基于作物Cd富集系数的土壤有效态Cd化学浸提方法筛选

doi:10.13745/j.esf.sf.2024.1.13

摘要/Abstract

摘要：

土壤中镉(Cd)被作物吸收的程度及其生态风险取决于土壤中Cd的赋存形态,基于Cd有效形态的污染土壤风险评价及在此基础上制订污染土壤修复安全阈值是Cd污染农田土壤风险评价和治理亟待解决的问题。目前针对土壤中重金属有效态的化学浸提方法较多,但缺乏针对不同性质土壤中有效态Cd的普适性浸提方法已成为Cd污染土壤风险评价技术瓶颈。本研究采集了全国9个不同性质农田土壤,以水稻、小白菜和玉米为测试作物,通过外源添加方法制备Cd污染土壤,结合土壤培养和盆栽实验,测定了5种常用化学浸提方法,包括中性无机盐浸提方法(CaCl₂浸提法)、弱酸浸提法(HCl浸提法)、络合螯合剂浸提方法(DTPA和ETPA浸提法)和组合浸提方法(Mehlich-3(M3)浸提法)对不同性质土壤中有效态Cd浸提效果及其与作物Cd吸收的量化关系,筛选适用于不同性质土壤中有效态Cd的通用浸提方法。结果表明,不同化学浸提法提取的土壤有效态Cd含量间具有显著差异,不同浸提方法对土壤中Cd的浸提率(%)为DTPA≈EDTA≈HCl> M3≈CaCl₂。不同化学浸提态Cd与作物Cd吸收的相关系数间具有显著差异,基于综合相关系数方法,得出5种不同浸提态Cd与作物Cd吸收的综合相关系数为I_M3=0.765,I_EDTA=0.641,I_DTPA=0.627,I_HCl=0.606,$I_{CaCl_{2}}=0.711$,M3浸提态Cd含量与不同性质土壤中水稻、小白菜和玉米植株地上部Cd相关性最高,可作为不同性质土壤中有效态Cd通用浸提方法。相关研究结果可为农田土壤中Cd有效态评价及Cd污染农田的修复提供理论依据。

关键词: 镉, 污染土壤, 富集系数, 化学浸提方法, 筛选

Abstract:

The degree of cadmium (Cd) uptake and transport in plants and its ecological risk are largely determined by the chemical form it takes in soils. In risk assessment of Cd contaminated farmland soils two urgent issues need to be addressed: risk assessment based on the effective form of Cd in soil, and formulation of safety threshold values for heavy metal remediation. Currently, although many effective chemical extraction methods are available for heavy metal remediation, there lacks a versatile extraction method for bioavailable Cd in soils with different soil properties. In this study, farmland soil samples of nine soil types in China are collected for soil culture and pot experiments using rice, Chinese cabbage, and corn as test crops. Chromium contaminated soil samples are prepared by exogenous addition methods. Overall, five commonly used chemical extraction methods—neutral inorganic salt (CaCl₂), weak acid (HCl), chelating agent (DTPA, ETPA), and combined (Mehlich-3, or M3) extraction methods—are tested to quantitatively evaluate the effectiveness of these methods for Cd extraction under different soil types and the relationship between Cd extracted from soils and Cd accumulation in crops, with the goal of finding an extraction method that is widely applicable in different soil types. Chromium bioavailability determined by different methods differed significantly (p<0.05), and the extraction rates (%) followed the order of DTPA≈EDTA≈HCl>M3≈CaCl₂. Through comprehensive correlation analysis, the comprehensive correlation coefficients (I_p) between Cd extracted from soil and Cd uptake in the shoots of crops were calculated for each method, yielding I_M3=0.765, I_EDTA=0.641, I_DTPA=0.627, I_HCl=0.606, $I_{CaCl_{2}}=0.711$. Thus, M3 was considered a versatile extraction method which showed the highest I_p values for rice, Chinese cabbage, and corn in soils with different soil properties. The above results provide a theoretical basis for the evaluation of Cd bioavailability in farmland soils and remediation of Cd contaminated farmland.

Key words: Cd, polluted soil, bioconcentration factor, chemical extraction method, screening

中图分类号:

俞磊, 孙晓艺, 秦璐瑶, 王静, 王萌, 陈世宝. 基于作物Cd富集系数的土壤有效态Cd化学浸提方法筛选[J]. 地学前缘, 2024, 31(2): 111-120.

YU Lei, SUN Xiaoyi, QIN Luyao, WANG Jing, WANG Meng, CHEN Shibao. Screening chemical extraction methods for bioavailable Cd in soils based on bioconcentration factor in crops[J]. Earth Science Frontiers, 2024, 31(2): 111-120.

图/表 4

参考文献 29

[1]	环境保护部, 国土资源部. 全国土壤污染状况调查公报[EB/OL]. (2014-04-17) [2014-04-17]. http://www.gov.cn/foot/2014-04/17/content_2661768.htm.
[2]	中国科技网. 科技日报: 重金属污染, 无法承受之“重”?[N/OL]. (2013-06-27) [2013-06-27]. https://www.chinanews.com/ny/2013/06-27/4976931.shtml.
[3]	LUO L, MA Y B, ZHANG S Z, et al. An inventory of trace element inputs to agricultural soils in China[J]. Journal of Environmental Management, 2009, 90(8): 2524-2530.
[4]	SMOLDERS E, MERTENS J. Cadmium[M]// ALLOWAYB J. Heavy Metals in Soils: Trace Metals and Metalloids in Soils and Their Bioavailability. Germany, Berlin: Springer, 2013, 283-311.
[5]	施姜丹, 史可欣, 黄雨佳, 等. 中国大米和蔬菜重金属/类金属污染及其健康风险[J]. 环境卫生学杂志, 2022, 12(7): 479-487.
[6]	GAO Y, DUAN Z Q, ZHANG L X, et al. The status and research progress of cadmium pollution in rice- (Oryza sativa L.) and wheat- (Triticum aestivum L.) cropping systems in China: a critical review[J]. Toxics, 2022, 10(12): 794.
[7]	杨洁, 瞿攀, 王金生, 等. 土壤中重金属的生物有效性分析方法及其影响因素综述[J]. 环境污染与防治, 2017, 39(2): 217-223.
[8]	朱广云, 蒋宝, 李菊梅, 等. 土壤Mehlich-3可浸提态镍对大麦根伸长的毒性[J]. 中国环境科学, 2018, 38(8): 3143-3150.
[9]	赵娜, 崔岩山, 付彧, 等. 乙二胺四乙酸(EDTA)和乙二胺二琥珀酸(EDDS)对污染土壤中Cd、Pb的浸提效果及其风险评估[J]. 环境化学, 2011, 30(5): 958-963.
[10]	TESSIER A, CAMPBELL P G C, BISSON M. Sequential extraction procedure for the speciation of particulate trace metals[J]. Analytical Chemistry, 1979, 51(7): 844-851.
[11]	QUEVAUVILLER P, RAURET G, GRIEPINK B. Single and sequential extraction in sediments and soils[J]. International Journal of Environmental Analytical Chemistry, 1993, 51(1/2/3/4): 231-235.
[12]	鲁如坤. 土壤农业化学分析方法[M]. 北京: 中国农业科技出版社, 1999.
[13]	王建乐, 谢仕斌, 王冠, 等. 不同提取剂提取土壤中重金属能力的对比研究[J]. 华南师范大学学报(自然科学版), 2020, 52(1): 55-62.
[14]	李吉宏, 聂达涛, 刘梦楠, 等. 广东典型镉污染稻田土壤镉的生物有效性测定方法及风险管控值初探[J]. 农业资源与环境学报, 2021, 38(6): 1094-1101.
[15]	陈灿明, 卫泽斌, 彭建兵, 等. 土壤有效态镉与稻米镉污染风险广东案例研究[J]. 农业环境科学学报, 2022, 41(2): 295-303.
[16]	刘彬, 孙聪, 陈世宝, 等. 水稻土中外源Cd老化的动力学特征与老化因子[J]. 中国环境科学, 2015, 35(7): 2137-2145.
[17]	WANG M, CHEN S B, WANG D, et al. Agronomic management for cadmium stress mitigation[M]// HASANUZZAMANM, PRASADM N V, NAHARK. Cadmium tolerance in plants:agronomic, molecular, signaling, and omic approaches. Nertherlands, Amsterdam: Elsevier, 2019: 69-112.
[18]	LOGANATHAN P, VIGNESWARAN S, KANDASAMY J, et al. Cadmium sorption and desorption in soils: a review[J]. Critical Reviews in Environmental Science and Technology, 2012, 42(5): 489-533.
[19]	KOMÁREK M, KORETSKY C M, STEPHEN K J, et al. Competitive adsorption of Cd(II), Cr(VI), and Pb(II) onto nanomaghemite: a spectroscopic and modeling approach[J]. Environmental Science and Technology, 2015, 49(21): 12851-12859.
[20]	LIU L, WANG X M, ZHU M Q, et al. The speciation of Cd in Cd-Fe coprecipitates: does Cd substitute for Fe in goethite structure?[J]. ACS Earth and Space Chemistry, 2019, 3(10): 2225-2236.
[21]	LÜTZENKIRCHEN J, HEBERLING F, SUPLJIKA F, et al. Structure-charge relationship: the case of hematite (001)[J]. Faraday Discussions, 2015, 180: 55-79.
[22]	MCLAUGHLIN M J, LANNO R. Use of “Bioavailability” as a term in ecotoxicology[J]. Integrated Environmental Assessment and Management, 2014, 10(1): 138-140.
[23]	SORIANO-DISLA J M, SPEIR T W, GÓMEZ I, et al. Evaluation of different extraction methods for the assessment of heavy metal bioavailability in various soils[J]. Water, Air, and Soil Pollution, 2010, 213(1): 471-483.
[24]	PUEYO M, LÓPEZ-SÁNCHEZ J, RAURET G. Assessment of CaCl₂, NaNO₃ and NH₄NO₃ extraction procedures for the study of Cd, Cu, Pb and Zn extractability in contaminated soils[J]. Analytica Chimica Acta, 2003, 504(2): 217-226.
[25]	VÁZQUEZ S, MORENO E, CARPENA R O. Bioavailability of metals and as from acidified multicontaminated soils: use of white lupin to validate several extraction methods[J]. Environmental Geochemistry and Health, 2008, 30(2): 193-198.
[26]	HIEMSTRA T. Surface structure controlling nanoparticle behavior: magnetism of ferrihydrite, magnetite, and maghemite[J]. Environmental Science: Nano, 2018, 5(3): 752-764.
[27]	LU H L, LI K W, NKOH J N, et al. Effects of the increases in soil pH and pH buffering capacity induced by crop residue biochars on available Cd contents in acidic paddy soils[J]. Chemosphere, 2022, 301: 134674.
[28]	MONTERROSO C, ALVAREZ E, FERNÁNDEZ MARCOS M L. Evaluation of Mehlich 3 reagent as a multielement extractant in mine soils[J]. Land Degradation and Development, 1999, 10(1): 35-47.
[29]	熊英, 王亚平, 韩张雄, 等. 全国土壤污染状况详查重金属元素可提取态提取试剂的选择[J]. 岩矿测试, 2022, 41(3): 384-393.

地点	土壤类型	pH (1∶5H₂O)	EC/ (μS·cm^-1)	CEC/ (cmol·kg^-1)	OC含量/%	无定形铁含量/ (g·kg^-1)	黏粒含量/%	Cd含量/ (mg·kg^-1)
广州	砖红壤	5.24	49.6	7.12	0.97	7.29	36.8	0.143
祁阳	红壤	4.57	74.2	7.47	0.88	5.23	46.1	0.121
嘉兴	水稻土	6.64	203.4	12.82	2.46	2.14	28.1	0.119
重庆	紫色土	7.02	71.3	18.41	1.79	3.10	27.3	0.207
北京	棕壤	7.47	104.8	22.70	2.28	19.9	21.2	0.095
郑州	潮土	8.64	169.6	8.51	2.67	15.9	26.9	0.172
公主岭	黑土	7.31	147.1	28.81	2.89	2.26	28.6	0.086
呼和浩特	黑钙土	7.71	141.7	22.7	2.66	37.1	20.2	0.104
咸阳	垆土	8.71	75.6	8.46	0.62	27.5	16.6	0.168

地点	土壤类型	pH (1∶5H₂O)	EC/ (μS·cm^-1)	CEC/ (cmol·kg^-1)	OC含量/%	无定形铁含量/ (g·kg^-1)	黏粒含量/%	Cd含量/ (mg·kg^-1)
广州	砖红壤	5.24	49.6	7.12	0.97	7.29	36.8	0.143
祁阳	红壤	4.57	74.2	7.47	0.88	5.23	46.1	0.121
嘉兴	水稻土	6.64	203.4	12.82	2.46	2.14	28.1	0.119
重庆	紫色土	7.02	71.3	18.41	1.79	3.10	27.3	0.207
北京	棕壤	7.47	104.8	22.70	2.28	19.9	21.2	0.095
郑州	潮土	8.64	169.6	8.51	2.67	15.9	26.9	0.172
公主岭	黑土	7.31	147.1	28.81	2.89	2.26	28.6	0.086
呼和浩特	黑钙土	7.71	141.7	22.7	2.66	37.1	20.2	0.104
咸阳	垆土	8.71	75.6	8.46	0.62	27.5	16.6	0.168

土壤类型	Cd含量/(mg·kg^-1)	富集系数(BCF)
土壤类型	Cd含量/(mg·kg^-1)	水稻	小白菜	玉米
砖红壤	0.143	1.685^a	1.370^b	0.650^c
	1.306	1.470^a	1.251^a	0.615^b
	3.048	1.434^a	1.102^b	0.580^c
红壤	0.121	1.580^a	1.291^a	0.603^b
	1.293	1.404^a	1.120^b	0.509^c
	3.084	1.353^a	1.044^a	0.529^b
水稻土	0.119	1.143^a	0.773^b	0.689^b
	1.263	0.981^a	0.654^b	0.444^c
	3.196	0.885^a	0.726^ab	0.564^b
紫色土	0.207	1.377^a	0.836^b	0.544^b
	1.336	1.161^a	0.806^b	0.451^c
	3.102	1.051^a	0.820^a	0.511^b
棕壤	0.095	1.063^a	0.696^b	0.467^c
	1.224	0.954^a	0.627^b	0.459^b
	2.931	0.948^a	0.741^ab	0.572^b
潮土	0.172	1.158^a	0.808^b	0.564^c
	1.267	0.935^a	0.705^ab	0.529^b
	3.204	1.003^a	0.712^b	0.515^c
黑土	0.086	0.972^a	0.824^ab	0.654^b
	1.100	0.870^a	0.732^ab	0.550^b
	2.967	0.944^a	0.853^a	0.480^b
黑钙土	0.104	0.787^a	0.637^ab	0.518^b
	1.402	0.701^a	0.628^a	0.417^b
	3.180	0.803^a	0.661^b	0.424^c
垆土	0.168	0.807^a	0.770^a	0.551^b
	1.236	0.711^a	0.620^ab	0.548^b
	3.081	0.605^a	0.612^a	0.423^b

土壤类型	Cd含量/(mg·kg^-1)	富集系数(BCF)
土壤类型	Cd含量/(mg·kg^-1)	水稻	小白菜	玉米
砖红壤	0.143	1.685^a	1.370^b	0.650^c
	1.306	1.470^a	1.251^a	0.615^b
	3.048	1.434^a	1.102^b	0.580^c
红壤	0.121	1.580^a	1.291^a	0.603^b
	1.293	1.404^a	1.120^b	0.509^c
	3.084	1.353^a	1.044^a	0.529^b
水稻土	0.119	1.143^a	0.773^b	0.689^b
	1.263	0.981^a	0.654^b	0.444^c
	3.196	0.885^a	0.726^ab	0.564^b
紫色土	0.207	1.377^a	0.836^b	0.544^b
	1.336	1.161^a	0.806^b	0.451^c
	3.102	1.051^a	0.820^a	0.511^b
棕壤	0.095	1.063^a	0.696^b	0.467^c
	1.224	0.954^a	0.627^b	0.459^b
	2.931	0.948^a	0.741^ab	0.572^b
潮土	0.172	1.158^a	0.808^b	0.564^c
	1.267	0.935^a	0.705^ab	0.529^b
	3.204	1.003^a	0.712^b	0.515^c
黑土	0.086	0.972^a	0.824^ab	0.654^b
	1.100	0.870^a	0.732^ab	0.550^b
	2.967	0.944^a	0.853^a	0.480^b
黑钙土	0.104	0.787^a	0.637^ab	0.518^b
	1.402	0.701^a	0.628^a	0.417^b
	3.180	0.803^a	0.661^b	0.424^c
垆土	0.168	0.807^a	0.770^a	0.551^b
	1.236	0.711^a	0.620^ab	0.548^b
	3.081	0.605^a	0.612^a	0.423^b