CN102632074A - Method for repairing heavy metal polluted soil by using radix achyranthis bidentatae as manganese hyperaccumulator - Google Patents
Method for repairing heavy metal polluted soil by using radix achyranthis bidentatae as manganese hyperaccumulator Download PDFInfo
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Abstract
Description
技术领域 technical field
本发明涉及重金属污染土壤植物修复技术领域,具体是一种利用锰超富集植物牛膝修复重金属污染土壤的方法。 The invention relates to the technical field of phytoremediation of heavy metal-contaminated soil, in particular to a method for remediating heavy metal-contaminated soil by using a manganese hyperaccumulator plant Achyranthes bidentata.
背景技术 Background technique
重庆市锰矿资源丰富,但在锰矿的开采和加工过程中造成的环境污染也非常严重。其中重庆市秀山县与湖南省花垣县、贵州省松桃县因锰矿资源丰富而并称为中国锰矿“金三角”,是目前世界最大的锰矿石和电解锰生产基地,被誉为“世界第一锰都”。秀山县从2001年开始发展锰产业,锰产业对当地财政的贡献率达70%。但在经济高速发展的同时,当地的生态环境也遭受了严重的污染和破坏。在锰矿的开采和加工过程中,由于技术落后、设备简陋、管理不善造成的废水、废气任意排放,废渣不经处理随意堆积在田间野外,导致当地河流污浊、酸雾弥漫。大面积的农作物及野生植被在锰毒的侵蚀下死亡,大量良田因受锰污染而丧失其原有的生态功能和生产能力。因此,如何控制和减轻锰毒对环境的污染和危害已成为一个日益突出的问题。而常规的污染土壤修复方法,如客土换土法、淋洗法、热处理、固化等,由于其技术要求高或经济成本昂贵或对土壤结构破坏严重等原因,致使大规模推广存在许多问题。植物修复技术是利用超富集植物从被污染的环境介质中去除重金属污染物或降低重金属污染风险的一类新技术,它既可以修复重金属污染土地,也可以改善矿区生态环境,还能从低品位的尾矿或土地中富集贵金属,实现土地环境保护和金属矿产资源高效回收利用的统一。与传统治理方法相比,这项技术以其潜在的高效、经济及其生态协调性等优势显示出巨大的生命力。 Chongqing is rich in manganese ore resources, but the environmental pollution caused by manganese ore mining and processing is also very serious. Among them, Xiushan County of Chongqing City, Huayuan County of Hunan Province, and Songtao County of Guizhou Province are called the "Golden Triangle" of China's manganese ore due to their rich manganese ore resources. All". Xiushan County started to develop the manganese industry in 2001, and the contribution rate of the manganese industry to the local finance reached 70%. But at the same time of rapid economic development, the local ecological environment has also suffered serious pollution and damage. During the mining and processing of manganese ore, due to backward technology, poor equipment, and poor management, waste water and waste gas are discharged randomly, and waste residues are piled up in the field without treatment, resulting in the pollution of local rivers and acid mist. A large area of crops and wild vegetation died under the erosion of manganese poisoning, and a large number of fertile fields lost their original ecological functions and production capacity due to manganese pollution. Therefore, how to control and reduce the environmental pollution and harm of manganese poisoning has become an increasingly prominent problem. However, the conventional methods of remediation of contaminated soil, such as soil replacement method, leaching method, heat treatment, curing, etc., have many problems in large-scale promotion due to their high technical requirements, high economic costs, or serious damage to soil structure. Phytoremediation technology is a new type of new technology that uses hyperaccumulator plants to remove heavy metal pollutants from polluted environmental media or reduce the risk of heavy metal pollution. It can not only repair heavy metal polluted land, but also improve the ecological environment of mining areas. High-grade tailings or precious metals are enriched in the land, realizing the unity of land environmental protection and efficient recycling of metal mineral resources. Compared with traditional governance methods, this technology has shown great vitality due to its potential advantages of high efficiency, economy and its ecological coordination.
广义上的植物修复是指利用植物(包括草、灌、乔)去除污染土壤和废水中重金属的技术,包括植物萃取、根际过滤、植物挥发和植物固定。其中最有前景的是植物萃取,亦即通常所指的植物修复。植物萃取技术是指利用金属富集植物或超富集植物的根系将土壤中的金属提取出来并运移至植物地上部,通过收割地上部物质带走土壤中重金属的一种方法。超富集植物是植物修复的基础,寻找开发生物量大、富集重金属能力强的超富集植物是植物修复技术走向工程应用的首要任务。目前,关于锰超富集植物的衡量标准包括3项指标:一是临界含量特征,锰超富集植物叶片或地上部(干重)中含锰达到10000 mg/kg;二是具有转移特征,植物体地上部锰含量大于其根部含量;三是超富集植物具有耐性特征和富集特征。利用超富集植物修复重金属污染土壤是目前研究最多、最有发展前景的方法。 Phytoremediation in a broad sense refers to the technology of using plants (including grasses, shrubs, and trees) to remove heavy metals in polluted soil and wastewater, including phytoextraction, rhizosphere filtration, plant volatilization, and phytofixation. The most promising of these are phytoextracts, commonly referred to as phytoremediation. Phytoextraction technology refers to a method that uses the roots of metal-enriched plants or hyper-accumulated plants to extract metals from the soil and transport them to the aboveground parts of plants, and remove heavy metals in the soil by harvesting the aboveground materials. Hyperaccumulator plants are the basis of phytoremediation, and finding and developing hyperaccumulator plants with large biomass and strong ability to accumulate heavy metals is the primary task of phytoremediation technology towards engineering applications. At present, the measurement standards for manganese hyperaccumulator plants include three indicators: one is the critical content characteristics, the manganese content in the leaves or shoots (dry weight) of manganese hyperaccumulator plants reaches 10000 mg/kg; the other is the transfer characteristics, The content of manganese in the aboveground part of the plant is greater than that in the root; the third is that the hyperaccumulator has the characteristics of tolerance and enrichment. The use of hyperaccumulators to remediate heavy metal-contaminated soils is currently the most researched and most promising method.
发明内容 Contents of the invention
本发明的目的在于提供一种利用锰超富集植物牛膝修复重金属污染土壤的方法,该方法在不破坏土壤原状结构,保持土壤微生物活性的情况下,将牛膝种植在锰污染土壤上,利用牛膝的根系从土壤中吸收大量的锰元素并转运到地上部分累积,植物成熟后将其收获并移出土壤以达到修复的目的。该方法绿色安全,具有投入成本低、工程量小、没有二次污染,能减少土壤侵蚀等优点。 The object of the present invention is to provide a kind of method utilizing manganese super-enrichment plant Achyranthes bidentata to restore heavy metal-contaminated soil, the method does not destroy soil original structure, under the situation of keeping soil microbial activity, Achyranthes bidentata is planted on the manganese-contaminated soil, The root system of Achyranthes bidentata is used to absorb a large amount of manganese from the soil and transport it to the aboveground part for accumulation. After the plant matures, it is harvested and removed from the soil to achieve the purpose of restoration. The method is green and safe, and has the advantages of low input cost, small engineering quantity, no secondary pollution, and reduced soil erosion.
为实现上述目的,本发明的技术方案如下: To achieve the above object, the technical scheme of the present invention is as follows:
利用锰超富集植物牛膝修复重金属污染土壤,在锰污染土壤上种植牛膝,待牛膝植株生长成熟后,将整株植物移出污染土壤,并妥善处理,以实现修复的目的。 The manganese hyperaccumulator plant Achyranthes bidentata was used to remediate heavy metal-contaminated soil. Achyranthes bidentata was planted on the manganese-contaminated soil. After the Achyranthes bidentata plant grew and matured, the whole plant was removed from the contaminated soil and properly treated to achieve the purpose of restoration.
本发明中所用植物牛膝是是用种子繁殖,所属植物为锰富集植物。 The plant Achyranthes bidentata used in the present invention is propagated by seeds, and the plants belong to manganese-enriched plants.
本发明中所用植物牛膝在播种前将种子用30℃温水浸泡8-12h,捞出并放入容器内,覆盖湿布保湿,待50%种子萌芽时,取出并拌入适量细土,进行撒播。 The plant Achyranthes bidentata used in the present invention soaks the seeds in warm water at 30°C for 8-12 hours before sowing, removes them and puts them in a container, covers them with a damp cloth to keep them moist, and when 50% of the seeds germinate, takes them out and mixes them with an appropriate amount of fine soil, and spreads them .
本发明中所用植物牛膝,在锰污染土壤上种植牛膝,牛膝从污染土壤中吸收锰并向地上部分转移,当牛膝植株生长成熟后,将整株植物从污染土壤上移除,通过连续种植牛膝,重复上述操作,直至土壤中的锰含量达到环境安全标准。 Plant Achyranthes bidentata used in the present invention, plant Achyranthes bidentata on manganese-contaminated soil, Achyranthes bidentata absorbs manganese from polluted soil and transfers to above-ground part, after Achyranthes bidentata plant grows mature, whole plant is removed from polluted soil, By continuously planting Achyranthes bidentata, the above operations are repeated until the manganese content in the soil reaches the environmental safety standard.
本发明所用植物为牛膝:牛膝(Achyranthes bidentata),多年生草本,高70-120cm。根细长,黄白色,肉质。茎有棱,疏被柔毛,节膨大如膝。叶对生,椭圆形或坡针形,两面疏生细柔毛,沿主脉较密。穗状花序顶生和腋生,花后总花梗伸长,花向下折而贴靠总花便;苞片1,膜质,宽卵形,顶端渐尖,小苞片2,刺状,长约3毫米,基部两侧各有1卵状膜片,长约0.3毫米,苞片及小苞片均无缘毛;花被片5,绿色,多具1脉;雄蕊5,花丝下部合生,退化雄蕊短于花丝,舌状,顶端平圆或浅波状;子房上位。胞果长圆形。花期7-9月份,果期9-10月份。
The plant used in the present invention is Achyranthes bidentata: Achyranthes bidentata , a perennial herb with a height of 70-120cm. Roots are slender, yellowish-white, fleshy. Stem ribbed, sparsely pilose, nodes swollen like knees. The leaves are opposite, oval or needle-shaped, sparsely pubescent on both sides, and denser along the main vein. Spikes are terminal and axillary, the peduncle is elongated after flowering, and the flowers are folded downward and close to the total flower; bract 1, membranous, broadly ovate, apex acuminate, bracteole 2, spiny, long About 3 mm, with 1 egg-shaped membrane on both sides of the base, about 0.3 mm long, bracts and bracteoles without ciliates;
本发明所具有的优点: The advantages that the present invention has:
1.本发明所采用植物牛膝,生物量大,生长迅速,繁殖力强,对锰具有很强的耐性、吸收以及超富集能力。将牛膝种植在锰污染土壤中,通过植物根系从土壤中吸收大量的锰元素并转运到地上,待植物成熟后将其整株移出土壤,并进行妥善处理,从而达到快速有效、绿色安全的修复锰污染土壤的目的。 1. The plant Achyranthes bidentata adopted in the present invention has large biomass, rapid growth, strong fecundity, and strong tolerance, absorption and super-enrichment ability to manganese. Achyranthes knuckles are planted in manganese-contaminated soil, and a large amount of manganese is absorbed from the soil through the plant roots and transported to the ground. After the plant matures, the whole plant is removed from the soil and treated properly, so as to achieve fast, effective, green and safe. The purpose of remediating manganese-contaminated soil.
2. 本发明采用牛膝修复锰污染土壤,绿色安全,具有投入成本低、工程量小、没有二次污染,能减少土壤侵蚀等优点。 2. The present invention uses Achyranthes bidentata to restore manganese-contaminated soil, which is green and safe, and has the advantages of low input cost, small engineering volume, no secondary pollution, and reduced soil erosion.
附图说明 Description of drawings
图1为不同浓度锰处理牛膝生物量的检测图 Figure 1 is the detection chart of Achyranthes knuckle biomass treated with different concentrations of manganese
图2为不同浓度锰处理牛膝根长和株高的检测图 Figure 2 is the detection chart of root length and plant height of Achyranthes knuckle treated with different concentrations of manganese
图3为不同浓度锰处理牛膝锰含量的检测图 Figure 3 is the detection chart of manganese content in Achyranthes knuckle treated with different concentrations of manganese
图4为不同浓度锰处理牛膝锰积累量的检测图。 Figure 4 is the detection chart of manganese accumulation in Achyranthes knuckle treated with different concentrations of manganese.
具体实施方式 Detailed ways
实验土壤类型为紫色土,每盆装土2 kg,按盆栽作物对养分的需求(N 200 mg·kg-1, P2O5100 mg·kg-1, K2O 150—200 mg·kg-1)分别加入尿素、磷酸二氢钾和硫酸钾400, 200, 300 mg·kg-1。实验共设8个处理,分别为:CK(对照,不添加锰)、3000、4000、5000、6000、7000、8000、9000和10000 mg/kg,以MnCl2.4H2O的形式加入,每个处理3个重复。平衡1周后,将种子用30℃温水浸泡8-12h,捞出并放入容器内,覆盖湿布保湿,待50%种子萌芽时,取出并拌入适量细土,撒播在锰污染土壤表层,待种子苗出齐后,间苗,每盆留1株。根据盆中土壤缺水状况,不定期浇水,使土壤含水量保持在田间持水量的75-80%左右,盆下放置塑料托盘并将土壤水分渗漏液倒回盆中,植物生长时间为3个月。 The experimental soil type is purple soil, and each pot contains 2 kg of soil. According to the nutrient requirements of potted crops (N 200 mg·kg -1 , P 2 O 5 100 mg·kg -1 , K 2 O 150—200 mg·kg -1 ) Add 400, 200, 300 mg·kg -1 of urea, potassium dihydrogen phosphate and potassium sulfate respectively. A total of 8 treatments were set up in the experiment, namely: CK (control, no manganese added), 3000, 4000, 5000, 6000, 7000, 8000, 9000 and 10000 mg/kg, added in the form of MnCl 2 .4H 2 O, each 3 replicates per treatment. After equilibrating for 1 week, soak the seeds in warm water at 30°C for 8-12 hours, remove them and put them in a container, cover them with a damp cloth to keep them moist, and when 50% of the seeds germinate, take them out and mix them with an appropriate amount of fine soil, and spread them on the surface of the manganese-contaminated soil. After the seedlings have emerged, thin the seedlings, leaving 1 plant in each pot. According to the soil water shortage in the pot, water it from time to time to keep the soil water content at about 75-80% of the field water holding capacity. Place a plastic tray under the pot and pour the soil moisture seepage back into the pot. The plant growth time is 3 months.
将收获的牛膝样品反复用自来水冲洗干净,去除粘附于植物样品上的泥土和污物,然后用去离子水冲洗干净,用吸水纸把表面水吸干。将样品分为地上部分和根系,测定其株高、根长以及各部分鲜重,鲜样在105℃下杀青30分钟,然后在70℃下烘干至恒重,测定其干物质量,最后用不锈钢粉碎机磨细,过60目尼龙网筛,供分析测定用。植物样品用HNO3 - HClO4消化,用原子吸收分光光度计测定其中的锰含量。 The harvested Achyranthes bidentata samples were repeatedly rinsed with tap water to remove the soil and dirt adhering to the plant samples, then rinsed with deionized water, and the surface water was blotted dry with absorbent paper. Divide the samples into aerial part and root system, and measure the plant height, root length and fresh weight of each part. Fresh samples were killed at 105°C for 30 minutes, then dried at 70°C to constant weight, and the dry matter was measured. Grind with a stainless steel pulverizer and pass through a 60-mesh nylon mesh sieve for analysis and determination. The plant samples were digested with HNO 3 -HClO 4 and the manganese content was determined by atomic absorption spectrophotometer.
采用Microsoft Excel 2003进行平均值和标准差的运算,以平均值±标准差的形式表示,并采用最小显著性差异检验(LSD检验)进行植物样品间差异显著性检验。 Microsoft Excel 2003 was used to calculate the mean value and standard deviation, expressed in the form of mean ± standard deviation, and the least significant difference test (LSD test) was used to test the significance of the difference between plant samples.
实验结果如下: The experimental results are as follows:
锰污染对牛膝生长发育的影响。参见图1、图2可知,随着介质中锰浓度的升高,除了牛膝根长无明显变化外,根、地上生物量及株高都显著降低(p<0.01),表明往土壤中添加锰抑制了牛膝的生长和发育。与对照相比,当锰添加浓度为3000 mg/kg时,地上和根生物量分别减少了43%和66%,株高减少了24%;当锰添加浓度为4000 mg/kg时,地上和根生物量分别减少了90%和84%,株高减少了67%,而超过4000 mg/kg后,牛膝已无法存活。 Effects of manganese pollution on the growth and development of Achyranthes knuckles. Referring to Figure 1 and Figure 2, it can be seen that with the increase of manganese concentration in the medium, except for the root length of Achyranthes bidentata, the root, aboveground biomass and plant height were all significantly reduced (p<0.01), indicating that adding Manganese inhibits the growth and development of Achyranthes knuckles. Compared with the control, when the manganese concentration was 3000 mg/kg, aboveground and root biomass decreased by 43% and 66%, respectively, and plant height decreased by 24%. The root biomass decreased by 90% and 84%, respectively, and the plant height decreased by 67%. After exceeding 4000 mg/kg, Achyranthes bidentata could no longer survive.
牛膝对锰的吸收。参见图3可知,牛膝地上部分锰含量随着锰供应水平的增加而升高(p<0.01),同时根系锰含量也随之升高(p<0.05)。当锰添加浓度为4000 mg/kg时,牛膝地上部分锰含量为18809.91 mg/kg,远超过了锰超富集植物临界含量10000 mg/kg标准。 Absorption of manganese by Achyranthes knuckles. Referring to Figure 3, it can be seen that the manganese content in the aerial part of Achyranthes knuckles increased with the increase of manganese supply level (p<0.01), and the manganese content in the roots also increased (p<0.05). When the manganese concentration was 4000 mg/kg, the manganese content in the aerial part of Achyranthes bidentata was 18809.91 mg/kg, far exceeding the critical content of 10000 mg/kg in manganese hyperaccumulator plants.
参见表1可知,牛膝对锰有很强的吸收和富集能力,生物富集系数是指植物体内某种重金属含量与土壤中同种重金属含量的比值,反映植物对土壤重金属元素的富集能力,富集系数越高,表明植物对重金属的吸收累积能力就越强,就越有利于植物对重金属污染土壤的提取和修复。当锰添加浓度为3000和4000 mg/kg时,生物富集系数分别为1.79和2.55,均大于1,表明牛膝具备了锰超富集植物的富集系数特征。 Referring to Table 1, it can be seen that Achyranthes bidentata has a strong ability to absorb and enrich manganese. The bioconcentration coefficient refers to the ratio of the content of a certain heavy metal in the plant to the content of the same heavy metal in the soil, reflecting the enrichment of heavy metal elements in the soil by plants. The higher the enrichment factor, the stronger the ability of plants to absorb and accumulate heavy metals, which is more conducive to the extraction and restoration of heavy metal-contaminated soil by plants. When the manganese concentration was 3000 and 4000 mg/kg, the bioaccumulation coefficients were 1.79 and 2.55, respectively, both greater than 1, indicating that Achyranthes bidentata possessed the characteristics of the enrichment coefficient of manganese hyperaccumulator plants.
表1 不同锰处理浓度下牛膝对锰的富集系数、转移系数和提取率 Table 1 Enrichment coefficient, transfer coefficient and extraction rate of manganese in Achyranthes bidentata under different manganese treatment concentrations
生物转移系数是指植物地上部重金属含量与根部重金属含量之比,用来评价植物将重金属从根系向地上部运输和积累的能力。生物转移系数越高,则重金属从地下向地上器官的运输能力就越强。参见表1可知,当锰添加浓度为3000和4000 mg/kg时,生物转移系数分别为7.46和9.07,均大于1,符合超富集植物积累金属的一般特征。锰在牛膝地上部和根系中的分布存在显著差异,整个植株吸收的锰超过95%都分布在地上部,表明牛膝根系吸收的锰有很强的向地上部分转运的能力。 The biotransfer coefficient refers to the ratio of the heavy metal content in the aboveground part of the plant to the heavy metal content in the root, which is used to evaluate the ability of the plant to transport and accumulate heavy metals from the root system to the aboveground part. The higher the biological transfer coefficient, the stronger the transport capacity of heavy metals from underground to aboveground organs. Referring to Table 1, it can be seen that when the manganese concentration was 3000 and 4000 mg/kg, the biotransfer coefficients were 7.46 and 9.07, respectively, both greater than 1, which conformed to the general characteristics of metal accumulation in hyperaccumulator plants. The distribution of manganese in Achyranthes bidentata shoots and root system was significantly different, and more than 95% of the manganese absorbed by the whole plant was distributed in the shoot, indicating that the manganese absorbed by Achyranthes bidentata root system had a strong ability to transport to the shoot.
重金属的提取率是指植物重金属积累量与土壤中重金属含量之比,是一个用来评价超富集植物提取修复重金属污染土壤潜力的重要指标。参见表1可知,当锰添加浓度为3000和4000 mg/kg时,提取率分别为0.72%和0.19%,提取率随着土壤中锰浓度的升高而降低。 The extraction rate of heavy metals refers to the ratio of the accumulation of heavy metals in plants to the content of heavy metals in soil. Referring to Table 1, it can be seen that when the manganese concentration is 3000 and 4000 mg/kg, the extraction rate is 0.72% and 0.19%, respectively, and the extraction rate decreases with the increase of manganese concentration in the soil.
参见图4可知,牛膝地上部锰累积量(ug/盆)远大于根部(p<0.01),当锰添加浓度为3000 mg/kg时,地上部和根部锰积累量分别为77439.19和1463.61 ug/盆,地上部是根部的52.91倍,当锰添加浓度为4000 mg/kg时,地上部和根部锰积累量分别降低为26521.98和1098.67 ug/盆,地上部为根部的24.14倍。因此,通过收获植株的地上部,也能达到去除土壤中锰污染的目的。 Referring to Figure 4, it can be seen that the manganese accumulation in the aerial part of Achyranthes knuckles (ug/pot) is much greater than that in the root (p<0.01). When the manganese concentration is 3000 mg/kg, the manganese accumulation in the aerial part and root are 77439.19 and 1463.61 ug respectively / basin, the shoot is 52.91 times that of the root. When the concentration of manganese is 4000 mg/kg, the accumulation of manganese in the shoot and root is reduced to 26521.98 and 1098.67 ug/basin, respectively, and the shoot is 24.14 times that of the root. Therefore, by harvesting the above-ground parts of the plants, the purpose of removing manganese pollution in the soil can also be achieved.
通过上述实验结果表明,本发明所采用植物牛膝对锰有很强的富集和积累能力,将牛膝种植在锰污染土壤上,当土壤中锰添加浓度为4000 mg/kg,牛膝地上部锰浓度为18809.91 mg/kg,远超过了锰超富集植物临界含量10000 mg/kg标准,此时生物转移系数和富集系数分别为9.07和2.55,均达到了锰超富集植物的标准。当牛膝成熟后,将整株植物从土壤移除并妥善处理,从而达到去除土壤中过量锰的目的。在锰污染土壤上连续种植牛膝,并不断的整株收获和移除土壤,直至土壤中锰含量达到环境安全标准。采用本发明既能修复重金属污染土壤,还能美化环境,是一种廉价、绿色、安全的土壤治理技术。 Show by above-mentioned experimental result, plant Achyranthes bidentata adopted in the present invention has very strong enrichment and accumulation ability to manganese, Achyranthes bidentata is planted on the manganese polluted soil, when manganese addition concentration is 4000 mg/kg in the soil, Achyranthes bidentata above ground The local manganese concentration was 18809.91 mg/kg, which far exceeded the critical content of 10000 mg/kg for manganese hyperaccumulator plants. At this time, the biotransfer coefficient and enrichment coefficient were 9.07 and 2.55, respectively, which reached the standard of manganese hyperaccumulator plants. . When the achyranthes is mature, remove excess manganese from the soil by removing the entire plant from the soil and disposing of it properly. Achyranthes bidentata was planted continuously on the manganese-contaminated soil, and the whole plant was harvested continuously and the soil was removed until the manganese content in the soil reached the environmental safety standard. By adopting the invention, the soil polluted by heavy metals can be repaired and the environment can be beautified, and it is a cheap, green and safe soil treatment technology.
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