CN115990328B - Composite preparation for efficiently degrading soil glyphosate, and use method and application thereof - Google Patents
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- 239000002689 soil Substances 0.000 title claims abstract description 118
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 65
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 30
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 30
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 35
- 239000003337 fertilizer Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000009472 formulation Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000618 nitrogen fertilizer Substances 0.000 claims description 5
- 239000003516 soil conditioner Substances 0.000 claims description 4
- 239000002686 phosphate fertilizer Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- KMQAPZBMEMMKSS-UHFFFAOYSA-K calcium;magnesium;phosphate Chemical compound [Mg+2].[Ca+2].[O-]P([O-])([O-])=O KMQAPZBMEMMKSS-UHFFFAOYSA-K 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 2
- 229940072033 potash Drugs 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- 235000015320 potassium carbonate Nutrition 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- 239000001166 ammonium sulphate Substances 0.000 claims 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims 1
- 229910000389 calcium phosphate Inorganic materials 0.000 claims 1
- 235000019691 monocalcium phosphate Nutrition 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 21
- 238000006731 degradation reaction Methods 0.000 abstract description 21
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 18
- 230000004720 fertilization Effects 0.000 abstract description 5
- 235000015097 nutrients Nutrition 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract description 2
- 229940078916 carbamide peroxide Drugs 0.000 abstract 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 23
- 240000008042 Zea mays Species 0.000 description 15
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 15
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- 238000006243 chemical reaction Methods 0.000 description 11
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- 241000196324 Embryophyta Species 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
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- 230000009418 agronomic effect Effects 0.000 description 4
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- 241000894006 Bacteria Species 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
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- 239000004471 Glycine Substances 0.000 description 1
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- 108090000913 Nitrate Reductases Proteins 0.000 description 1
- 108010046334 Urease Proteins 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
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- Fertilizers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
技术领域Technical Field
本发明属于土壤修复与农业技术领域。具体地,涉及一种高效降解土壤草甘膦的复合制剂及其使用方法和应用。The present invention belongs to the field of soil remediation and agricultural technology, and specifically relates to a composite preparation for efficiently degrading soil glyphosate, and a use method and application thereof.
背景技术Background technique
草甘膦[N-(磷酸甲基)甘氨酸]作为一种广谱且高效的除草剂,为农田消除杂草,粮食作物增收增产等提供了保障。但随着草甘膦的广泛使用与不合理施用,农田土壤、水体的草甘膦残留问题越来越突出。近几十年来,多项研究表明,草甘膦或以草甘膦作为基础配方的除草剂会对包括微生物在内的非目标水生生物产生毒害作用,如两栖动物、无脊椎动物、水生植物、虾等,草甘膦在经过食物链的传递后,甚至会对人体产生毒害作用。2017年10月27日,世界卫生组织国际癌症研究机构公布的致癌物清单初步整理参考,草甘膦在2A类致癌物清单中。Glyphosate [N-(phosphomethyl)glycine] is a broad-spectrum and highly effective herbicide that provides protection for eliminating weeds in farmland and increasing the income and yield of grain crops. However, with the widespread use and irrational application of glyphosate, the problem of glyphosate residues in farmland soil and water bodies has become increasingly prominent. In recent decades, many studies have shown that glyphosate or herbicides based on glyphosate can have toxic effects on non-target aquatic organisms, including microorganisms, such as amphibians, invertebrates, aquatic plants, shrimp, etc. Glyphosate can even have toxic effects on humans after being transmitted through the food chain. On October 27, 2017, the World Health Organization's International Agency for Research on Cancer published a preliminary list of carcinogens for reference, and glyphosate is on the list of Class 2A carcinogens.
目前有关草甘膦降解的方法主要通过微生物降解。但大部分专利筛选出的降解菌大多为单株菌种,或者两种到三种菌株。而微生物降解草甘膦还局限于实验室研究阶段,且在复杂土壤体系中,存在大量的土壤土著(先锋)微生物菌种,很难保证人工添加降解菌对草甘膦降解的效果。而如何实现草甘膦降解的同时增加农田肥力的研究甚少。因此,提供一种高效、经济、简单易操作、补肥并高效降解土壤草甘膦的复合制剂和方法非常重要。At present, the method for glyphosate degradation is mainly through microbial degradation. However, most of the degradation bacteria screened out in most patents are single strains, or two to three strains. Microbial degradation of glyphosate is still limited to the laboratory research stage, and in complex soil systems, there are a large number of soil indigenous (pioneer) microbial strains, and it is difficult to ensure the effect of artificially added degradation bacteria on glyphosate degradation. There is little research on how to achieve glyphosate degradation while increasing farmland fertility. Therefore, it is very important to provide a composite preparation and method that is efficient, economical, simple and easy to operate, and can supplement fertilizer and efficiently degrade soil glyphosate.
发明内容Summary of the invention
本发明的目的在于针对现有技术中的上述不足,提供一种高效降解土壤草甘膦的复合制剂及其使用方法和应用。The purpose of the present invention is to provide a composite formulation for efficiently degrading soil glyphosate and a method for using and application thereof in view of the above-mentioned deficiencies in the prior art.
本发明的第一目的是提供一种高效降解土壤草甘膦的复合制剂。The first object of the present invention is to provide a composite formulation for efficiently degrading soil glyphosate.
本发明的另一目的是提供上述高效降解土壤草甘膦复合制剂的应用。Another object of the present invention is to provide the application of the above-mentioned highly efficient soil degradation glyphosate composite formulation.
本发明的再一目的是提供上述高效降解土壤草甘膦复合制剂的使用方法。Another object of the present invention is to provide a method for using the above-mentioned highly efficient soil-degrading glyphosate composite formulation.
本发明上述目的通过以下技术方案实现:The above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种高效降解土壤草甘膦的复合制剂,所述复合制剂的有效成分为过氧化尿素和硫酸亚铁盐。A composite preparation for efficiently degrading soil glyphosate, wherein the active ingredients of the composite preparation are urea peroxide and ferrous sulfate.
本发明旨在利用具有供氧与缓释的过氧化尿素与硫酸亚铁复配出可自主促发(类)芬顿效应的复合制剂以有效降解土壤草甘膦。该复合制剂通过过氧化尿素缓释产生土壤微摩尔级浓度的过氧化氢,并通过优化配比Fe2+的催化作用,从而高效促进草甘膦的降解。使用该复合制剂不仅可以高效降解土壤草甘膦,还可以保证土壤养分的供给,是一种操作简单、减少劳动力的投入的方法。The present invention aims to utilize urea peroxide with oxygen supply and slow release and ferrous sulfate to prepare a composite preparation that can autonomously trigger a (quasi) Fenton effect to effectively degrade soil glyphosate. The composite preparation generates soil micromolar concentration of hydrogen peroxide through the slow release of urea peroxide, and efficiently promotes the degradation of glyphosate by optimizing the catalytic effect of Fe 2+ . The composite preparation can not only efficiently degrade soil glyphosate, but also ensure the supply of soil nutrients, and is a method that is simple to operate and reduces labor input.
优选地,所述过氧化尿素与硫酸亚铁盐的浓度比为1~3:0.5~1。Preferably, the concentration ratio of the urea peroxide to the ferrous sulfate is 1-3:0.5-1.
更优选地,所述过氧化尿素与硫酸亚铁盐的浓度比为1~2:1。More preferably, the concentration ratio of the urea peroxide to the ferrous sulfate is 1 to 2:1.
优选地,所述复合制剂中过氧化尿素含量为2~6mmol/kg,硫酸亚铁盐含量为1~2mmol/kg。Preferably, the content of urea peroxide in the composite preparation is 2-6 mmol/kg, and the content of ferrous sulfate is 1-2 mmol/kg.
优选地,所述过氧化尿素的氮含量为28~32%,活性氧质量分数为12~16%,过氧化氢含量为34~38%。Preferably, the nitrogen content of the urea peroxide is 28-32%, the active oxygen mass fraction is 12-16%, and the hydrogen peroxide content is 34-38%.
更优选地,所述过氧化尿素的氮含量为30~31%,活性氧质量分数为14~15%,过氧化氢含量为35~36%。More preferably, the nitrogen content of the urea peroxide is 30-31%, the active oxygen mass fraction is 14-15%, and the hydrogen peroxide content is 35-36%.
优选地,所述的硫酸亚铁盐包括七水硫酸亚铁或硫酸亚铁。Preferably, the ferrous sulfate salt includes ferrous sulfate heptahydrate or ferrous sulfate.
优选地,所述的复合制剂可以配施10~35mg/kg的土壤调节剂;所述土壤调节剂包括以下重量份数的原料:10~19份氮肥、6~19份磷肥、5~34份钾肥。Preferably, the composite formulation can be formulated with 10-35 mg/kg of a soil conditioner; the soil conditioner comprises the following raw materials in parts by weight: 10-19 parts of nitrogen fertilizer, 6-19 parts of phosphorus fertilizer, and 5-34 parts of potassium fertilizer.
优选地,所述氮肥为尿素、硫铵、磷铵的一种或多种;所述磷肥为过磷酸钙、钙镁磷肥的一种或多种;所述钾肥为硫酸钾、氯酸钾的一种或多种。Preferably, the nitrogen fertilizer is one or more of urea, ammonium sulfate, and ammonium phosphate; the phosphate fertilizer is one or more of superphosphate and calcium magnesium phosphate; and the potassium fertilizer is one or more of potassium sulfate and potassium chlorate.
本发明还提供了所述的复合制剂在制备降解土壤草甘膦产品中的应用。在本发明较佳的实施例中,在培养初期,UHP、Fe+UHP处理组能较快地去除水稻土和红壤中的草甘膦,且效果较好。The present invention also provides the use of the composite formulation in the preparation of a soil degrading glyphosate product. In a preferred embodiment of the present invention, in the early stage of cultivation, the UHP and Fe+UHP treatment groups can remove glyphosate in paddy soil and red soil more quickly and with better effects.
优选地,所述土壤的pH为6.0~7.0。Preferably, the pH of the soil is 6.0-7.0.
优选地,所述土壤为南方红壤或水稻土。本发明尤其适用于受草甘膦污染的水稻土与南方红壤,可同步实现草甘膦的降解与氮肥施用。Preferably, the soil is southern red soil or paddy soil. The present invention is particularly suitable for paddy soil and southern red soil contaminated by glyphosate, and can simultaneously achieve glyphosate degradation and nitrogen fertilizer application.
本发明还提供了所述复合制剂的使用方法,主要包括以下步骤:The present invention also provides a method for using the composite preparation, which mainly comprises the following steps:
S1.选择受草甘膦影响的土壤,经过晾干后翻匀;草甘膦含量为8~15mg/kg;S1. Select the soil affected by glyphosate, dry it and turn it evenly; the glyphosate content is 8-15 mg/kg;
S2.将所述复合制剂添加到受污染土壤中搅匀;施用量为每亩12~15公斤;S2. Add the composite preparation to the contaminated soil and mix well; the application rate is 12 to 15 kg per mu;
S3.在施用复合制剂后,浇水/灌水保持土壤含水量30%~60%;S3. After applying the compound preparation, water/irrigate to maintain the soil moisture content at 30% to 60%;
S4.在施肥处理5-10天后,进行作物移栽。S4. Transplant crops 5-10 days after fertilization.
优选地,所述草甘膦含量为10~11mg/kg。Preferably, the glyphosate content is 10-11 mg/kg.
优选地,在施肥处理7-8天后,进行作物移栽。Preferably, crops are transplanted 7-8 days after fertilization.
本发明通过选用过氧化尿素(UHP)配以硫酸亚铁(Fe),以介导芬顿反应或者类芬顿反应促进土壤草甘膦的降解效果更佳。在培养的第1、7、14、28天,Fe+UHP组对草甘膦的降解率分别为31.71%、46.66%、50.24%、70.74%,显著高于其他处理组。第一天施用后,水稻土的施氮组UHP与Fe+UHP的铵态氮含量比对照组分别升高了2.86倍、和2.84倍;红壤中的UHP与Fe+UHP的铵态氮含量比对照组分别升高了3.73倍、和3.15倍。水稻土和红壤的铵态氮变化范围分别为11.29~100.03mg/kg和2.73~73.19mg/kg。与对照相比,施氮组的铵态氮含量在28天的培养期内均显著更高,并大幅度提高了土壤中铵态氮含量和脲酶活性,降低了硝酸还原酶、过氧化氢酶活性。The present invention selects urea peroxide (UHP) and ferrous sulfate (Fe) to mediate Fenton reaction or Fenton-like reaction to promote the degradation of soil glyphosate, which has a better effect. On the 1st, 7th, 14th and 28th days of cultivation, the degradation rates of glyphosate in the Fe+UHP group were 31.71%, 46.66%, 50.24% and 70.74%, respectively, which were significantly higher than those in other treatment groups. After the first day of application, the ammonium nitrogen content of the UHP and Fe+UHP in the nitrogen application group of paddy soil increased by 2.86 times and 2.84 times respectively compared with the control group; the ammonium nitrogen content of the UHP and Fe+UHP in the red soil increased by 3.73 times and 3.15 times respectively compared with the control group. The ammonium nitrogen variation ranges of paddy soil and red soil were 11.29-100.03 mg/kg and 2.73-73.19 mg/kg, respectively. Compared with the control, the ammonium nitrogen content in the nitrogen application group was significantly higher during the 28-day incubation period, and the ammonium nitrogen content and urease activity in the soil were greatly increased, and the activities of nitrate reductase and catalase were reduced.
在本发明中,水稻土中的铵态氮含量普遍高于红壤;而且,施加过氧化尿素、尿素以及硫酸亚铁到草甘膦污染土壤中,施氮组的氮素转化情况相差较小,在去除草甘膦的同时可正常提供氮素营养;其次,与对照组相比,施加复配制剂后均有利于玉米幼苗地下部生长,促进其茎粗生长,其中过氧化尿素可以显著提高幼苗的根长。另外,与对照组相比,过氧化尿素和普通尿素两种氮肥的施氮组间氮素转化情况没有显著差异,但过氧化尿素可促进草甘膦残留更快降解,在正常提供氮素营养的同时降低草甘膦残留的毒害,促进玉米生长。In the present invention, the ammonium nitrogen content in paddy soil is generally higher than that in red soil; moreover, when urea peroxide, urea and ferrous sulfate are applied to glyphosate-contaminated soil, the nitrogen conversion of the nitrogen-applying group is relatively small, and nitrogen nutrition can be normally provided while removing glyphosate; secondly, compared with the control group, the application of the compound preparation is beneficial to the underground growth of corn seedlings and promotes the growth of its stem thickness, wherein urea peroxide can significantly increase the root length of the seedlings. In addition, compared with the control group, there is no significant difference in nitrogen conversion between the nitrogen-applying groups of urea peroxide and ordinary urea, but urea peroxide can promote faster degradation of glyphosate residues, reduce the toxicity of glyphosate residues while providing nitrogen nutrition normally, and promote corn growth.
与现有技术相比,本发明具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
与常用的微生物降解土壤草甘膦的方法相比,本发明提供一种高效降解土壤草甘膦的复合制剂及其使用方法和应用。通过利用具有供氧与缓释的过氧化尿素与硫酸亚铁盐配成可自主促发(类)芬顿效应的复合制剂以有效降解土壤草甘膦。该方法不仅可以高效降解土壤草甘膦,还可以保证土壤养分的供给,是一种操作简单、减少劳动力的投入的方法。本发明解决了草甘膦污染农田土壤修复与农业补肥难以兼顾的问题,具有良好的环境效益、经济效益和社会效益,具有很好的推广应用价值。Compared with the commonly used method of microbial degradation of soil glyphosate, the present invention provides a composite preparation for efficiently degrading soil glyphosate and its use method and application. By using urea peroxide and ferrous sulfate with oxygen supply and slow release to form a composite preparation that can autonomously trigger (quasi) Fenton effect, the soil glyphosate can be effectively degraded. The method can not only efficiently degrade soil glyphosate, but also ensure the supply of soil nutrients, and is a method that is simple to operate and reduces labor input. The present invention solves the problem that it is difficult to balance the restoration of glyphosate-contaminated farmland soil and agricultural fertilization, has good environmental benefits, economic benefits and social benefits, and has good promotion and application value.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是配施过氧化尿素与硫酸亚铁盐后水稻土中草甘膦的残留浓度。Figure 1 shows the residual concentration of glyphosate in paddy soil after the application of urea peroxide and ferrous sulfate.
图2是配施过氧化尿素与硫酸亚铁盐后水稻土铵态氮含量。Figure 2 shows the ammonium nitrogen content in paddy soil after the application of urea peroxide and ferrous sulfate.
图3是配施过氧化尿素与硫酸亚铁盐后南方红壤中草甘膦的残留浓度。Figure 3 shows the residual concentration of glyphosate in southern red soil after applying urea peroxide and ferrous sulfate.
图4是配施过氧化尿素与硫酸亚铁盐后红壤铵态氮含量。Figure 4 shows the ammonium nitrogen content in red soil after the application of urea peroxide and ferrous sulfate.
图5是配施过氧化尿素与硫酸亚铁盐后水稻土与红壤实验图。Figure 5 is an experimental picture of paddy soil and red soil after applying urea peroxide and ferrous sulfate.
图6是配施过氧化尿素与硫酸亚铁盐后玉米的生长照片。Figure 6 is a photo of the growth of corn after the application of urea peroxide and ferrous sulfate.
图7是不同肥料配比下的草甘膦污染土壤中的玉米幼苗农艺性状图;其中,(a)株高;(b)茎粗;(c)根长;(d)地上部鲜重;(e)地上部干重;(f)地下部鲜重;(g)地下部干重。Figure 7 is a graph of agronomic traits of corn seedlings in glyphosate-contaminated soil under different fertilizer ratios; among them, (a) plant height; (b) stem thickness; (c) root length; (d) aboveground fresh weight; (e) aboveground dry weight; (f) underground fresh weight; and (g) underground dry weight.
具体实施方式Detailed ways
以下结合具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。在不背离本发明精神和实质的情况下,对本发明方法、步骤或条件所作的简单修改或替换,均属于本发明的范围;若未特别指明,实施例中所用的技术手段为本领域技术人员所熟知的常规手段。The present invention is further described below in conjunction with specific examples, but the examples do not limit the present invention in any form. Without departing from the spirit and essence of the present invention, simple modifications or replacements made to the methods, steps or conditions of the present invention are within the scope of the present invention; unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述实施方式和实施例的目的,不是旨在于限制本发明。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing implementation modes and embodiments and are not intended to limit the present invention.
术语the term
除非另外说明或存在矛盾之处,本文中使用的术语或短语具有以下含义:Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:
本文所使用的术语“和/或”、“或/和”、“及/或”的选择范围包括两个或两个以上相关所列项目中任一个项目,也包括相关所列项目的任意的和所有的组合,所述任意的和所有的组合包括任意的两个相关所列项目、任意的更多个相关所列项目、或者全部相关所列项目的组合。需要说明的是,当用至少两个选自“和/或”、“或/和”、“及/或”的连词组合连接至少三个项目时,应当理解,在本申请中,该技术方案毫无疑问地包括均用“逻辑与”连接的技术方案,还毫无疑问地包括均用“逻辑或”连接的技术方案。比如,“A及/或B”包括A、B和A和B的组合三种并列方案。又比如,“A,及/或,B,及/或,C,及/或,D”的技术方案,包括A、B、C、D中任一项(也即均用“逻辑或”连接的技术方案),也包括A、B、C、D的任意的和所有的组合,也即包括A、B、C、D中任两项或任三项的组合,还包括A、B、C、D的四项组合(也即均用“逻辑与”连接的技术方案)。The terms "and/or", "or/and", and "and/or" used in this article have a selection range that includes any one of two or more related listed items, and also includes any and all combinations of related listed items, and the arbitrary and all combinations include any combination of two related listed items, any more related listed items, or all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and/or", "or/and", and "and/or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and/or B" includes three parallel solutions of A, B and the combination of A and B. For example, the technical solution of "A, and/or, B, and/or, C, and/or, D" includes any one of A, B, C, and D (that is, the technical solution that is all connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four of A, B, C, and D (that is, the technical solution that is all connected by "logical AND").
本文中,“优选”、“更好”、“更佳”、“为宜”仅为描述效果更好的实施方式或实施例,应当理解,并不构成对本发明保护范围的限制。如果一个技术方案中出现多处“优选”,如无特别说明,且无矛盾之处或相互制约关系,则每项“优选”各自独立。Herein, "preferred", "better", "more preferred" and "suitable" are only used to describe implementation methods or examples with better effects, and it should be understood that they do not constitute a limitation on the scope of protection of the present invention. If multiple "preferred" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "preferred" item is independent.
本发明中,“进一步”、“更进一步”、“特别”等用于描述目的,表示内容上的差异,但并不应理解为对本发明保护范围的限制。In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.
本发明中,“可选地”、“可选的”、“可选”,指可有可无,也即指选自“有”或“无”两种并列方案中的任一种。如果一个技术方案中出现多处“可选”,如无特别说明,且无矛盾之处或相互制约关系,则每项“可选”各自独立。In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.
本发明中,“第一方面”、“第二方面”、“第三方面”、“第四方面”等中,术语“第一”、“第二”、“第三”、“第四”等仅用于描述目的,不能理解为指示或暗示相对重要性或数量,也不能理解为隐含指明所指示的技术特征的重要性或数量。而且“第一”、“第二”、“第三”、“第四”等仅起到非穷举式的列举描述目的,应当理解并不构成对数量的封闭式限定。In the present invention, in the "first aspect", "second aspect", "third aspect", "fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.
本发明中,以开放式描述的技术特征中,包括所列举特征组成的封闭式技术方案,也包括包含所列举特征的开放式技术方案。In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.
本发明中,涉及到数值区间(也即数值范围),如无特别说明,该数值区间内可选的数值的分布视为连续,且包括该数值区间的两个数值端点(即最小值及最大值),以及这两个数值端点之间的每一个数值。如无特别说明,当数值区间仅仅指向该数值区间内的整数时,包括该数值范围的两个端点整数,以及两个端点之间的每一个整数,相当于直接列举了每一个整数。当提供多个数值范围描述特征或特性时,可以合并这些数值范围。换言之,除非另有指明,否则本文中所公开之数值范围应理解为包括其中所归入的任何及所有的子范围。该数值区间中的“数值”可以为任意的定量值,比如数字、百分比、比例等。“数值区间”允许广义地包括百分比区间、比例区间、比值区间等数值区间类型。In the present invention, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum value and the maximum value) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers in the numerical interval, including the two endpoint integers of the numerical range, and each integer between the two endpoints, is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical range disclosed herein should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows broadly including numerical interval types such as percentage intervals, ratio intervals, and ratio intervals.
本发明中的温度参数,如无特别限定,既允许为恒温处理,也允许在一定温度区间内存在变动。应当理解的是,所述的恒温处理允许温度在仪器控制的精度范围内进行波动。允许在如±5℃、±4℃、±3℃、±2℃、±1℃的范围内波动。The temperature parameters in the present invention, if not specifically limited, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the precision range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.
本发明中,术语“室温”或“常温”一般指4℃~35℃,例如20℃±5℃。在本发明的一些实施例中,“室温”或“常温”是指10℃~30℃。在本发明的一些实施例中,“室温”或“常温”是指20℃~30℃。In the present invention, the term "room temperature" or "normal temperature" generally refers to 4°C to 35°C, for example, 20°C ± 5°C. In some embodiments of the present invention, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of the present invention, "room temperature" or "normal temperature" refers to 20°C to 30°C.
在本发明中,涉及数据范围的单位,如果仅在右端点后带有单位,则表示左端点和右端点的单位是相同的。比如,3~5h表示左端点“3”和右端点“5”的单位都是h(小时)。In the present invention, when referring to the unit of the data range, if there is a unit only after the right endpoint, it means that the units of the left endpoint and the right endpoint are the same. For example, 3-5h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).
在本发明提及的所有文献都在本申请中引用作为参考,就如同每一篇文献被单独引用作为参考那样。除非和本申请的发明目的和/或技术方案相冲突,否则,本发明涉及的引用文献以全部内容、全部目的被引用。本发明中涉及引用文献时,相关技术特征、术语、名词、短语等在引用文献中的定义也一并被引用。本发明中涉及引用文献时,被引用的相关技术特征的举例、优选方式也可作为参考纳入本申请中,但以能够实施本发明为限。应当理解,当引用内容与本申请中的描述相冲突时,以本申请为准或者适应性地根据本申请的描述进行修正。All documents mentioned in the present invention are cited as references in this application, just as each document is cited as a reference separately. Unless they conflict with the invention purpose and/or technical solution of the present application, the cited documents involved in the present invention are cited with all contents and all purposes. When the present invention involves cited documents, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When the present invention involves cited documents, the examples and preferred embodiments of the cited relevant technical features may also be incorporated into this application as references, but are limited to the ability to implement the present invention. It should be understood that when the content of the citation conflicts with the description in this application, the present application shall prevail or be modified adaptively according to the description of this application.
本发明实施例说明书中所提到的相关成分的质量或重量不仅仅可以指代各组分的具体含量,也可以表示各组分间质量或重量的比例关系,因此,只要是按照本发明实施例说明书相关组分的含量按比例放大或缩小均在本发明实施例说明书公开的范围之内。具体地,本发明实施例说明书中所述的质量或重量可以是μg、mg、g、kg等化工领域公知的单位。The mass or weight of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also indicate the proportional relationship of the mass or weight between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the description of the embodiments of the present invention, it is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the mass or weight described in the description of the embodiments of the present invention may be units known in the chemical industry such as μg, mg, g, kg, etc.
本发明中过氧化尿素为农用级或工业级,其中氮含量为30%,活性氧质量分数为14%,过氧化氢含量为36%。The urea peroxide in the present invention is of agricultural grade or industrial grade, wherein the nitrogen content is 30%, the active oxygen mass fraction is 14%, and the hydrogen peroxide content is 36%.
除非特别说明,以下实施例所用试剂和材料均为市购。Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
实施例1一种高效降解水稻土壤中草甘膦的复合制剂及其使用方法Example 1 A composite formulation for efficiently degrading glyphosate in rice soil and its use method
以华南农业大学增城教学科研基地常年种植水稻、玉米等农作物的水稻土为实验土壤,经测试,该水稻土基础理化性质中的有机质含量为18.15g/kg,有效氮、磷、钾含量分别为18.18、6.96与32.10mg/kg,砂砾、粘粒与粉粒分别为56.75%、9.00%与0.10%,pH值为6.10,Eh值(氧化还原电位)为237mV,Ec值(电导率)为223μs/cm。The paddy soil in the Zengcheng teaching and research base of South China Agricultural University, where rice, corn and other crops are planted all year round, was used as the experimental soil. After testing, the organic matter content in the basic physical and chemical properties of the paddy soil was 18.15 g/kg, the effective nitrogen, phosphorus and potassium contents were 18.18, 6.96 and 32.10 mg/kg respectively, the gravel, clay and silt were 56.75%, 9.00% and 0.10% respectively, the pH value was 6.10, the Eh value (oxidation-reduction potential) was 237 mV, and the Ec value (conductivity) was 223 μs/cm.
具体包括以下步骤:The specific steps include:
S1.均取表层土(0~15cm)风干研磨粉碎后过2mm筛备用;S1. Take the topsoil (0-15 cm), air-dry it, grind it into powder, and then pass it through a 2 mm sieve for later use;
S2.将过筛后的土壤装入高11.7cm,顶部直径12cm,底部直径10.4cm的小白桶中,每个桶装1kg含有10mg/kg草甘膦的土壤中;S2. The sieved soil was placed into small white buckets with a height of 11.7 cm, a top diameter of 12 cm, and a bottom diameter of 10.4 cm. Each bucket contained 1 kg of soil containing 10 mg/kg of glyphosate.
S3.按照下表1的肥料配比方式,添加肥料到土壤中并混匀;S3. Add fertilizer to the soil and mix according to the fertilizer ratio in Table 1 below;
S4.加水保持水稻土30%的含水量,每2天通过称重法保持含水量;S4. Add water to maintain the moisture content of paddy soil at 30%, and maintain the moisture content by weighing every 2 days;
S5.待培养进行1天、7天、14天、28天后,取小桶内混合土样提取后以高效液相色谱法测定。S5. After 1 day, 7 days, 14 days and 28 days of cultivation, take the mixed soil sample in the small bucket and extract it, and then measure it by high performance liquid chromatography.
表1不同复合制剂中尿素及硫酸亚铁盐的配比表Table 1 The ratio of urea and ferrous sulfate in different compound preparations
注:CK为空白组,不添加硫酸亚铁、过氧化尿素和普通尿素;Fe为只添加3mmol/kg的七水硫酸亚铁,UHP为只添加3mmol/kg过氧化尿素;U为只添加含氮量一致的普通尿素;Fe+UHP为添加3mmol/kg的七水硫酸亚铁和过氧化尿素;Fe+U为添加3mmol/kg的七水硫酸亚铁和尿素。下同。Note: CK is the blank group, without adding ferrous sulfate, urea peroxide and ordinary urea; Fe is only adding 3mmol/kg of ferrous sulfate heptahydrate, UHP is only adding 3mmol/kg of urea peroxide; U is only adding ordinary urea with the same nitrogen content; Fe+UHP is adding 3mmol/kg of ferrous sulfate heptahydrate and urea peroxide; Fe+U is adding 3mmol/kg of ferrous sulfate heptahydrate and urea. The same below.
表2施用后水稻土有机质的含量Table 2 Organic matter content of paddy soil after application
注:不同处理用相同小写字母标记条上的数据在p<0.05(平均值±标准误,n=3)上没有显著差异。Note: Data with the same lowercase letters between different treatments were not significantly different at p < 0.05 (mean ± s.e.m., n = 3).
由图1、表2和图2可知,本实施例在草甘膦污染的水稻土中,在培养的第1、7、14、28天后,添加硫酸亚铁和过氧化尿素的处理组(Fe+UHP)草甘膦降解率分别为31.71%、46.66%、50.54%、70.74%,对草甘膦的去除效率均显著高于其他处理组。CK组草甘膦残留量在第1、14、28天均显著高于其他处理组。其中,以硫酸亚铁和过氧化尿素组合施用(Fe+UHP)体系的草甘膦残留浓度下降最快。As shown in Figure 1, Table 2 and Figure 2, in the paddy soil contaminated with glyphosate, the glyphosate degradation rates of the treatment group (Fe+UHP) with the addition of ferrous sulfate and urea peroxide were 31.71%, 46.66%, 50.54% and 70.74% respectively after the 1st, 7th, 14th and 28th days of cultivation, and the glyphosate removal efficiency was significantly higher than that of the other treatment groups. The glyphosate residues in the CK group were significantly higher than those in the other treatment groups on the 1st, 14th and 28th days. Among them, the glyphosate residue concentration in the system with the combination of ferrous sulfate and urea peroxide (Fe+UHP) decreased the fastest.
不同处理条件下,水稻土的有机质含量在培养期内均未达到显著性差异水平(p>0.05)。水稻土中的有机质含量在15.9~20.99mg/kg范围内。然而,所有的处理组均随培养时间的延长而缓慢升高,随后趋于稳定的动态变化趋势。Under different treatment conditions, the organic matter content of paddy soil did not reach a significant difference level during the incubation period (p>0.05). The organic matter content in paddy soil was in the range of 15.9-20.99 mg/kg. However, all treatment groups slowly increased with the extension of incubation time, and then tended to a stable dynamic change trend.
在整个反应时期,添加氮素(UHP组、U组、Fe+UHP组、Fe+U组)处理组的铵态氮含量显著高于无尿素添加处理组,且施加氮素组的铵态氮含量呈现先升高,随后缓慢下降的变化趋势。从第1天到第7天,所有的处理组铵态氮含量均有不同幅度的增高,CK、Fe、UHP、U、Fe+UHP和Fe+U在第7d比第1d分别增加了39.10%,63.45%、24.54%、21.12%、15.36%和18.96%。在28d内,水稻土的铵态氮含量变化范围为11.29~100.03mg/kg。During the entire reaction period, the ammonium nitrogen content of the treatment groups with nitrogen addition (UHP group, U group, Fe+UHP group, Fe+U group) was significantly higher than that of the treatment groups without urea addition, and the ammonium nitrogen content of the nitrogen-added groups showed a trend of first increasing and then slowly decreasing. From the first day to the seventh day, the ammonium nitrogen content of all treatment groups increased to varying degrees. CK, Fe, UHP, U, Fe+UHP and Fe+U increased by 39.10%, 63.45%, 24.54%, 21.12%, 15.36% and 18.96% on the seventh day compared with the first day, respectively. Within 28 days, the ammonium nitrogen content of paddy soil varied from 11.29 to 100.03 mg/kg.
这些结果表明,配施过氧化尿素和硫酸亚铁,能介导芬顿反应或者类芬顿反应促进土壤草甘膦的降解。在培养初期,Fe+UHP处理组能较快地去除水稻土中的草甘膦,可作为原位修复治理的农艺措施之一。同时,施加过氧化尿素和硫酸亚铁到草甘膦污染土壤中,在去除草甘膦的同时可正常提供氮素营养。These results show that the application of urea peroxide and ferrous sulfate can mediate the Fenton reaction or Fenton-like reaction to promote the degradation of soil glyphosate. In the early stage of cultivation, the Fe+UHP treatment group can quickly remove glyphosate from paddy soil, which can be used as one of the agronomic measures for in situ remediation. At the same time, applying urea peroxide and ferrous sulfate to glyphosate-contaminated soil can provide nitrogen nutrition normally while removing glyphosate.
实施例2一种高效降解南方红壤中草甘膦的复合制剂及其使用方法Example 2 A composite formulation for efficiently degrading glyphosate in southern red soil and its use method
以华南农业大学园艺学院试验基地红壤为实验土壤,红壤土采集处为荒地,杂草较多。经测试,该红壤基础理化性质中的有机质含量为13.38g/kg,有效氮、磷、钾含量分别为11.29、17.20与5.27mg/kg,砂砾、粘粒与粉粒分别为55.74%、46.16%与0.10%,pH值为6.90,Eh值(氧化还原电位)为196mV,Ec值(电导率)为384μs/cm。The red soil of the experimental base of the College of Horticulture of South China Agricultural University was used as the experimental soil. The red soil was collected from wasteland with many weeds. According to the test, the organic matter content of the basic physical and chemical properties of the red soil was 13.38g/kg, the effective nitrogen, phosphorus and potassium contents were 11.29, 17.20 and 5.27mg/kg respectively, the gravel, clay and silt were 55.74%, 46.16% and 0.10% respectively, the pH value was 6.90, the Eh value (oxidation-reduction potential) was 196mV, and the Ec value (conductivity) was 384μs/cm.
具体包括以下步骤:The specific steps include:
S1.均取表层土(0~15cm)风干研磨粉碎后过2mm筛备用;S1. Take the topsoil (0-15 cm), air-dry it, grind it into powder, and then pass it through a 2 mm sieve for later use;
S2.将过筛后的土壤装入高11.7cm,顶部直径12cm,底部直径10.4cm的小白桶中,每个桶装1kg含10mg/kg草甘膦的土壤中;S2. The sieved soil was placed in small white buckets with a height of 11.7 cm, a top diameter of 12 cm, and a bottom diameter of 10.4 cm. Each bucket contained 1 kg of soil containing 10 mg/kg glyphosate.
S3.按照上表1的肥料配比方式,添加肥料到土壤中并混匀,S3. Add fertilizer to the soil and mix well according to the fertilizer ratio in Table 1 above.
S4.加水保持红壤30%的含水量,每2天通过称重法保持含水量;S4. Add water to maintain the water content of the red soil at 30%, and maintain the water content by weighing every 2 days;
S5.待培养进行1天、7天、14天、28天后,取小桶内混合土样提取后以高效液相色谱法测定。S5. After 1 day, 7 days, 14 days and 28 days of cultivation, take the mixed soil sample in the small bucket and extract it, and then measure it by high performance liquid chromatography.
表3施用后红壤有机质的含量Table 3 Organic matter content of red soil after application
由图3、表3和图4、图5、可知,本实施例在草甘膦污染的红壤中,在反应初期(第1天),草甘膦残留量从高到低依次为:Fe>U>CK>Fe+UHP>Fe+U>UHP,草甘膦降解率分别为7.88%、14.58%、25.97%、34.73%、36.14%、51.66%。在培养后的第1与7天,红壤的6个处理组间的有机质含量并无太大变化,随后在第14天土壤急剧升高后再缓慢下降。添加氮素后的处理组的铵态氮含量显著高于无氮素添加的处理组,且施氮组的铵态氮含量都呈现随反应时间延长而整体下降的趋势,无氮素添加处理组(CK组和Fe组)之间在每次取样时间铵态氮含量无显著性差异(p>0.05)。在第1天,Fe+UHP组的铵态氮含量在第7与14天显著高于其他处理组。红壤中铵态氮含量变化范围为2.37~73.19mg/kg。综合对比两种土壤的草甘膦浓度,可以看出,在施加肥料后,红壤比水稻土更容易去除土壤中的草甘膦。As shown in Figure 3, Table 3, Figure 4 and Figure 5, in the red soil contaminated with glyphosate, in the initial stage of the reaction (day 1), the glyphosate residues in this embodiment are from high to low: Fe>U>CK>Fe+UHP>Fe+U>UHP, and the glyphosate degradation rates are 7.88%, 14.58%, 25.97%, 34.73%, 36.14% and 51.66%, respectively. On the 1st and 7th days after cultivation, the organic matter content of the 6 treatment groups of red soil did not change much, and then the soil increased sharply on the 14th day and then slowly decreased. The ammonium nitrogen content of the treatment group after nitrogen addition was significantly higher than that of the treatment group without nitrogen addition, and the ammonium nitrogen content of the nitrogen application group showed an overall downward trend with the extension of the reaction time. There was no significant difference in the ammonium nitrogen content between the treatment groups without nitrogen addition (CK group and Fe group) at each sampling time (p>0.05). On the first day, the ammonium nitrogen content of the Fe+UHP group was significantly higher than that of the other treatment groups on the 7th and 14th days. The range of ammonium nitrogen content in red soil was 2.37-73.19 mg/kg. A comprehensive comparison of the glyphosate concentrations of the two soils showed that after the application of fertilizers, red soil was easier to remove glyphosate from the soil than paddy soil.
实施例3一种高效降解土壤中草甘膦的复合制剂对玉米生长的影响Example 3 Effect of a composite formulation for efficiently degrading glyphosate in soil on corn growth
红壤采自华南农业大学园艺学院试验基地,水稻土采自华南农业大学增城教学科研基地。红壤土采集处为荒地,杂草较多;水稻土常年种植水稻、玉米等农作物。经测试,水稻土基础理化性质中的有机质含量为18.15g/kg,有效氮、磷、钾含量分别为18.18、6.96与32.10mg/kg,砂砾、粘粒与粉粒分别为56.75%、9.00%与0.10%,pH值为6.10,Eh值(氧化还原电位)为237mV,Ec值(电导率)为223μs/cm。红壤基础理化性质中的有机质含量为13.38g/kg,有效氮、磷、钾含量分别为11.29、17.20与5.27mg/kg,砂砾、粘粒与粉粒分别为55.74%、46.16%与0.10%,pH值为6.90,Eh值(氧化还原电位)为196mV,Ec值(电导率)为384μs/cm。The red soil was collected from the experimental base of the College of Horticulture of South China Agricultural University, and the paddy soil was collected from the Zengcheng teaching and research base of South China Agricultural University. The red soil was collected from wasteland with many weeds; paddy soil is used to grow rice, corn and other crops all year round. According to tests, the organic matter content in the basic physical and chemical properties of paddy soil is 18.15g/kg, the effective nitrogen, phosphorus and potassium contents are 18.18, 6.96 and 32.10mg/kg respectively, the gravel, clay and silt are 56.75%, 9.00% and 0.10% respectively, the pH value is 6.10, the Eh value (oxidation-reduction potential) is 237mV, and the Ec value (conductivity) is 223μs/cm. The basic physical and chemical properties of red soil include organic matter content of 13.38 g/kg, effective nitrogen, phosphorus and potassium contents of 11.29, 17.20 and 5.27 mg/kg respectively, gravel, clay and silt contents of 55.74%, 46.16% and 0.10% respectively, pH value of 6.90, Eh value (oxidation-reduction potential) of 196 mV and Ec value (conductivity) of 384 μs/cm.
具体包括以下步骤:The specific steps include:
S1.均取表层土(0~15cm)风干研磨粉碎后过2mm筛备用;S1. Take the topsoil (0-15 cm), air-dry it, grind it into powder, and then pass it through a 2 mm sieve for later use;
S2.将过筛后的土壤装入高11.7cm,顶部直径12cm,底部直径10.4cm的小白桶中,每个桶装1kg含10mg/kg草甘膦的土壤中;S2. The sieved soil was placed into small white buckets with a height of 11.7 cm, a top diameter of 12 cm, and a bottom diameter of 10.4 cm. Each bucket contained 1 kg of soil containing 10 mg/kg glyphosate.
S3.按照上表1的肥料配比方式,添加肥料到土壤中并混匀,每个处理3个重复;S3. Add fertilizer to the soil and mix well according to the fertilizer ratio in Table 1 above, with 3 replicates for each treatment;
S4.在施肥处理7天后移植玉米幼苗;S4. Transplanting corn seedlings 7 days after fertilization treatment;
S5.在玉米移植生长7天后取样测定,测定玉米的农艺性状。S5. Take samples from corn 7 days after transplantation and measure the agronomic traits of corn.
由图6和图7可知,施加过氧化尿素或者尿素的同时混合施加硫酸亚铁可以提高水稻土及红壤中的玉米幼苗期的株高,单独施加过氧化尿素提高水稻土中的玉米幼苗的根长,单独施加尿素会降低水稻土和红壤中的玉米根长。As shown in Figures 6 and 7, applying urea peroxide or urea mixed with ferrous sulfate can increase the plant height of corn seedlings in paddy soil and red soil. Applying urea peroxide alone can increase the root length of corn seedlings in paddy soil, and applying urea alone can reduce the root length of corn in paddy soil and red soil.
实施例4~8Embodiments 4 to 8
实施例4~8和实施例1在相同的环境条件下,相同的管理措施,相同的喷施方法进行处理,实施例4~8的处理试剂配方如下:Examples 4 to 8 and Example 1 were treated under the same environmental conditions, the same management measures, and the same spraying method. The treatment reagent formulas of Examples 4 to 8 are as follows:
表4实施例4~8不同实施例的成分及第28天后的草甘膦降解率Table 4 Compositions of different embodiments of Examples 4 to 8 and glyphosate degradation rates after 28 days
综上所述,本发明以过氧化尿素配施硫酸亚铁,能介导芬顿反应或者类芬顿反应促进土壤草甘膦的降解。在培养初期,Fe+UHP处理组能较快地去除水稻土和红壤中的草甘膦,且效果较好,可作为原位修复治理的农艺措施之一。施加过氧化尿素以及硫酸亚铁到草甘膦污染土壤中会影响土壤的理化性质,但施氮组的氮素转化情况相差较小,在去除草甘膦的同时可正常提供氮素营养。在玉米幼苗种植前施加过氧化尿素可降低两种土壤中的草甘膦浓度,且过氧化尿素的施加有利于玉米幼苗地下部的生长。In summary, the present invention uses urea peroxide and ferrous sulfate to mediate the Fenton reaction or Fenton-like reaction to promote the degradation of soil glyphosate. In the early stage of cultivation, the Fe+UHP treatment group can quickly remove glyphosate in paddy soil and red soil, and the effect is good, which can be used as one of the agronomic measures for in-situ remediation and management. Applying urea peroxide and ferrous sulfate to glyphosate-contaminated soil will affect the physical and chemical properties of the soil, but the nitrogen conversion of the nitrogen-applying group is less different, and nitrogen nutrition can be provided normally while removing glyphosate. Applying urea peroxide before planting corn seedlings can reduce the glyphosate concentration in the two soils, and the application of urea peroxide is beneficial to the growth of the underground part of corn seedlings.
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
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