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富硒核心区周围土壤中硒酸盐的赋存形态及解吸/吸附的 LCD 模型。

Modes of selenium occurrence and LCD modeling of selenite desorption/adsorption in soils around the selenium-rich core, Ziyang County, China.

机构信息

Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing, 100083, People's Republic of China.

Department of Soil Quality, Wageningen University, P.O. Box 47, 6700 AA, Wageningen, The Netherlands.

出版信息

Environ Sci Pollut Res Int. 2018 May;25(15):14521-14531. doi: 10.1007/s11356-018-1595-0. Epub 2018 Mar 11.

Abstract

Studying the modes of selenium occurrence in high-Se soils and its behaviors can improve understanding and evaluating its cycling, flux, and balance in geo-ecosystems and its influence on health. In this paper, using a modified sequential chemical extraction technique, seven operationally defined selenium fractions and Se valence distribution were determined about five soils in which paddy was planted (W1, W2, W3, W4, W5) and five soils in which maize was planted (H1, H2, H3, H4, H5) around the selenium-rich core, Ziyang County, Shaanxi Province, China. The results show that selenium fractions in the soils mainly include sulfide/selenide and base-soluble Se, and ligand-exchangeable Se is also high for five soils in which paddy was planted. For water-soluble Se, Se (IV) is main Se valence and almost no Se (VI) was determined about five soils in which paddy was planted, while almost 1:1 of Se (IV) and Se (VI) coexist about five soils in which maize was planted. For exchangeable Se, similar results were found. For the first time, two typical high-Se soils (W1 soil and H1 soil) were chosen to measure the pH-dependent solid-solution distribution of selenite in the pH range 3-9, and the results were explained using LCD (ligand and charge distribution) adsorption modeling. The desorbed selenite concentrations from the two soils are in general underestimated by the model due to a comparable binding affinity of phosphate and selenite on goethite and much lower amount of total selenite than total reactively adsorbed phosphate. The pH dependency of adsorption of selenite added to the soil can be successfully described with the LCD model for W1 soil. Whereas considering the influence of Al-oxides, by lowering selenite adsorption affinity constant K of Se adsorption on goethite by 16 times, the LCD model can describe the adsorption much better. The results can help to understand selenium cycling, flux, and balance in typical high-Se soils.

摘要

研究高硒土壤中硒的赋存形态及其行为,可以提高对硒在地球生态系统中循环、通量和平衡及其对健康影响的认识和评价。本研究采用改进的连续化学提取技术,对陕西省紫阳县富硒核心区周围种植水稻的 5 个土壤(W1、W2、W3、W4、W5)和种植玉米的 5 个土壤(H1、H2、H3、H4、H5)中 7 种操作定义的硒形态和硒价态分布进行了测定。结果表明,土壤中硒形态主要包括硫化物/硒化物和碱溶态硒,种植水稻的 5 个土壤中配位交换态硒含量也较高。对于水溶性硒,硒(IV)是主要的硒价态,种植水稻的 5 个土壤中几乎没有检测到硒(VI),而种植玉米的 5 个土壤中硒(IV)和硒(VI)几乎 1:1 共存。对于可交换态硒,也得到了相似的结果。首次选择 2 个典型的高硒土壤(W1 土壤和 H1 土壤),在 pH 3-9 范围内测量亚硒酸盐在固液分配中的 pH 依赖性,并使用 LCD(配体和电荷分布)吸附模型解释实验结果。由于磷酸根和亚硒酸盐在针铁矿上的结合亲和力相当,且总反应性吸附的磷酸根量远低于总亚硒酸盐量,因此模型对这 2 个土壤中解吸的亚硒酸盐浓度的预测普遍偏低。对于 W1 土壤,添加到土壤中的亚硒酸盐的吸附的 pH 依赖性可以用 LCD 模型成功描述。而考虑到 Al-氧化物的影响,通过将针铁矿上 Se 吸附亲和力常数 K 降低 16 倍,LCD 模型可以更好地描述吸附。研究结果有助于了解典型高硒土壤中硒的循环、通量和平衡。

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