本文選題：環(huán)境材料 + 重金屬　； 參考：《中國(guó)礦業(yè)大學(xué)(北京)》2016年博士論文

【摘要】：土壤污染特別是耕地污染問題事關(guān)食品安全和國(guó)家長(zhǎng)遠(yuǎn)發(fā)展戰(zhàn)略。農(nóng)田土壤重金屬污染、氮肥利用率低及面源污染等問題并存,威脅農(nóng)業(yè)可持續(xù)發(fā)展和人體健康。因此,重金屬污染治理和肥料增效等多重目標(biāo)同步是農(nóng)田土壤改良技術(shù)的重要目標(biāo),而尋求適宜的環(huán)境材料是獲得多重目標(biāo)同步的關(guān)鍵。環(huán)境材料是一類具有最大使用功能和最小環(huán)境負(fù)荷的材料,其特點(diǎn)是具有鮮明的功能性,環(huán)境友好性和經(jīng)濟(jì)性。為揭示環(huán)境材料對(duì)土壤鉛鎘固化和氮肥增效同步效應(yīng)機(jī)理,本研究選用納米碳、蛇紋石及褐煤腐殖酸三種環(huán)境材料,采用吸附解吸試驗(yàn)、砂柱及土柱淋溶試驗(yàn)、玉米發(fā)芽試驗(yàn)和盆栽種植等試驗(yàn)方法,開展三種環(huán)境材料對(duì)重金屬鉛、鎘和氮素的吸附解吸特性、土壤鉛、鎘及氮素淋溶規(guī)律和效果、土壤有效態(tài)重金屬鉛、鎘含量、重金屬生物有效性和氮肥利用效率、土壤理化性質(zhì)及其作物生長(zhǎng)和品質(zhì)影響的研究。結(jié)合材料表征分析,探討了環(huán)境材料對(duì)重金屬鉛鎘固化和氮肥增效同步效應(yīng)機(jī)理,為納米碳、蛇紋石及褐煤腐殖酸三種環(huán)境材料在土壤污染治理和土壤改良中的應(yīng)用提供科學(xué)依據(jù)和技術(shù)參考。主要取得以下成果:1.通過模擬試驗(yàn),研究了納米碳、蛇紋石及褐煤腐殖酸三種環(huán)境材料對(duì)重金屬鉛(Pb~(2+))、鎘(Cd~(2+))和銨(NH_4~+)離子的吸附特征、吸附穩(wěn)定性及吸附機(jī)制。(1)獲得了納米碳、蛇紋石及褐煤腐殖酸對(duì)Pb~(2+)、Cd~(2+)和NH_4~+的最佳吸附條件。三種環(huán)境材料對(duì)Pb~(2+)、Cd~(2+)最佳吸附條件:納米碳、蛇紋石及褐煤腐殖酸用量分別為2.5g/L、10.0 g/L和5.0g/L。溶液Pb~(2+)和Cd~(2+)初始濃度分別為600 mg/L和100 mg/L,反應(yīng)溫度25℃,p H=6.5,吸附時(shí)間180 min。三種環(huán)境材料對(duì)NH_4~+最佳吸附條件:納米碳、蛇紋石及褐煤腐殖酸用量均為12.5 g/L,溶液NH_4~+初始濃度100 mg/L,反應(yīng)溫度25℃,p H=6.5(褐煤腐殖酸為4.5),吸附時(shí)間1440 min。(2)通過等溫吸附試驗(yàn)及吸附動(dòng)力學(xué)試驗(yàn)獲得了三種環(huán)境材料對(duì)Pb~(2+)、Cd~(2+)和NH_4~+吸附機(jī)理及吸附性能。三種環(huán)境材料對(duì)Pb~(2+)和Cd~(2+)等溫吸附曲線,使用Langumir等溫吸附模型擬合度更好;納米碳、蛇紋石及褐煤腐殖酸對(duì)Pb~(2+)的最大飽和吸附量分別為322.58 mg/g、55.87 mg/g和135.14 mg/g;納米碳、蛇紋石及褐煤腐殖酸對(duì)Cd~(2+)的最大飽和吸附量分別為74.63 mg/g、15.24 mg/g和33.90mg/g;三種環(huán)境材料對(duì)Pb~(2+)和Cd~(2+)等溫吸附過程屬于優(yōu)惠吸附、是吸熱反應(yīng)、吸附過程存在化學(xué)單層吸附;三種環(huán)境材料對(duì)Pb~(2+)和Cd~(2+)吸附動(dòng)力學(xué)曲線,服從二級(jí)動(dòng)力學(xué)模型,化學(xué)吸附占主導(dǎo)地位。三種環(huán)境材料對(duì)NH_4~+等溫吸附曲線,使用Freundlich等溫吸附模型擬合度更好;三種環(huán)境材料對(duì)對(duì)NH_4~+吸附過程屬于優(yōu)惠吸附、是吸熱反應(yīng)、吸附過程存在表面吸附,且為多層吸附;三種環(huán)境材料對(duì)NH_4~+吸附動(dòng)力學(xué)曲線,服從二級(jí)動(dòng)力學(xué)曲線,說明吸附過程存在化學(xué)吸附,但物理吸附占據(jù)主導(dǎo)地位。(3)獲得了三種環(huán)境材料對(duì)Pb~(2+)、Cd~(2+)及NH_4~+最佳吸附穩(wěn)定性條件。納米碳、蛇紋石及褐煤腐殖酸對(duì)Pb~(2+)、Cd~(2+)吸附比較穩(wěn)定。當(dāng)6.5p H7.5時(shí),Pb~(2+)、Cd~(2+)脫附率分別只有0.43%-0.95%。極端強(qiáng)酸性條件(p H=2.5),Pb~(2+)、Cd~(2+)脫附率分別低于21.53%和24.37%。納米碳、蛇紋石及褐煤腐殖酸對(duì)NH_4~+吸附不穩(wěn)定。當(dāng)6.5p H7.5時(shí),NH_4~+脫附率達(dá)到17.98%-19.91%。極端強(qiáng)酸性條件(p H=2.5),NH_4~+脫附率分別大于43.23%。這種性質(zhì)對(duì)于其在土壤中的緩釋效應(yīng)具有重要意義。2.探討了環(huán)境材料作用下Pb~(2+)、Cd~(2+)及NH_4~+的淋溶規(guī)律、淋溶效果,并獲得了對(duì)Pb~(2+)、Cd~(2+)固化和NH_4~+保持效應(yīng)最好的材料組合。(1)納米碳對(duì)Pb~(2+)保持效果最好,褐煤腐殖酸對(duì)Cd~(2+)、NH_4~+保持效果最好;納米碳及褐煤腐殖酸處理Pb~(2+)、Cd~(2+)及NH_4~+淋出率峰值出現(xiàn)在第二次淋溶試驗(yàn),較CK及蛇紋石處理出現(xiàn)延遲;四次淋溶后,Pb~(2+)、Cd~(2+)及NH_4~+累積淋出率趨于穩(wěn)定;三種環(huán)境材料對(duì)Pb~(2+)、Cd~(2+)及NH_4~+累積淋出率曲線能夠按照Logistics模型擬合,納米碳處理Pb~(2+)最大淋溶速率拐點(diǎn)出現(xiàn)最晚,褐煤腐殖酸處理Cd~(2+)、NH_4~+最大淋溶速率拐點(diǎn)出現(xiàn)最晚。(2)獲得了對(duì)Pb~(2+)、Cd~(2+)固化及NH_4~+保持效應(yīng)最佳環(huán)境材料及氮素組合:CN4AS4HA2N2。在土柱淋溶試驗(yàn)中,環(huán)境材料處理Pb~(2+)、Cd~(2+)及NH_4~+累積淋出率分別較對(duì)照CK降低14.62%-58.75%,12.81%-53.46%和1.03%-90.83%。3.以鉛、鎘脅迫下種子萌發(fā)試驗(yàn)和盆栽試驗(yàn)為基礎(chǔ),研究了三種環(huán)境材料對(duì)Pb~(2+)、Cd~(2+)生物有效性、環(huán)境材料及氮肥用量對(duì)作物生長(zhǎng)、產(chǎn)量及品質(zhì)的影響。(1)獲得了影響玉米種子發(fā)芽的最低抑制濃度和玉米幼苗不同部位對(duì)Pb~(2+)、Cd~(2+)脅迫響應(yīng)差異。Pb~(2+)、Cd~(2+)離子對(duì)玉米種子發(fā)芽率、發(fā)芽勢(shì)的影響表現(xiàn)出低濃度促進(jìn),高濃度抑制,且濃度愈高抑制作用愈明顯;玉米種子萌發(fā)對(duì)Cd~(2+)脅迫較Pb~(2+)敏感;Pb~(2+)、Cd~(2+)離子無論濃度高低,對(duì)于玉米種子芽長(zhǎng)和根長(zhǎng)伸長(zhǎng)均起到抑制作用;玉米種子根長(zhǎng)伸長(zhǎng)對(duì)Pb~(2+)、Cd~(2+)離子脅迫響應(yīng)較芽長(zhǎng)伸長(zhǎng)更為敏感。Pb~(2+)和Cd~(2+)抑制種子萌發(fā)的濃度分別為25 mg/L和15 mg/L。(2)環(huán)境材料能夠促進(jìn)重金屬Pb~(2+)、Cd~(2+)脅迫下玉米發(fā)芽與生長(zhǎng)。環(huán)境材料能夠降低Pb~(2+)、Cd~(2+)脅迫對(duì)玉米種子的抑制作用,對(duì)于Pb~(2+)脅迫,納米碳處理作用效果最佳,對(duì)于Cd~(2+)脅迫,褐煤腐殖酸處理作用效果最佳。(3)環(huán)境材料能夠促進(jìn)玉米增產(chǎn),隨氮肥用量增加玉米增產(chǎn)效應(yīng)下降。環(huán)境材料處理玉米籽粒產(chǎn)量和地上部分干物質(zhì)量較對(duì)照提高19.99%-59.72%和5.86%-30.35%。單一材料處理,納米碳作用效果最佳;復(fù)合材料處理,納米碳+褐煤腐殖酸+蛇紋石(CN+AS+HA)作用效果最佳;氮肥用量小于500 mg/kg時(shí),玉米籽粒產(chǎn)量及地上部分干物質(zhì)積累量隨氮肥用量增大而增大;氮肥用量大于500 mg/kg時(shí),玉米籽粒產(chǎn)量及地上部分干物質(zhì)積累量隨氮肥用量增大而減小。(4)環(huán)境材料可提高玉米可食用部分品質(zhì),氮肥用量增加降低玉米品質(zhì)。環(huán)境材料處理玉米秸稈Pb~(2+)、Cd~(2+)含量較CK最大降幅分別為36.55%和40.72%;環(huán)境材料處理玉米籽粒Pb~(2+)、Cd~(2+)含量較CK最大降幅分別為39.66%和41.33%;單一環(huán)境材料處理,納米碳作用效果最佳;復(fù)合材料處理,納米碳+褐煤腐殖酸+蛇紋石(CN+AS+HA)作用效果最佳。玉米秸稈及籽粒重金屬Pb~(2+)、Cd~(2+)含量隨氮肥用量增加而增加。4.環(huán)境材料能夠固化重金屬、提高氮肥利用效率,改善土壤理化性質(zhì);氮肥用量增加能活化重金屬,降低氮肥利用效率,不利于土壤理化性質(zhì)改善。(1)環(huán)境材料能夠固化重金屬,降低有效態(tài)土壤重金屬含量;增加氮肥用量則增加有效態(tài)土壤重金屬含量。環(huán)境材料處理土壤有效態(tài)重金屬Pb~(2+)、Cd~(2+)含量較CK降低4.38%-11.87%和2.78%-9.13%。單一材料處理,納米碳作用效果最好。復(fù)合材料處理,納米碳、蛇紋石及褐煤腐殖酸(CN+AS+HA)處理作用效果最好。土壤有效態(tài)重金屬Pb~(2+)、Cd~(2+)含量隨氮肥用量增加而增加。(2)環(huán)境材料能夠提高氮肥利用效率,增加氮肥用量降低氮肥利用效率。環(huán)境材料處理氮肥利用效率(NUE)較對(duì)照提高3.41%-17.65%。單一材料處理,褐煤腐殖酸作用效果最佳。復(fù)合材料處理,納米碳、蛇紋石及褐煤腐殖酸(CN+AS+HA)處理效果最佳。氮肥利用效率隨氮肥用量增加而降低。(3)環(huán)境材料能改善土壤理化性質(zhì),增加氮肥用量不利于土壤理化性質(zhì)改善。環(huán)境材料處理土壤有機(jī)質(zhì)(SOM)和0.25-5.00 mm土壤團(tuán)聚體含量較CK提高3.28%-32.36%和0.13%-11.02%。環(huán)境材料處理可減小土壤酸堿度(p H)、電導(dǎo)率(EC)和土壤陽離子交換量(CEC)降幅。單一材料處理,褐煤腐殖酸處理效果最佳。復(fù)合材料處理,納米碳、蛇紋石及褐煤腐殖酸(CN+AS+HA)處理效果最佳。當(dāng)?shù)视昧啃∮?00 mg/kg時(shí),土壤有機(jī)質(zhì)(SOM)含量隨氮肥用量的提高而升高;當(dāng)?shù)视昧看笥?00 mg/kg時(shí),土壤有機(jī)質(zhì)(SOM)含量隨氮肥用量的提高而降低。當(dāng)?shù)视昧啃∮?00 mg/kg時(shí),0.25-5.00 mm團(tuán)聚體含量隨氮肥用量增大而增大;當(dāng)?shù)视昧看笥?00 mg/kg時(shí),0.25-5.00 mm團(tuán)聚體含量占比隨氮肥用量的提高而降低。土壤酸堿度(p H)隨土壤氮肥施用增大而降低,電導(dǎo)率(EC)和土壤陽離子交換量(CEC)隨氮肥用量增大而增大;種植玉米前后土壤酸堿度(p H)、電導(dǎo)率(EC)和土壤陽離子交換量(CEC)降幅隨氮肥施用量增大而增大。5.通過材料表征技術(shù),獲得了環(huán)境材料的基本性能、官能團(tuán)及形貌特征,探討了環(huán)境材料對(duì)土壤鉛、鎘固化和氮肥增效機(jī)理。(1)獲得了材料基本性能信息。納米碳元素組成以C、H、O元素為主要組成部分;D50=11.37 nm,D90=61.53 nm;比表面積、孔徑及孔體積分別為265.88 m2/g、4.63 nm和0.061 cm3/g。蛇紋石是一種富鎂硅酸鹽礦物;D50=18.82μm,D90=74.99μm;比表面積、孔徑及孔體積分別為141.59 m2/g、10.36 nm和0.024 cm3/g。腐植酸主要由C、H、O、S等元素組成;D50=15.46μm,D90=63.47μm;比表面積、孔徑及孔體積分別為13.64 m2/g、18.13 nm和0.004 cm3/g。電負(fù)性大小順序:蛇紋石納米碳褐煤腐殖酸。(2)明確了環(huán)境材料的化學(xué)官能團(tuán)、形貌特征及化學(xué)組成,并分析了吸附前后化學(xué)官能團(tuán)、形貌特征和化學(xué)組成變化的原因。FT-IR圖譜表明,納米碳、蛇紋石及褐煤腐殖酸中含有大量活性基團(tuán),其中部分官能團(tuán)參與了Pb~(2+)、Cd~(2+)及NH_4~+離子吸附反應(yīng),吸附過程存在化學(xué)鍵的形成和斷裂;場(chǎng)發(fā)射掃描電鏡(SEM)結(jié)果顯示,納米碳、蛇紋石及褐煤腐殖酸表面微球、微孔及微球之間的空隙提供了吸附反應(yīng)的場(chǎng)所;電子能譜(EDS)分析表明,Pb~(2+)、Cd~(2+)及NH_4~+吸附在了納米碳、蛇紋石及褐煤腐殖酸表面。(3)探討了納米碳、蛇紋石及褐煤腐殖酸三種環(huán)境材料對(duì)土壤重金屬鉛、鎘固化及氮肥增效作用機(jī)制。環(huán)境材料對(duì)重金屬鉛、鎘固化及氮肥增效機(jī)理包含兩個(gè)層面,一是環(huán)境材料直接與重金屬鉛、鎘及氮素離子發(fā)生化學(xué)、物理吸附,降低有效態(tài)重金屬含量,減緩氮素釋放,提高氮素利用效率;二是通過環(huán)境材料對(duì)土壤理化性質(zhì)改變,如通過提高土壤有機(jī)質(zhì)含量、0.25-5.00 mm土壤團(tuán)聚體含量、減小土壤電導(dǎo)率、陽離子交換量及土壤p H降幅,間接改變土壤有效態(tài)重金屬含量,提高氮肥利用效率。
[Abstract]:The problem of soil pollution, especially the pollution of cultivated land, is related to food safety and the strategy of national parents' far development. The problems of heavy metal pollution in farmland, low utilization rate of nitrogen fertilizer and non-point source pollution are coexisting, which threaten the sustainable development of agriculture and human health. Therefore, multiple targets, such as heavy metal pollution control and fertilizer increase, are the technology of farmland soil improvement. The key objective is to seek suitable environmental materials, which is the key to the synchronization of multiple targets. The environmental material is a kind of material with the maximum use function and minimum environmental load. It is characterized by its distinctive function, environmental friendliness and economy. In this study, three kinds of environmental materials such as carbon nanoscale, serpentine and lignite humic acid were used. The adsorption and desorption test, sand column and soil column leaching test, Corn Germination Test and potted planting were used to carry out the adsorption and desorption characteristics of heavy metal lead, cadmium and nitrogen, soil lead, cadmium and nitrogen leaching laws and effects, soil soil, soil, soil, soil, soil, soil, soil and soil. The effects of heavy metal lead, cadmium content, bioavailability and nitrogen use efficiency of heavy metals, soil physical and chemical properties and crop growth and quality were studied. Combined with the analysis of material characterization, the mechanism of simultaneous effect of environmental materials on heavy metal lead and cadmium solidification and nitrogen fertilizer synergism was discussed, which were three environmental materials for nano carbon, serpentine and lignite humic acid. The scientific basis and technical reference are provided in the application of soil pollution control and soil improvement. The following achievements are made as follows: 1. through simulation experiments, the adsorption characteristics, adsorption stability and adsorption mechanism of three environmental materials of nano carbon, serpentine and lignite humic acid on heavy metal lead (Pb~ (2+)), cadmium (Cd~ (2+)) and ammonium (NH_4~+) ions were studied. (1) the optimum adsorption conditions for Pb~ (2+), Cd~ (2+) and NH_4~+ were obtained from nano carbon, serpentine and lignite humic acid. The best adsorption conditions for Pb~ (2+) and Cd~ (2+) were obtained by three environmental materials: the dosage of nano carbon, serpentine and lignite humic acid were 2.5g/L, 10 g/L and 5.0g/L. solutions were 600 and 100 respectively. The optimum adsorption conditions for NH_4~+ were at 25 C, P H=6.5, and adsorption time 180 min.. The dosage of nano carbon, serpentine and lignite humic acid were 12.5 g/L, the initial concentration of NH_4~+ was 100 mg/L, the reaction temperature was 25, P H=6.5 (lignite humic acid 4.5), and adsorption time 1440 min. (2) through isothermal adsorption test and adsorption kinetics test. The adsorption mechanism and adsorption properties of three environmental materials on Pb~ (2+), Cd~ (2+) and NH_4~+ were obtained. The adsorption curves of Pb~ (2+) and Cd~ (2+) by three environmental materials were better than that of Langumir isothermal adsorption model, and the maximum saturated adsorption capacity of nano carbon, serpentine and lignite humic acid to Pb~ (2+) was 322.58, 55.87 and 135. respectively. 14 mg/g; the maximum saturated adsorption capacity of nano carbon, serpentine and lignite humic acid to Cd~ (2+) was 74.63 mg/g, 15.24 mg/g and 33.90mg/g, respectively. The isothermal adsorption process of Pb~ (2+) and Cd~ (2+) was preferential adsorption for three environmental materials, endothermic reaction, and adsorption process with chemical monolayer adsorption; three environmental materials adsorbed Pb~ (2+) and adsorbents. The mechanical curve is subject to the two stage dynamic model, chemical adsorption is dominant. Three kinds of environmental materials have better fitting degree to NH_4~+ isothermal adsorption curve and Freundlich isothermal adsorption model; three kinds of environmental materials have preferential adsorption to NH_4~+ adsorption process, endothermic reaction, adsorption process surface adsorption, and multi-layer adsorption; three kinds of adsorption; The adsorption kinetics curve of the environmental material obeys the two order kinetics curve, which shows that the adsorption process is chemisorption, but physical adsorption occupies the dominant position. (3) the optimum adsorption stability conditions of three environmental materials for Pb~ (2+), Cd~ (2+) and NH_4~+ are obtained. The adsorption of nano carbon, serpentine and lignite humic acid on Pb~ (2+) and Cd~ (2+) is stable. When 6.5p H7.5, the desorption rate of Pb~ (2+) and Cd~ (2+) is only the extreme strong acidic condition of 0.43%-0.95%. (P H=2.5), Pb~ (2+), and the desorption rate of the Cd~ is less than 21.53% and nanometer carbon respectively. The desorption rate of + + is greater than 43.23%., which is of great significance to the slow release effect in soil..2. explores the leaching laws of Pb~ (2+), Cd~ (2+) and NH_4~+, leaching effect, and obtained the best combination of Pb~ (2+), Cd~ (2+) curing and NH_4~+ holding effect. (1) carbon nanoscale keeps the most effective. Well, lignite humic acid has the best effect on Cd~ (2+) and NH_4~+, and the peak value of Pb~ (2+), Cd~ (2+) and NH_4~+ leaching rate in the second leaching tests, compared with CK and serpentine treatment, is delayed, and Pb~ (2+), Cd~ (2+) and accumulation rate tend to be stable after four leaching; three environmental materials The cumulative leaching rate of NH_4~+ can be fitted to the Logistics model. The maximum leaching rate of Pb~ (2+) is the latest, Cd~ (2+) is treated with lignite humic acid, and the maximum inflexion point of the leaching rate of NH_4~+ is the latest. (2) the best environmental material and nitrogen combination for Pb~ (2+), Cd~ (2+) curing and NH_4~+ retention effect are obtained. In the soil column leaching test, the cumulative leaching rate of Pb~ (2+), Cd~ (2+) and NH_4~+ decreased by 14.62%-58.75%, 12.81%-53.46% and 1.03%-90.83%.3. were based on the seed germination test and pot experiment under lead, cadmium stress, and three kinds of environmental materials were studied for the Pb~ (2+), the environmental material and the nitrogen fertilizer. The influence of quantity on crop growth, yield and quality. (1) the minimum inhibitory concentration of Maize Seed Germination and the difference of Pb~ (2+), Cd~ (2+) stress response of maize seedlings to different parts were.Pb~ (2+). The effect of Cd~ (2+) ions on the germination rate and germination potential of maize showed low concentration promotion, high concentration inhibition and higher inhibition effect. The germination of maize seeds was more sensitive to Cd~ (2+) stress than that of Pb~ (2+); Pb~ (2+), Cd~ (2+) ions, regardless of the concentration, could inhibit the bud length and length elongation of maize seeds, and the length elongation of maize seed root length to Pb~ (2+), Cd~ (2+) stress should be more sensitive than the length of bud length. Not 25 mg/L and 15 mg/L. (2) environmental materials can promote the germination and growth of heavy metals under the stress of Pb~ (2+), Cd~ (2+) stress. Environmental materials can reduce Pb~ (2+), Cd~ (2+) stress on maize seeds, for Pb~ (2+) stress, the effect of carbon nanoscale treatment is the best. (3) the effect of lignite humic acid treatment is the best. Environmental materials could increase the yield of maize, and the effect of maize yield increased with the amount of nitrogen fertilizer. The yield of maize grain and the quality of the dry matter on the ground were improved by 19.99%-59.72% and 5.86%-30.35%. single material treatment, and the effect of carbon nanomaterials was the best. A) the effect was the best. When the amount of nitrogen fertilizer was less than 500 mg/kg, the yield of corn grain and the accumulation of dry matter on the ground increased with the increase of nitrogen fertilizer. When the amount of nitrogen fertilizer was greater than 500 mg/kg, the grain yield and the accumulation of dry matter on the ground decreased with the increase of the amount of nitrogen fertilizer. (4) the quality of edible part of corn could be improved by environmental materials. The content of nitrogen fertilizer increased to reduce the quality of corn. The content of maize straw Pb~ (2+) and Cd~ (2+) was 36.55% and 40.72%, respectively. The content of Pb~ (2+) and Cd~ (2+) in maize grains treated by environmental materials was 39.66% and 41.33%, respectively, compared with CK, and the effect of carbon nanomaterials was the best. The effect of M C + lignite humic acid + serpentine (CN+AS+HA) is the best. The content of heavy metal Pb~ (2+) and Cd~ (2+) in corn straw and grain increases with the increase of nitrogen fertilizer, and the.4. environment material can solidify heavy metals, improve the utilization efficiency of nitrogen fertilizer and improve the physical and chemical properties of soil; the increase of nitrogen fertilizer can activate heavy metals and reduce the utilization efficiency of nitrogen fertilizer. The physical and chemical properties of soil improved. (1) environmental materials can solidify heavy metals, reduce the content of heavy metals in effective soil, and increase the amount of effective soil heavy metals by increasing the amount of nitrogen fertilizer. Environmental materials treat soil available heavy metals Pb~ (2+), Cd~ (2+) content is lower than 4.38%-11.87% and 2.78%-9.13%. single material treatment, and the effect of carbon nanoscale The best effects were treated with composite materials, carbon nanoscale, serpentine and lignite humic acid (CN+AS+HA) treatment. The soil effective heavy metal Pb~ (2+), Cd~ (2+) content increased with the amount of nitrogen fertilizer. (2) environmental materials can improve nitrogen use efficiency and increase nitrogen fertilizer application efficiency. Rate (NUE) improved 3.41%-17.65%. single material treatment, lignite humic acid was the best. Composite treatment, carbon nanoscale, serpentine and lignite humic acid (CN+AS+HA) treatment was the best. Nitrogen utilization efficiency decreased with the increase of nitrogen fertilizer. (3) environmental material can improve soil physical and chemical properties, increasing the amount of nitrogen fertilizer is not conducive to soil. Improvement in physical and chemical properties. Soil organic matter (SOM) and 0.25-5.00 mm soil aggregate content is higher than CK, 3.28%-32.36% and 0.13%-11.02%. environmental material treatment can reduce soil pH (P H), conductivity (EC) and soil cation exchange (CEC) decrease. Single one material treatment, lignite humic acid treatment effect is the best. Treatment, carbon nanoscale, serpentine and lignite humic acid (CN+AS+HA) had the best treatment effect. When the amount of nitrogen fertilizer was less than 400 mg/kg, the content of soil organic matter (SOM) increased with the increase of the amount of nitrogen fertilizer. When the amount of nitrogen fertilizer was greater than 400 mg/kg, the content of soil organic matter (SOM) decreased with the increase of nitrogen fertilizer amount. When the amount of nitrogen fertilizer was less than 300 mg/kg, 0.25, the content of nitrogen fertilizer was less than 300 mg/kg. The content of -5.00 mm aggregates increased with the increase of nitrogen fertilizer amount; when the amount of nitrogen fertilizer was greater than 300 mg/kg, the proportion of 0.25-5.00 mm aggregate content decreased with the increase of nitrogen fertilizer. The soil pH (P H) decreased with the increase of soil nitrogen application, and the conductivity (EC) and the exchange amount of soil Yang (CEC) increased with the increase of nitrogen fertilizer. The soil pH (P H), electrical conductivity (EC) and soil cation exchange capacity (CEC) decreased with the increase of nitrogen fertilizer amount and increased.5. through material characterization technology. The basic properties of environmental materials, functional groups and morphology characteristics were obtained. The mechanism of environmental materials on soil lead, cadmium solidification and nitrogen fertilizer synergism was discussed. (1) the basic properties of the materials were obtained. C, H, and O elements are the main components, D50=11.37 nm, D90=61.53 nm, the specific surface area, the pore size and the pore volume are 265.88 m2/g, 4.63 nm and 0.061 cm3/g. serpentine are magnesium rich silicate minerals, D50=18.82 micron m, and the pore size and pore volume are 141.59, 10.36 and 0.024, respectively. Cm3/g. humic acid mainly consists of C, H, O, S and other elements; D50=15.46 mu m, D90=63.47 mu m; the specific surface area, pore size and pore volume are 13.64 m2/g, 18.13 nm and 0.004 cm3/g. electronegativity sequence: serpentine nano carbon lignite humic acid. (2) clear the environmental material of the chemical group, morphology and chemical composition, and analyzed the adsorption before and after adsorption .FT-IR maps of chemical functional groups, morphologies and chemical composition changes show that carbon nanoscale, serpentine and lignite humic acid contain a large number of active groups, in which some functional groups are involved in Pb~ (2+), Cd~ (2+) and NH_4~+ ion adsorption, and the adsorption process has the formation and fracture of chemical bonds; field emission scanning electron microscopy (SEM) results show that Nanoscale, serpentine and lignite humic acid surface microspheres, micropores and microspheres provide a place for adsorption reaction. EDS analysis shows that Pb~ (2+), Cd~ (2+) and NH_4~+ are adsorbed on carbon nanoscale, serpentine and lignite humic acid. (3) three environmental materials of nano carbon, serpentine and lignite humic acid are discussed. The mechanism of heavy metal lead, cadmium solidification and nitrogen fertilizer synergism. There are two levels of environmental materials on heavy metal lead, cadmium solidification and nitrogen fertilizer synergistic mechanism.
【學(xué)位授予單位】：中國(guó)礦業(yè)大學(xué)(北京)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：S153;X53

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