本文選題：尿素 + 脲酶抑制劑��； 參考：《浙江大學(xué)》2017年博士論文

【摘要】：尿素是我國(guó)農(nóng)業(yè)生產(chǎn)中廣泛應(yīng)用的氮(N)肥種類(lèi),如何減少稻田尿素N損失對(duì)提高水稻氮肥利用率、減少環(huán)境污染至關(guān)重要。從土壤中N素生物化學(xué)轉(zhuǎn)化的過(guò)程入手,采用脲酶/硝化抑制劑進(jìn)行雙重調(diào)控,是從源頭上控制農(nóng)田N素污染、實(shí)現(xiàn)高效利用尿素N的有效措施。本文采用室內(nèi)培養(yǎng)試驗(yàn)研究脲酶抑制劑N-丁基硫代磷酰三胺(NBPT)和硝化抑制劑2-氯-6-(三氯甲基)吡啶(CP)及其兩者組合對(duì)尿素態(tài)N在黃泥田土壤中的轉(zhuǎn)化作用效果及氨(NH3)揮發(fā)累積特性的影響,以及土壤溫度和含水量互作對(duì)生化抑制劑組合抑制N素轉(zhuǎn)化效果的影響;對(duì)比土壤或純脲酶中N-丙基硫代磷酰三胺(NPPT)與NBPT抑制尿素水解效果,評(píng)價(jià)抑制脲酶性能,并通過(guò)分子對(duì)接和分子動(dòng)力學(xué)模擬研究其與洋刀豆脲酶的相互作用機(jī)制。采用土柱淋溶試驗(yàn),研究N肥配施生化抑制劑組合對(duì)N、鉀(K)在黃泥田土體中淋溶損失,及土壤CO2、CH4和N2O累積排放和全球增溫潛勢(shì)(GWP)的影響。采用田間試驗(yàn)研究生化抑制劑組合與施肥模式互作對(duì)黃泥田水稻產(chǎn)量、群體質(zhì)量和養(yǎng)分利用率、稻季田面水和滲漏液N素濃度動(dòng)態(tài)變化、NH3揮發(fā)及稻季溫室氣體(CH4和N2O)排放通量的影響。取得的主要研究結(jié)果如下:1.生化抑制劑組合對(duì)黃泥田土壤尿素態(tài)氮轉(zhuǎn)化及氨揮發(fā)累積特性的影響:不同劑量NBPT處理可以緩釋尿素施入3～9 d,有效抑制土壤脲酶活性,減緩尿素分解,顯著降低NH3揮發(fā)速率峰值34.98%。不同劑量CP處理可以有效抑制NH4+-N向NO3--N轉(zhuǎn)化,其有效調(diào)控時(shí)間長(zhǎng)達(dá)72 d以上,但加劇NH3的揮發(fā)損失,顯著增加NH3揮發(fā)速率峰值10.89%。NBPT+CP組合既能緩釋尿素3～9d,有效抑制脲酶活性,減緩尿素水解,又能保持土壤中較高NH4+-N含量的時(shí)間超過(guò)72 d,且降低施肥初期的NH3揮發(fā)速率,減少NH3揮發(fā)損失。在黃泥田土壤中施用生化抑制劑時(shí),NBPT和CP選用范圍分別為≤0.5%和≤0.3%。2. NPPT與NBPT的脲酶抑制效應(yīng)比較:壤土和黏土中,尿素作用時(shí)間≤9d,NBPT/NPPT可以延長(zhǎng)尿素水解時(shí)間超過(guò)3d。砂土中,尿素分解過(guò)程相對(duì)緩慢,NBPT/NPPT顯著降低土壤脲酶活性,抑制NH4+-N生成。不同尿素用量條件下,脲酶抑制劑在不同質(zhì)地土壤中脲酶抑制效果表現(xiàn)為高施N量?jī)?yōu)于低施N量,且砂土黏土壤土。不同劑量NPPT與土壤或洋刀豆脲酶反應(yīng)顯著抑制脲酶活性,延緩尿素水解,效果與NBPT類(lèi)似。分子對(duì)接顯示,NPPT/NBPT與洋刀豆脲酶之間的作用模式相似:兩者均滲入脲酶活性催化位點(diǎn),與洋刀豆脲酶催化部位的鎳離子和不同氨基酸的殘基密切結(jié)合。模擬計(jì)算得出,NPPT和NBPT與洋刀豆脲酶的結(jié)合能(AGdock)分別為-66.04 kcal·mol-1 和-66.36 kcal·mol-1。NPPT由于其產(chǎn)品熱穩(wěn)定性高、適于尿素融漿的加工過(guò)程,有利于尿基肥料應(yīng)用在以后的生產(chǎn)中。3. 土壤溫度和含水量互作對(duì)生化抑制劑組合抑制氮素轉(zhuǎn)化效果的影響:土壤溫度和土壤含水量對(duì)生化抑制劑組合在黃泥田土壤中抑制尿素水解效應(yīng)顯著,以土壤溫度影響更大。隨著土壤溫度增加,尿素水解轉(zhuǎn)化增強(qiáng),有效作用時(shí)間降低,硝化作用增強(qiáng),脲酶和硝化抑制效應(yīng)減弱;隨著土壤含水量降低,尿素水解轉(zhuǎn)化緩慢,有效作用時(shí)間延長(zhǎng),硝化作用減弱,脲酶和硝化抑制效應(yīng)增強(qiáng)。不同土壤溫度和含水量條件下,NBPT/NPPT或配施CP處理有效抑制黃泥田土壤中脲酶活性,延緩尿素水解;CP或配施NBPT/NPPT處理有效抑制NH4+-N向NO3--N轉(zhuǎn)化,保持土壤中較高NH4+-N含量長(zhǎng)時(shí)間的存在。黃泥田土壤中生化抑制劑組合最佳應(yīng)用的土壤溫度和含水量分別為25℃和60%WHC。4.氮肥配施生化抑制劑組合對(duì)黃泥田土壤氮、鉀淋溶損失及溫室氣體排放的影響:不同N肥種類(lèi)NBPT處理可以有效抑制淋溶液中NH4+-N生成,延緩淋洗出峰時(shí)間,減少NH4+-N流失;CP處理可以有效抑制NH4+-N向NO3--N轉(zhuǎn)化,減少NO3--N流失,有效調(diào)控時(shí)間超過(guò)72d; NBPT+CP組合既能保持土壤中較高NH4+-N含量,又能降低淋溶液中NO3--N濃度。與單施NBPT相比,配施CP可以減少黃泥田土壤中NO3-淋溶,增加土壤晶格對(duì)K+的吸附,減輕K+淋失風(fēng)險(xiǎn),有效時(shí)間長(zhǎng)達(dá)72 d。不同種類(lèi)N肥添加CP延遲并顯著降低N2O排放通量峰值。CP或配施NBPT分別減少土壤N2O排放量32.66%和24.72% (尿素)、29.85%和29.44% (尿素硝銨);尿素配施NBPT顯著減少N2O排放量10.56%。添加抑制劑有效減少各種N肥的GWP,以NBPT+CP組合降幅最大(24.68%)。5.生化抑制劑組合與施肥模式對(duì)黃泥田水稻產(chǎn)量、群體質(zhì)量、養(yǎng)分累積及利用率的影響:尿素分次施用處理水稻產(chǎn)量和經(jīng)濟(jì)效益較一次性施用處理分別顯著提高14.2%和14.6%;水稻有效莖蘗數(shù)、有效葉面積指數(shù)(LAI)、抽穗至成熟期干物質(zhì)累積和抽穗期SPAD值分別提高0.8%、24.0%、9.3%和1.5%;水稻成熟期N、P、K吸收量分別提高11.0%、0.9%、4.2%; N肥吸收利用率和N肥農(nóng)學(xué)利用率分別顯著提高27.5%和70.8%。不同施肥模式下,配施生化抑制劑組合(NBPT/NPPT+CP)顯著提高水稻有效莖蘗數(shù)及莖蘗成穗率,增大有效LAI,增加抽穗期SPAD值,提高水稻粒葉比,改善源庫(kù)關(guān)系;增加水稻N、P、K吸收量,促進(jìn)抽穗后干物質(zhì)生產(chǎn)和N素積累,提高籽粒中的養(yǎng)分分配及N素利用效率。6.生化抑制劑組合與施肥模式對(duì)黃泥田稻季田面水和滲漏液氮素動(dòng)態(tài)變化、氨揮發(fā)及溫室氣體排放的影響:尿素分次施用處理稻季NH3揮發(fā)凈損失率較一次性施用處理顯著降低24.6%; CH4和N2O排放總量、GWP及GHGI分別顯著降低13.5%、20.7%、14.4%和25.0%。不同施肥模式下,CP顯著提高稻季田面水NH4+-N濃度和NH3揮發(fā)速率峰值,增加稻田NH3揮發(fā)損失量,而NBPT/NPPT或配施CP有效降低田面水NH4+-N和NH3揮發(fā)速率峰值,減少稻田NH3揮發(fā)損失量;CP顯著降低稻季滲漏液N03--N濃度和N2O排放通量峰值,減少稻季CH4和N2O排放總量,而CP或配施NBPT/NPPT有效降低滲漏液NO3--N峰值,減少稻季CH4和N2O排放,降低GWP和GHGI。
[Abstract]:Urea is a kind of nitrogen (N) fertilizer widely used in agricultural production in China. How to reduce the loss of urea N in rice field is very important to improve the nitrogen utilization rate and reduce environmental pollution. Starting with the process of bioconversion of N in the soil, the dual regulation of urease / nitrification inhibitor is used to control the pollution of N in farmland from the source and to achieve high level of pollution. The effective measures for using urea N. In this paper, the effect of urease inhibitor N- butyl thiophen three amine (NBPT) and nitrification inhibitor 2- chlorine -6- (CP) pyridine (CP) and their combination on the urea state N in the yellow mud field soil and the effect of the ammonia (NH3) volatilization accumulation, as well as the soil temperature and the soil temperature are studied in this paper. The effect of water content interaction on the inhibition of N transformation by biochemical inhibitor combinations; the inhibition of urea hydrolysis by N- propyl thiophosphoryl three amine (NPPT) and NBPT in soil or pure urease to inhibit urease performance, and to study the interaction mechanism of the urease with the urease by molecular docking and molecular dynamics simulation. Experiments were conducted to study the effects of N fertilizer and biochemical inhibitor combination on the leaching loss of N, potassium (K) in soil and the soil CO2, CH4 and N2O cumulative emission and global warming potential (GWP). The dynamic changes of N concentration, NH3 volatilization and the effect of greenhouse gas (CH4 and N2O) emission fluxes in the rice season. The main results are as follows: 1. the effects of biochemical inhibitor combination on the transformation of urea nitrogen and the accumulation of ammonia volatilization in the soil of the yellow mud field: different doses of NBPT treatment can release urea into 3~9 D and effectively inhibit soil urea Enzyme activity, slowing down the decomposition of urea, significantly reducing the peak NH3 volatilization rate 34.98%., CP treatment can effectively inhibit the transformation of NH4+-N to NO3--N, its effective regulation time is up to 72 D, but it aggravates the volatilization loss of NH3 and increases the peak value of NH3 volatilization, which can not only release urea 3 ~ 9D, but also effectively inhibit urease activity. Reducing the hydrolysis of urea and keeping the time of high NH4+-N content in the soil more than 72 D, and reducing the NH3 volatilization rate at the early stage of fertilization and reducing the loss of NH3 volatilization. The selection range of NBPT and CP is less than 0.5% and the urease inhibition effect of 0.3%.2. NPPT and NBPT, respectively, in the loam soil and clay, in the loam soil and clay. The action time of the element is less than 9D, and the hydrolysis time of the urea can extend the hydrolysis time of urea to exceed the 3D. sand, the urea decomposition process is relatively slow, the urease activity of the soil is decreased and the NH4+-N formation is inhibited by NBPT/NPPT. The urease inhibitors in different soil conditions show that the urease inhibition effect of urease inhibitors is higher than the low application of N in the soil with high application of N and the sand soil. The reaction of different doses of NPPT to soil or yanagan urease significantly inhibited urease activity and delayed urea hydrolysis. The effect was similar to that of NBPT. Molecular docking showed that the mode of action between NPPT/NBPT and yanagan urease was similar: both were infiltrated into urease active site, and nickel ions and different amino groups in the catalytic site of yanagan urease. The simulation results show that the binding energy of NPPT and NBPT with yanagan urease (AGdock) is -66.04 kcal, mol-1 and -66.36 kcal. Mol-1.NPPT, respectively, because of the high thermal stability of the product, which is suitable for the process of urea melting, which is beneficial to the interaction of the soil temperature and water content in the later production of the urea based fertilizer. The effects of inhibitor combination on nitrogen conversion were inhibited: soil temperature and soil water content inhibited the effect of urea hydrolysis on the combination of biochemical inhibitors in the yellow mud field soil, and the effect of soil temperature was greater. With the increase of soil temperature, the hydrolysis of urea was enhanced, the time of effective action was reduced, nitrification was enhanced, urease and nitrification were increased. The inhibition effect was weakened; with the decrease of soil water content, the conversion of urea hydrolysis was slow, the time of effective action was prolonged, nitrification was weakened, and the inhibition effect of urease and nitrification was enhanced. Under the conditions of different soil temperature and water content, NBPT/NPPT or CP treatment effectively inhibited urease activity in the yellow mud field soil, delayed the urea hydrolysis, CP or the application of NBPT/NPPT. The treatment effectively inhibited the transformation of NH4+-N into NO3--N and kept the high NH4+-N content in the soil for a long time. The soil temperature and water content of the best application of the biochemical inhibitor combination in the yellow mud field soil were 25 and 60%WHC.4., respectively, and the effects of the combination of nitrogen fertilizer and nitrogen fertilizer on the soil nitrogen, potassium leaching loss and greenhouse gas emission in the yellow mud field, respectively. NBPT treatment of different N fertilizers can effectively inhibit the formation of NH4+-N in the leaching solution, postpone the peak time of leaching and reduce the loss of NH4+-N. CP treatment can effectively inhibit the transformation of NH4+-N into NO3--N, reduce the loss of NO3--N, and effectively control the time more than 72d; NBPT+CP combination can not only keep the higher NH4+-N content in the soil, but also reduce the concentration of NO3--N in the leaching solution. Compared with the single application of NBPT, the application of CP could reduce the NO3- leaching in the soil of the yellow mud field, increase the adsorption of the lattice to K+, reduce the risk of K+ leaching, the effective time is 72 D. and the CP delay is added to different kinds of N fertilizers and the N2O emission flux peak.CP or 24.72% (urea), 29.85% and 29.44% (urea), 29.85% and 29.44%, respectively, respectively. (ammonium urea ammonium nitrate); Urea Combined with NBPT significantly reduced N2O emissions by 10.56%. adding inhibitors to effectively reduce GWP of various N fertilizers, and the maximum (24.68%).5. biochemical inhibitor combination and fertilization model on rice yield, population quality, nutrient accumulation and utilization rate in the yellow mud field by NBPT+CP combination: urea applied to rice yield and economy The efficiency of the treatment was increased by 14.2% and 14.6%, respectively, and the effective stem and tiller number, effective leaf area index (LAI), the accumulation of dry matter and the SPAD value of the heading stage were increased by 0.8%, 24%, 9.3% and 1.5%, and the absorption of N, P and K in the mature period of rice was 11%, 0.9%, 4.2%, and N fertilizer utilization and N fertilizer utilization ratio respectively. Under the different fertilization modes of 27.5% and 70.8%., the combination of biochemical inhibitor combination (NBPT/NPPT+CP) significantly increased the number of effective tillers and the percentage of tillers, increased the effective LAI, increased the SPAD value of the heading stage, increased the grain leaf ratio and improved the relationship between the source and reservoir, and increased the absorption of N, P and K in rice, and promoted the production of dry matter after heading and the accumulation of N in the heading. The effects of nutrient distribution and N utilization efficiency on the dynamic changes of nitrogen in rice water and leachate, ammonia volatilization and greenhouse gas emissions from rice water and leachate in yellow mud field were improved by.6. biochemical inhibitor combination and fertilization mode. The loss rate of volatile net volatilization of NH3 was significantly reduced by 24.6% compared with that of one-time application treatment in rice season, and CH4 and N2O emissions were total. Quantity, GWP and GHGI significantly decreased 13.5%, 20.7%, 14.4% and 25.0%., CP significantly increased the concentration of NH4+-N and the peak of NH3 volatilization in rice field, and increased the volatilization loss of NH3 in paddy field, while NBPT/NPPT or combined CP decreased the peak value of NH4+-N and NH3 volatilization rate of paddy field water and reduced the volatilization loss of paddy NH3. The concentration of N03--N and N2O emission flux peak in rice season leachate, decrease the total emission of CH4 and N2O in rice season, and CP or NBPT/NPPT to reduce NO3--N peak in leakage fluid, reduce CH4 and N2O emission in rice season, reduce GWP and GHGI..

【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：S153.6
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本文編號(hào)：1876787