土壤中硒的生物有效性表征方法及影响因素研究进展

A Summary of Research Progress on Bioavailability Assessment Method of Selenium in Soil and Its Influencing Factors

硒是人体必需的微量元素之一。土壤-植物体系是人体摄入硒的主要途径,但尚缺乏准确评价土壤中硒生物有效性的通用方法,且影响因素也复杂多样,这些问题制约了富硒土地资源的利用。本文通过追踪近年来国内外研究成果,系统地总结及比较了化学提取法、梯度扩散薄膜法、区域尺度硒生物有效性评价方法的优缺点。传统的化学提取法如单一提取和顺序提取在一定程度上能够表征土壤中生物有效性硒,但提取过程中存在影响因素多和提取不完全等问题。梯度扩散薄膜技术(DGT)能够模拟植物的根系吸收过程,相比顺序提取能更好地表征硒的生物有效性,但由于复杂的自然体系和不同元素结合相的差异,野外原位表征技术上仍存在难度。通过大规模的农作物-根系土样本,建立土壤-农作物硒元素评价模型,模型参数为影响土壤硒有效性的理化指标(如土壤酸碱度、有机质含量、土壤硒总量等),能较好地预测区域尺度上硒生物有效性。本文还总结了影响植物吸收土壤中硒的因素如地形、土壤类型、硒的存在形态、土壤理化性质、植物种类、土壤老化等,认为地形和土壤类型、硒的存在形态、酸碱度和有机质是影响有效硒的主要因素,植物种类与土壤老化为次要因素。完善DGT等原位分析检测技术、改进元素形态分析方法是未来发展的重要方向。

Selenium(Se)is a trace element that plays a crucial role in human health.It has antioxidant,anti-cancer and anti-viral properties and is essential for a healthy body.The level of Se in the human body is largely dependent on daily dietary intake,which is in turn influenced by the amount of Se that enters the food chain from the soil.The global distribution of Se in soil is uneven,with a large difference in concentrations ranging mainly between 0.01-2.0mg/kg.The average abundance of Se in the Earth’s crust is 0.07mg/kg,but in some Se-enriched areas,it can reach up to 1200mg/kg.The chemical behavior of Se in soils is complex and diverse,involving processes such as adsorption-desorption,precipitation-dissolution,oxidation-reduction,methylation-demethylation and complexation reactions,each of which affects the bioavailable Se and is influenced and conditioned by factors such as soil pH,soil organic matter,metal oxides,clay and microorganisms.Roots are the primary site for most plants to absorb Se,which is then transported,metabolized,and accumulated.Plants can directly absorb Se from the soil,including Se that exists in the form of free ions,carbonate-bound Se,and Se adsorbed on the surfaces of clay and humus in soil solutions.However,selenite and selenate can be reduced to solid,insoluble Se(0)and metal-Se precipitates that are not bioavailable in locally anaerobic areas(such as soil aggregates)or used by bacteria as terminal electron acceptors.Previous researchers have conducted a lot of work on chemical extraction methods,but there are still problems,such as insufficient extraction specificity and Se form transformation during the extraction process.Hence,an accurate approach for predicting the amount of soil Se that can be absorbed by plants is essential.However there are no clear paths for the choices of assessment methods and influencing factors of soil Se bioavailability.These problems have restricted the utilization of Se-enriched land resources.Thus,providing a scientific basis for the development and utilization of Se-enriched land resources is the goal here by summarizing the main assessment methods and dominant factors on soil Se bioavailability.Determining the activity of Se in soils comprehensively requires considering the complicated and varied effects of natural conditions on its bioavailability,which can be studied through characterization methods and identification of influencing factors.Therefore,it is of practical importance and a challenge to accurately determine the form of Se in soils and assess its bioavailability.Current methods for characterizing the bioavailability of soil Se include the traditional chemical extraction methods(single extraction and sequential extraction)and the emerging Diffusive Gradients in Thin films(DGT)technique.Chemical extraction is a process that involves separating a specific component or substance from a mixture using a solvent or a chemical reagent.The extraction method depends on the physical and chemical properties of the substance being extracted and the nature of the mixture.The general steps involved in a chemical extraction method are:choosing the appropriate solvent or chemical reagent that can selectively dissolve the desired substance while leaving the unwanted components behind,mixing the mixture and the solvent/reagent together to allow the selective extraction of the desired substance,separating the extracted substance from the mixture using various techniques such as filtration,centrifugation,or evaporation,and purifying and isolating the extracted substance by further chemical or physical methods if necessary.The DGT technique is an effective environmental chemistry method used for identifying elements and compounds in various aqueous environments,including natural waters,sediments,and soils.This technique is particularly useful for detecting bioavailable trace elements,and it can be applied for in-situ detection.The DGT technique involves using a specially-designed passive sampler that comprises a binding gel,a diffusive gel,and a membrane filter.The element or compound of interest passes through the membrane filter and diffusive gel before being assimilated by the binding gel in a rate-controlled manner.Subsequently,the binding gel is analyzed post-deployment,enabling the determination of the time-weighted-average bulk solution concentration of the element or compound via a simple equation.The advantages and limitations of chemical extraction methods,DGT technique and bioavailability assessment models of Se at a regional scale are compared.Traditional chemical extraction procedures such as single extraction or sequential extraction can be used to characterize the bioavailability of Se in the soil,to a certain extent.Still,the extraction process has many limits and incomplete extraction problems.The DGT method can be used to simulate the root uptake process of plants and can better characterize the bioavailability of Se compared to sequential extraction.One of the major advantages of the DGT technique is its ability to provide accurate and reliable results,even at low concentrations.Additionally,this technique is non-destructive and can be used in-situ,making it suitable for real-time monitoring of environmental conditions.However,there are also some limitations associated with the DGT technique.For instance,the binding gel used in this method may not be specific to the target element or compound,leading to the possibility of cross-reactivity with other substances.Additionally,the technique may be influenced by factors such as temperature,pH,and ionic strength,which could affect the accuracy of the results.Using large-scale crop-root soil samples,a soil-crop Se assessment model was developed with parameters of physicochemical indicators(e.g.soil pH,soil organic matter,soil Se,etc.),which can better predict Se bioavailability on a regional scale.Some major and minor influencing factors affecting the uptake of Se in soil by plants are discussed.In short,topography and soil type,Se species,pH and organic matter are the main factors affecting bioavailable Se,with plant species and soil aging as secondary factors.In brief,the main limitations of the characterization methods for the bioavailability of different forms of Se are:a single extraction method can be affected by soil properties,soil/solution ratio,extraction time,the pH value of the extraction agent,and other factors.Sequential extraction methods have problems with incomplete extraction,dilution of the extract,and Se loss during centrifugation and filtration.These traditional methods cannot be used to reflect the dynamic processes of the solid-phase soil-solution-root system.DGT technology is a method that disturbs the equilibrium between soil solution and solid phase,simulating the dynamic process of Se uptake by roots,and has advantages in assessing bioavailability.However,it is still questionable whether it can be used to fully predict the replenishment dynamics of Se in field soil.The main factors affecting the bioavailability of soil Se are:(1)Topographical factors such as altitude,slope,and terrain wetness index,which have some influence on soil Se content;there are large differences in organic matter,iron/aluminum hydroxides,and pH among different soil types,which can be controlled to affect Se migration and bioavailability;(2)Soluble and exchangeable Se are more easily absorbed by plants,and selenate with better mobility is easier to absorb,transport,and metabolize in plants than selenite;(3)Increasing soil pH can generally improve Se bioavailability,but this is not the case in organic-enriched soils.Currently,there is no universally applicable method for evaluating soil Se bioavailability,as it is influenced by many factors such as topography,soil type,and soil physicochemical properties.This makes it difficult to compare and verify different results.Improving in-situ DGT analysis technology and modifying the analysis of Se forms are important technical means for accurately evaluating soil Se bioavailability and are also important directions for future development.