恩施地区硒的地球化学研究及富硒作物栽培实验研究
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摘要
硒是人体必需的微量元素之一,近年来,随着人们对于微量元素硒认识的逐渐加深,对于硒的研究也逐渐引起人们的广泛关注,环境中硒含量的高低直接影响着各种生物机体的健康,硒缺乏或过量均会导致机体产生疾病；严重缺硒会引起地方病如克山病和大骨节病,适量的硒不仅能促进作物代谢生长、提高作物产量和品质,还能增强动物及人体免疫力,起到预防多种疾病的作用。土壤是生态环境的重要枢纽,土壤中硒的含量和形态直接影响着植物对硒的吸收,而植物无论是缺硒还是硒过量,都会影响其自身及动物的生长、发育和繁殖,并最终通过食物链影响人类的健康。硒在地球上分布广泛但又极不均匀,全世界有2/3的地区缺硒,其中1/3为世界公认的严重缺硒区,缺硒严重威胁人类健康和畜牧业的发展。因此适量补硒促进人体健康就显得尤为重要。我国约72%的县市存在不同程度的缺硒现象,全国约有7亿多人口的膳食结构中硒含量不足,造成人体低硒状态,因此富硒产业的打造和开发成为目前国内研究的热点,但是富硒产业的开发必须以基本的科学研究为依据,因此对富硒地区的地质、环境以及农业方面的研究显得极为迫切。
恩施地区是最典型最富硒的地区,恩施州之所以闻名于国内外是因为在恩施发现迄今唯一独立的硒矿床,打破了近200年“硒不能独立成工业矿床”的理论,2011年正式被国际人与动物微量元素营养学会授予“世界硒都”的称号,恩施州全州总面积中73%的土壤都属于高硒区,品位在230～46300克／吨之间,恩施硒资源的开发和应用是当前乃至将来恩施市政府甚至也是国家的重大战略之一。富硒产品开发初期的实践已证明要在高硒的自然土壤条件下开发富硒食品是很难达到的。因此,需要对土壤进行调节以获得大面积安全、稳定、可控的含硒土壤来培育富农产品。
本论文以环境地球化学和农业地球化学基本原理为指导,结合国内外硒研究的新思路和新方法,采用野外调查和室内实验相结合的方法在恩施典型富硒区开展系统调查和研究,本论文以恩施富硒土壤和植物为主要研究对象,系统调查不同富硒地层—耕作土壤—植物系统中硒及其伴生有益、有害元素的迁移转化规律及其主要影响因素,对富硒带土壤进行了生态地球化学评价,提出了优势富硒土地资源的规划建议和政府企业等的应对策略,为我国富硒地区绿色富硒产业开发提供了科学依据。
主要取得以下结论和认识：
(1)、通过选用硝酸-高氯酸-氢氟酸电热板法消解、原子荧光光谱法测定了恩施部分地区土壤中的总硒,优化了各项条件,建立了氢化物发生原子荧光测定环境样品中总硒含量的方法。最佳测试条件下,该方法的检出限为0.09μg·L-1、线性范围为0.12μg·L-1～100μg·L-1,加标回收率为97.8%～101.1%。利用此方法测定恩施部分地区的土壤、植物、粮食等样品的总硒含量。结果表明自然状态下恩施不同地区的土壤、植物和粮食总硒含量差异性比较大。渔塘坝等高硒区,土壤和食品的含硒量比较高,存在硒中毒风险。经过人为调节的恩施芭蕉玉露茶园土壤、茶叶硒含量相对稳定。因此,恩施富硒产品的开发可以利用硒含量中等偏下土壤进行调整,以获得更多更安全的富硒食品。
(2)、通过对富硒黑色岩系的成分研究,发现本区岩石样品的化学成分以SiO2为主,含量为48.37-87.83%,其次为Al203、CaO和Fe203,含量分别为0.99-10.07%,0.12-5.22%和0.26-2.32%,其它氧化物成分的含量则相对很低。研究区内的岩石样品中普遍富集B、Cd、Cr、Cu、 Ni、 Pb、 Sn、 Tl、V和Se,其平均含量分别达到25.52mg/kg、11.75mg/kg、296.25mg/kg、66.29mg/kg、46.35mg/kg、76.93mg/kg、15.53mg/kg、554.74mg/kg、667.73mg/kg和125.11mg/kg,这些数据与上陆壳的平均值相比,分别为1.7倍、119.9倍、8.47倍、2.65倍、2.32倍、3.85倍、2.82倍、739.65倍、11.13倍以及2502.2倍。
(3)、通过对恩施地区三个典型研究区的土壤性质和硒总量研究,发现鱼塘坝地区土壤中硒含量最高,达到高硒水平,芭蕉地区则为普通富硒地区,长平地区硒明显不足。此外,恩施三个地区土壤硒和有机质含量均呈显著性相关,说明恩施土壤硒与有机质结合在一起的部分较多,这影响了植物直接可以利用的硒比例。考虑到有机质的含量对于硒的生态效益具有双重性,一方面,它作为一种有机无机复合体粘粒吸附环境中的硒,但在特定的条件下可以将其吸附的硒释放出来,这是有利于硒的循环的,但是当它仅仅作为一种阴离子的环境宿体时,它可能会变成影响硒传输循环的屏障,因此有机质对硒的生态效应具有二重性。
(4)、通过对恩施地区典型富硒植物的研究,发现茶叶中所含的硒普遍较低,有些样品甚至无法检出,这说明茶叶的富硒能力并不是很强,部分样品没有达到富硒茶叶的相关标准。而富硒植物遏蓝菜中硒的含量却高达几十ppm,说明遏蓝菜由于长期生长在鱼塘坝附近的高硒区,植物体内已经有了耐受硒累积的基因,这是大自然长期进化的结果,通过这种高富集硒的植物可以提取出相应的有机硒化物,从而可以制成各种生物制剂,目前农业方面的研究人员已经开始尝试将这种野生的植物转化为家养的作物,从而可以大规模的生产和提取生物有机硒,玉米、土豆和黄豆三种作物中的硒含量略高于茶叶中的硒含量,但远远低于遏蓝菜中的硒含量。
(5)、通过对富硒土壤中硒的单提取实验研究,结果表明,对于土壤有效态硒的提取,本实验认为2.0mol/LK2HP04-KH2P04溶液为恩施地区土壤有效态硒的最佳提取剂,最佳提取条件为：土液比1：15,提取温度为30℃,振荡时间为120min。对富硒土壤中硒的顺序提取实验研究表面,富硒土壤中占比例绝大部分的是残渣态中的硒,它们主要赋存于矿物的晶格中,无法进入到环境中被植物吸收和利用,水溶态和可交换态硒的比例则较小。
(6)、通过对富硒土壤中的重金属继续研究发现,鱼塘坝地区的重金属污染水平已经达到了相当高的水平,尤其是Cd的污染以经达到及其严重的地步,Cd的超标倍数也最为严重,达到了8到800倍之间,其次Ni也有一定的污染,但是影响较轻微,此外,鱼塘坝地区的Cu、Zn、Cr等重金属也存在超标的问题,因此在鱼塘坝地区种植的农作物,要特别注意重金属元素特别是Cd的污染,防微杜渐才能保证所产出的食物安全。
(7)、通过富硒植物的栽培试验,对两种不同形式的硒肥进行了比较,即土壤中施加固态的硒肥和植物页面喷施液态硒肥进行对比研究,讨论了硒在植物体内的迁移和分布,结果表明液态的硒肥直接喷施在植物叶片上可以有效的提高硒肥的使用效率,植物可食部分的硒含量可以快速显著的提高,而传统的施肥方法直接将活化硒矿粉施加入土壤则显得效率较低。对于土壤中施加硒肥的植物来说,植物根系土中硒的含量与植物体内根茎叶中硒的含量呈显著的正相关性,相关系数分别为r=0.933(p≤0.01)、r=0.922(p≤0.01)和r=0.754(p≤0.05),而植物果肉中硒的含量与根系土中硒的含量则没有明显的相关性。此外,植物的根系从土壤中吸收的亚硒酸盐,主要赋存在根部并形成硒化物,因此很难向上迁移送达植物的各个组织和营养器官。页面喷施硒肥直接从叶片的气孔中被吸收进入植物体内,送达到植物可食部分的硒更快捷有效,因此要比从根系的吸收更为理想。
(8)、对于发展富硒产业,本人建议提出如下对策：1、科学研究奠定基础。首先要进行详细的地质调查工作,摸清自己的家底,例如富硒岩层的详细分布,可开采的储量估算,低硒煤矸石的综合利用,以及其他地质方面的研究。其次要进行富硒土壤的调查、利用和规划。最后要在农作物优良品种的选育和种植上进行研究。2、宣传策划把握市场。3、政府企业协同运作。
Selenium is an essential trace element for human body, in the recent years, with gradually deepened understanding of the trace element selenium, selenium is gradually attracted widespread attention. The level of the content of selenium in the environment has a direct impact on a variety of living organisms health, selenium deficiency or excess will cause the body to produce disease, serious lack of selenium can cause endemic diseases such as Keshan disease and Kashin-Beck disease, an appropriate amount of selenium is not only can promote the growth of crop metabolism, increase crop yields and quality, but also enhance animal and the human immune system, play a role in the prevention of many diseases. Soil is an important hub of the ecological environment, content and form of selenium in the soil directly affect plant absorption of selenium, while the plant is either selenium or selenium overdose, will affect the growth, development and reproduction of themselves and their animals, and finally through the food chain and affect human health. Selenium distribution on Earth widely but very unevenly around the world2/3of selenium,1/3the world recognized as a serious selenium District selenium a serious threat to human health and the development of animal husbandry. Therefore, the amount of selenium to promote human health is particularly important. China about72%of the counties there are different levels of selenium phenomenon, about more than700million people in the dietary pattern of the selenium content, resulting in low body selenium status, so rich in selenium industry to build and develop to become the research focus of the current domestic rich in selenium industry development in basic scientific research as the basis, so rich in selenium areas of geology, environment and agriculture is extremely urgent.
Enshi is the most typical of the most rich in selenium, Enshi Prefecture's well-known at home and abroad, breaking the nearly200years,"selenium can not be a separate industrial deposits" theory because so far the only independent selenium deposits found in Enshi,2011international human and animal trace element Nutrition Society was officially awarded the "World selenium" in the title,73%of the total area of Enshi Prefecture Chonju soil belong to the high-selenium area, the grade of between230to6300g/ton, Enshi selenium resources development and application of the current and even future Enshi city government even is also a major national strategy to rich in selenium product development early practice has proved rich in selenium food is difficult to achieve development in the high selenium in natural soil conditions. Therefore, you need to be adjusted on the soil to nurture the rich to get a large area of security, stability, controllability selenium soil of agricultural products.
In this paper, the basic principles of environmental geochemistry and agricultural geochemistry were combined with new ideas and new methods of selenium study at home and abroad, using field surveys and laboratory experiments a combination of methods to carry out a systematic investigation and research in Enshi typical rich in selenium, the paper the Enshi rich in selenium soil and plant research, Selenium and its associated beneficial and harmful elements in the migration and transformation of its main influencing factors in the systematic investigation of selenium-rich strata-tillage soil-plant system with a soil rich in selenium. Ecological geochemical assessment, proposed the coping strategies of the advantages of selenium-rich land resources planning proposals and government enterprises, provide a scientific basis for the development of our country rich in selenium green regions rich in selenium industry.
Obtained the following conclusions and understanding:
(1), Using the choice of nitric acid-perchloric acid-hydrofluoric acid, electric hot plate method digestion atomic fluorescence spectrometry method for the determination of total selenium in parts of the soil in Enshi, to optimize the conditions established by hydride generation atomic fluorescence determination of the total selenium content in the sample. The best test conditions, the method detection limit was0.09μg L-1, the linear range of0.12μg·L-1～100μg·L-1, the recovery rate of97.8%to101.1%. Using this method for the determination of the the Enshi parts of the total selenium content of soil, plants, food and other samples. The results show that relatively large differences of soil, plants and food of the total selenium content of Enshi in different parts of the state of nature. Yutangba high-selenium areas, soil and food Se than higher, there is the risk of selenium poisoning. Gyokuro tea garden soil artificially adjusted Enshi banana, tea selenium content is relatively stable.In Enshi rich in selenium product development can take advantage of the selenium content in the middle under the soil to adjust to a more secure Selenium Enriched Foods.
(2), By analyzing the composition of selenium-rich black shales, the chemical composition of the rock samples in the main content of48.37-87.83%SiO2, followed by0.99-10.07%Al2O3, CaO and Fe2O3content,0.12-5.22%and0.26-2.32%, the other oxide components of the content is relatively low. Rock samples in the study area generally enriched in B, Cd, Cr and Cu, Ni and Pb, Sn, Tl, V and of Se, the average concentration to reach25.52mg/kg,11.75mg/kg,296.25mg/kg,66.29mg/kg,46.35mg/kg,76.93mg/kg,15.53mg/kg,554.74mg/kg,667.73mg/kg and125.11mg/kg, these data and the average upper continental crust, respectively, compared to1.7times,119.9times,8.47times and2.65times,2.32times and3.85times,2.82times and739.65times,11.13times and2502.2times.
(3), Study the Enshi from three typical soil properties and total selenium found selenium content in the fish the embankments area soil, reaching a high selenium levels, the banana region, compared with the ordinary rich in selenium region, long flat region selenium is clearly insufficient. In addition, the the Enshi three soil selenium and organic matter content showed a significantly correlated, indicating that the Enshi soil selenium and organic matter in combination with the part more, which affects the plants can directly use the proportion of selenium. Taking into account the ecological benefits of organic matter content of selenium has a dual nature, on the one hand, as clay adsorption of an organic-inorganic complex environment of selenium, but under certain conditions to adsorption of selenium released, which is conducive to the cycle of selenium, but when it only as an anion environment places the body, it may become the barrier of the selenium transmission cycle, so the organic matter has the duality of the ecological effects of selenium.
(4), Enshi typical rich in selenium plant selenium contained in tea is generally low, some samples can not even detected, indicating that the tea rich in selenium capacity is not very strong, some samples did not meet the richselenium tea standards. Rich in selenium plants containing selenium content in the blue dish was as high as tens of ppm, indicating the blue dish containing long-term growth in high-selenium area of the fish embankments near the plants has been tolerated selenium accumulated genes, this is the nature of long-term the result of evolution, the high enrichment of selenium by this plant can be extracted out of organic selenium compounds, which can be made into a variety of biological agents, agricultural researchers have begun to try this kind of wild plants into domesticated crops, allowing large-scale production and extraction of bio-organic selenium, corn, potatoes and soybeans three crops in selenium content slightly higher than that of the selenium content of tea, but far less than the blue dish containing the selenium content.
(5), The experiment of single extract of selenium from selenium rich soil was studied, results show that this experiment that2.0mol/L K2HPO4-KH2PO4solution for optimum extraction of the Enshi area of soil available Se for the extraction of soil available selenium agent, the optimum extraction conditions:soil water ratio1:15, extraction temperature is30℃, the oscillation time of120min. Extraction of the surface, the order of selenium in selenium-rich soil rich in selenium in soil, the proportion of the vast majority of the residual selenium, and they mainly occur in the mineral lattice, can not enter to be absorbed by plants into the environment and use of a smaller proportion of water soluble and exchangeable selenium.
(6), Heavy metals in selenium rich soil was continue to study the fish embankments heavy metal pollution levels have reached a very high level, especially Cd pollution through to reach its serious stage, Cd exceeded the multiple the most serious, reaching8-800times, followed by Ni pollution, but the effect is minor, in addition, the heavy metals in fish embankments of Cu, Zn, Cr, also exists the problem of excessive, so the fish embankments area planted crops, pay special attention to heavy metal elements, especially Cd pollution as a preventive measure to ensure that the output of food security.
(7), Selenium rich in plant cultivation experiment, two different forms of selenium fertilizer compared, that is applied to the soil solid selenium fertilizer and plant pages spraying liquid selenium fertilizer comparative study of selenium in plants migration and distribution, the results show that liquid selenium fertilizer sprayed directly on plant leaves can effectively improve the efficiency in the use of selenium fertilizer, the selenium content of edible parts of plants can quickly and significantly improve traditional fertilization methods directly to the activation of selenium ore facilities to join the soil is much less efficient. For applying selenium fertilizer plant in the soil content of selenium in plant roots soil selenium content of plants, roots, stems and leaves showed a significant positive correlation, correlation coefficients were r=.933(p≤0.01), r=0.922(p≤0.01) and r=0.754(p≤0.05), while the content of selenium in the plant pulp and root soil content of selenium is no clear correlation. In addition, selenite absorption by plant roots from the soil, exist roots and the formation of the selenium compounds, making it difficult to migrate upward served on the plants, and vegetative organs. Page foliar application of selenium fertilizer directly from the stomatal be absorbed into the plants, sent to the edible parts of plants, selenium is more efficient and effective, and therefore even better than from the root absorption.
(8) For the development of the rich in selenium industry, I proposed the following measures:a scientific research foundation. The first detailed geological survey work, to find out their family property, such as selenium-rich rock distribution, mineable reserves estimates, the low-selenium coal gangue comprehensive utilization, and other geological research. Second, we must be rich in selenium soil survey, use and planning. Finally, in the breeding and cultivation of improved varieties of crops.2,promotion planning grasp the market.3,government enterprise collaboration.
恩施地区是最典型最富硒的地区,恩施州之所以闻名于国内外是因为在恩施发现迄今唯一独立的硒矿床,打破了近200年“硒不能独立成工业矿床”的理论,2011年正式被国际人与动物微量元素营养学会授予“世界硒都”的称号,恩施州全州总面积中73%的土壤都属于高硒区,品位在230～46300克／吨之间,恩施硒资源的开发和应用是当前乃至将来恩施市政府甚至也是国家的重大战略之一。富硒产品开发初期的实践已证明要在高硒的自然土壤条件下开发富硒食品是很难达到的。因此,需要对土壤进行调节以获得大面积安全、稳定、可控的含硒土壤来培育富农产品。
本论文以环境地球化学和农业地球化学基本原理为指导,结合国内外硒研究的新思路和新方法,采用野外调查和室内实验相结合的方法在恩施典型富硒区开展系统调查和研究,本论文以恩施富硒土壤和植物为主要研究对象,系统调查不同富硒地层—耕作土壤—植物系统中硒及其伴生有益、有害元素的迁移转化规律及其主要影响因素,对富硒带土壤进行了生态地球化学评价,提出了优势富硒土地资源的规划建议和政府企业等的应对策略,为我国富硒地区绿色富硒产业开发提供了科学依据。
主要取得以下结论和认识：
(1)、通过选用硝酸-高氯酸-氢氟酸电热板法消解、原子荧光光谱法测定了恩施部分地区土壤中的总硒,优化了各项条件,建立了氢化物发生原子荧光测定环境样品中总硒含量的方法。最佳测试条件下,该方法的检出限为0.09μg·L-1、线性范围为0.12μg·L-1～100μg·L-1,加标回收率为97.8%～101.1%。利用此方法测定恩施部分地区的土壤、植物、粮食等样品的总硒含量。结果表明自然状态下恩施不同地区的土壤、植物和粮食总硒含量差异性比较大。渔塘坝等高硒区,土壤和食品的含硒量比较高,存在硒中毒风险。经过人为调节的恩施芭蕉玉露茶园土壤、茶叶硒含量相对稳定。因此,恩施富硒产品的开发可以利用硒含量中等偏下土壤进行调整,以获得更多更安全的富硒食品。
(2)、通过对富硒黑色岩系的成分研究,发现本区岩石样品的化学成分以SiO2为主,含量为48.37-87.83%,其次为Al203、CaO和Fe203,含量分别为0.99-10.07%,0.12-5.22%和0.26-2.32%,其它氧化物成分的含量则相对很低。研究区内的岩石样品中普遍富集B、Cd、Cr、Cu、 Ni、 Pb、 Sn、 Tl、V和Se,其平均含量分别达到25.52mg/kg、11.75mg/kg、296.25mg/kg、66.29mg/kg、46.35mg/kg、76.93mg/kg、15.53mg/kg、554.74mg/kg、667.73mg/kg和125.11mg/kg,这些数据与上陆壳的平均值相比,分别为1.7倍、119.9倍、8.47倍、2.65倍、2.32倍、3.85倍、2.82倍、739.65倍、11.13倍以及2502.2倍。
(3)、通过对恩施地区三个典型研究区的土壤性质和硒总量研究,发现鱼塘坝地区土壤中硒含量最高,达到高硒水平,芭蕉地区则为普通富硒地区,长平地区硒明显不足。此外,恩施三个地区土壤硒和有机质含量均呈显著性相关,说明恩施土壤硒与有机质结合在一起的部分较多,这影响了植物直接可以利用的硒比例。考虑到有机质的含量对于硒的生态效益具有双重性,一方面,它作为一种有机无机复合体粘粒吸附环境中的硒,但在特定的条件下可以将其吸附的硒释放出来,这是有利于硒的循环的,但是当它仅仅作为一种阴离子的环境宿体时,它可能会变成影响硒传输循环的屏障,因此有机质对硒的生态效应具有二重性。
(4)、通过对恩施地区典型富硒植物的研究,发现茶叶中所含的硒普遍较低,有些样品甚至无法检出,这说明茶叶的富硒能力并不是很强,部分样品没有达到富硒茶叶的相关标准。而富硒植物遏蓝菜中硒的含量却高达几十ppm,说明遏蓝菜由于长期生长在鱼塘坝附近的高硒区,植物体内已经有了耐受硒累积的基因,这是大自然长期进化的结果,通过这种高富集硒的植物可以提取出相应的有机硒化物,从而可以制成各种生物制剂,目前农业方面的研究人员已经开始尝试将这种野生的植物转化为家养的作物,从而可以大规模的生产和提取生物有机硒,玉米、土豆和黄豆三种作物中的硒含量略高于茶叶中的硒含量,但远远低于遏蓝菜中的硒含量。
(5)、通过对富硒土壤中硒的单提取实验研究,结果表明,对于土壤有效态硒的提取,本实验认为2.0mol/LK2HP04-KH2P04溶液为恩施地区土壤有效态硒的最佳提取剂,最佳提取条件为：土液比1：15,提取温度为30℃,振荡时间为120min。对富硒土壤中硒的顺序提取实验研究表面,富硒土壤中占比例绝大部分的是残渣态中的硒,它们主要赋存于矿物的晶格中,无法进入到环境中被植物吸收和利用,水溶态和可交换态硒的比例则较小。
(6)、通过对富硒土壤中的重金属继续研究发现,鱼塘坝地区的重金属污染水平已经达到了相当高的水平,尤其是Cd的污染以经达到及其严重的地步,Cd的超标倍数也最为严重,达到了8到800倍之间,其次Ni也有一定的污染,但是影响较轻微,此外,鱼塘坝地区的Cu、Zn、Cr等重金属也存在超标的问题,因此在鱼塘坝地区种植的农作物,要特别注意重金属元素特别是Cd的污染,防微杜渐才能保证所产出的食物安全。
(7)、通过富硒植物的栽培试验,对两种不同形式的硒肥进行了比较,即土壤中施加固态的硒肥和植物页面喷施液态硒肥进行对比研究,讨论了硒在植物体内的迁移和分布,结果表明液态的硒肥直接喷施在植物叶片上可以有效的提高硒肥的使用效率,植物可食部分的硒含量可以快速显著的提高,而传统的施肥方法直接将活化硒矿粉施加入土壤则显得效率较低。对于土壤中施加硒肥的植物来说,植物根系土中硒的含量与植物体内根茎叶中硒的含量呈显著的正相关性,相关系数分别为r=0.933(p≤0.01)、r=0.922(p≤0.01)和r=0.754(p≤0.05),而植物果肉中硒的含量与根系土中硒的含量则没有明显的相关性。此外,植物的根系从土壤中吸收的亚硒酸盐,主要赋存在根部并形成硒化物,因此很难向上迁移送达植物的各个组织和营养器官。页面喷施硒肥直接从叶片的气孔中被吸收进入植物体内,送达到植物可食部分的硒更快捷有效,因此要比从根系的吸收更为理想。
(8)、对于发展富硒产业,本人建议提出如下对策：1、科学研究奠定基础。首先要进行详细的地质调查工作,摸清自己的家底,例如富硒岩层的详细分布,可开采的储量估算,低硒煤矸石的综合利用,以及其他地质方面的研究。其次要进行富硒土壤的调查、利用和规划。最后要在农作物优良品种的选育和种植上进行研究。2、宣传策划把握市场。3、政府企业协同运作。
Selenium is an essential trace element for human body, in the recent years, with gradually deepened understanding of the trace element selenium, selenium is gradually attracted widespread attention. The level of the content of selenium in the environment has a direct impact on a variety of living organisms health, selenium deficiency or excess will cause the body to produce disease, serious lack of selenium can cause endemic diseases such as Keshan disease and Kashin-Beck disease, an appropriate amount of selenium is not only can promote the growth of crop metabolism, increase crop yields and quality, but also enhance animal and the human immune system, play a role in the prevention of many diseases. Soil is an important hub of the ecological environment, content and form of selenium in the soil directly affect plant absorption of selenium, while the plant is either selenium or selenium overdose, will affect the growth, development and reproduction of themselves and their animals, and finally through the food chain and affect human health. Selenium distribution on Earth widely but very unevenly around the world2/3of selenium,1/3the world recognized as a serious selenium District selenium a serious threat to human health and the development of animal husbandry. Therefore, the amount of selenium to promote human health is particularly important. China about72%of the counties there are different levels of selenium phenomenon, about more than700million people in the dietary pattern of the selenium content, resulting in low body selenium status, so rich in selenium industry to build and develop to become the research focus of the current domestic rich in selenium industry development in basic scientific research as the basis, so rich in selenium areas of geology, environment and agriculture is extremely urgent.
Enshi is the most typical of the most rich in selenium, Enshi Prefecture's well-known at home and abroad, breaking the nearly200years,"selenium can not be a separate industrial deposits" theory because so far the only independent selenium deposits found in Enshi,2011international human and animal trace element Nutrition Society was officially awarded the "World selenium" in the title,73%of the total area of Enshi Prefecture Chonju soil belong to the high-selenium area, the grade of between230to6300g/ton, Enshi selenium resources development and application of the current and even future Enshi city government even is also a major national strategy to rich in selenium product development early practice has proved rich in selenium food is difficult to achieve development in the high selenium in natural soil conditions. Therefore, you need to be adjusted on the soil to nurture the rich to get a large area of security, stability, controllability selenium soil of agricultural products.
In this paper, the basic principles of environmental geochemistry and agricultural geochemistry were combined with new ideas and new methods of selenium study at home and abroad, using field surveys and laboratory experiments a combination of methods to carry out a systematic investigation and research in Enshi typical rich in selenium, the paper the Enshi rich in selenium soil and plant research, Selenium and its associated beneficial and harmful elements in the migration and transformation of its main influencing factors in the systematic investigation of selenium-rich strata-tillage soil-plant system with a soil rich in selenium. Ecological geochemical assessment, proposed the coping strategies of the advantages of selenium-rich land resources planning proposals and government enterprises, provide a scientific basis for the development of our country rich in selenium green regions rich in selenium industry.
Obtained the following conclusions and understanding:
(1), Using the choice of nitric acid-perchloric acid-hydrofluoric acid, electric hot plate method digestion atomic fluorescence spectrometry method for the determination of total selenium in parts of the soil in Enshi, to optimize the conditions established by hydride generation atomic fluorescence determination of the total selenium content in the sample. The best test conditions, the method detection limit was0.09μg L-1, the linear range of0.12μg·L-1～100μg·L-1, the recovery rate of97.8%to101.1%. Using this method for the determination of the the Enshi parts of the total selenium content of soil, plants, food and other samples. The results show that relatively large differences of soil, plants and food of the total selenium content of Enshi in different parts of the state of nature. Yutangba high-selenium areas, soil and food Se than higher, there is the risk of selenium poisoning. Gyokuro tea garden soil artificially adjusted Enshi banana, tea selenium content is relatively stable.In Enshi rich in selenium product development can take advantage of the selenium content in the middle under the soil to adjust to a more secure Selenium Enriched Foods.
(2), By analyzing the composition of selenium-rich black shales, the chemical composition of the rock samples in the main content of48.37-87.83%SiO2, followed by0.99-10.07%Al2O3, CaO and Fe2O3content,0.12-5.22%and0.26-2.32%, the other oxide components of the content is relatively low. Rock samples in the study area generally enriched in B, Cd, Cr and Cu, Ni and Pb, Sn, Tl, V and of Se, the average concentration to reach25.52mg/kg,11.75mg/kg,296.25mg/kg,66.29mg/kg,46.35mg/kg,76.93mg/kg,15.53mg/kg,554.74mg/kg,667.73mg/kg and125.11mg/kg, these data and the average upper continental crust, respectively, compared to1.7times,119.9times,8.47times and2.65times,2.32times and3.85times,2.82times and739.65times,11.13times and2502.2times.
(3), Study the Enshi from three typical soil properties and total selenium found selenium content in the fish the embankments area soil, reaching a high selenium levels, the banana region, compared with the ordinary rich in selenium region, long flat region selenium is clearly insufficient. In addition, the the Enshi three soil selenium and organic matter content showed a significantly correlated, indicating that the Enshi soil selenium and organic matter in combination with the part more, which affects the plants can directly use the proportion of selenium. Taking into account the ecological benefits of organic matter content of selenium has a dual nature, on the one hand, as clay adsorption of an organic-inorganic complex environment of selenium, but under certain conditions to adsorption of selenium released, which is conducive to the cycle of selenium, but when it only as an anion environment places the body, it may become the barrier of the selenium transmission cycle, so the organic matter has the duality of the ecological effects of selenium.
(4), Enshi typical rich in selenium plant selenium contained in tea is generally low, some samples can not even detected, indicating that the tea rich in selenium capacity is not very strong, some samples did not meet the richselenium tea standards. Rich in selenium plants containing selenium content in the blue dish was as high as tens of ppm, indicating the blue dish containing long-term growth in high-selenium area of the fish embankments near the plants has been tolerated selenium accumulated genes, this is the nature of long-term the result of evolution, the high enrichment of selenium by this plant can be extracted out of organic selenium compounds, which can be made into a variety of biological agents, agricultural researchers have begun to try this kind of wild plants into domesticated crops, allowing large-scale production and extraction of bio-organic selenium, corn, potatoes and soybeans three crops in selenium content slightly higher than that of the selenium content of tea, but far less than the blue dish containing the selenium content.
(5), The experiment of single extract of selenium from selenium rich soil was studied, results show that this experiment that2.0mol/L K2HPO4-KH2PO4solution for optimum extraction of the Enshi area of soil available Se for the extraction of soil available selenium agent, the optimum extraction conditions:soil water ratio1:15, extraction temperature is30℃, the oscillation time of120min. Extraction of the surface, the order of selenium in selenium-rich soil rich in selenium in soil, the proportion of the vast majority of the residual selenium, and they mainly occur in the mineral lattice, can not enter to be absorbed by plants into the environment and use of a smaller proportion of water soluble and exchangeable selenium.
(6), Heavy metals in selenium rich soil was continue to study the fish embankments heavy metal pollution levels have reached a very high level, especially Cd pollution through to reach its serious stage, Cd exceeded the multiple the most serious, reaching8-800times, followed by Ni pollution, but the effect is minor, in addition, the heavy metals in fish embankments of Cu, Zn, Cr, also exists the problem of excessive, so the fish embankments area planted crops, pay special attention to heavy metal elements, especially Cd pollution as a preventive measure to ensure that the output of food security.
(7), Selenium rich in plant cultivation experiment, two different forms of selenium fertilizer compared, that is applied to the soil solid selenium fertilizer and plant pages spraying liquid selenium fertilizer comparative study of selenium in plants migration and distribution, the results show that liquid selenium fertilizer sprayed directly on plant leaves can effectively improve the efficiency in the use of selenium fertilizer, the selenium content of edible parts of plants can quickly and significantly improve traditional fertilization methods directly to the activation of selenium ore facilities to join the soil is much less efficient. For applying selenium fertilizer plant in the soil content of selenium in plant roots soil selenium content of plants, roots, stems and leaves showed a significant positive correlation, correlation coefficients were r=.933(p≤0.01), r=0.922(p≤0.01) and r=0.754(p≤0.05), while the content of selenium in the plant pulp and root soil content of selenium is no clear correlation. In addition, selenite absorption by plant roots from the soil, exist roots and the formation of the selenium compounds, making it difficult to migrate upward served on the plants, and vegetative organs. Page foliar application of selenium fertilizer directly from the stomatal be absorbed into the plants, sent to the edible parts of plants, selenium is more efficient and effective, and therefore even better than from the root absorption.
(8) For the development of the rich in selenium industry, I proposed the following measures:a scientific research foundation. The first detailed geological survey work, to find out their family property, such as selenium-rich rock distribution, mineable reserves estimates, the low-selenium coal gangue comprehensive utilization, and other geological research. Second, we must be rich in selenium soil survey, use and planning. Finally, in the breeding and cultivation of improved varieties of crops.2,promotion planning grasp the market.3,government enterprise collaboration.
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