe(Ⅱ) 和As(III) 的影响

Figure 9 Effects of different treatments on Fe(II) and As(III) in soil pore water

表4 土壤孔隙水As(III) 质量浓度与土壤砷形态质量分数相关性分析

Table 4 Correlation analysis between As (III) concentration in soil pore water and As speciation of in soils, Fe/Mn oxides mass fraction, Eh value

孔隙水离子 Ion in pore water	土壤铁、锰、砷形态和Eh Speciation of Fe, Mn, As in soils and soil Eh
孔隙水离子 Ion in pore water	S1	S2	S3	S4	S5	无定形铁 Amorphous Fe	无定形锰 Amorphous Mn	游离铁 Free Fe	游离锰 Free Mn	Eh
As(III)	0.052	0.331**	-0.245	-0.522**	0.252	-0.476**	-0.48**	0.097	-0.447**	-0.759**

图10 不同处理对水稻上部叶、下部叶、茎、根砷质量分数的影响

Figure 10 Effect of different treatments on As mass fraction in upper leaves, lower leaves stems and roots of rice

图11 不同处理对水稻籽粒砷质量分数的影响

Figure 11 Effects of different treatments on As mass fraction in grains

图12 不同处理对水稻上部叶、下部叶、茎、根砷富集系数的影响

Figure 12 Effects of different treatments on As enrichment coefficients in upper leaves, lower leaves, stems and roots of rice

图13 不同处理对水稻籽粒砷富集系数的影响

Figure 13 Effects of different treatments on As enrichment coefficients in grains

表5 水稻各部位砷质量分数与土壤中各形态砷质量分数的相关性分析

Table 5 Correlation analysis between As mass fraction in different parts of rice and As mass fraction in soils

砷形态 As speciation	水稻各部位的总砷质量分数 Total As mass fraction in different parts of rice
砷形态 As speciation	茎 Stems	根 Roots	上部叶 Upper leaves	下部叶 Lower leaves	籽粒 Grains
S1	0.582**	0.574**	0.809**	0.798**	0.745**
S2	-0.237	-0.243	-0.299*	-0.329*	-0.032
S3	-0.413**	-0.616**	-0.597**	-0.721**	-0.519*
S4	0.182	-0.117	0.151	-0.076	0.191
S5	-0.174	-0.137	-0.241	-0.069	-0.683**

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锰对土壤砷形态转化及水稻吸收砷的影响

Effect of Manganese on Arsenic Speciation in Soil and Arsenic Migration to Rice

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