本文選題：土壤污染 + 重金屬��； 參考：《廣東工業(yè)大學(xué)》2015年碩士論文

【摘要】：土壤重金屬污染具有隱蔽性、難降解性、生物積累性等特點(diǎn),治理難度大、成本高。累積在土壤中的重金屬不僅能夠破壞土壤微生物群落結(jié)構(gòu),抑制農(nóng)作物的生長(zhǎng),造成糧食減產(chǎn),還能通過食物鏈不斷傳播并在生物體內(nèi)富集,最終威脅人類健康。我國(guó)土壤重金屬污染形勢(shì)嚴(yán)峻,農(nóng)田土壤的重金屬污染已經(jīng)嚴(yán)重威脅到了我國(guó)的糧食安全和人民群眾的生命健康。原位鈍化技術(shù)是修復(fù)重金屬污染土壤的重要手段之一。原位鈍化技術(shù)是指通過向土壤中施加一些有機(jī)或無機(jī)的化學(xué)物質(zhì),改變土壤理化性質(zhì),或使加入的化學(xué)物質(zhì)與土壤中的重金屬發(fā)生物理化學(xué)反應(yīng),從而改變重金屬在土壤中的賦存形態(tài),降低其在土壤環(huán)境中的生物有效性和遷移性,達(dá)到修復(fù)污染土壤的技術(shù)。與其他修復(fù)技術(shù)相比,該方法具有修復(fù)效果好、修復(fù)周期短、成本低廉、操作簡(jiǎn)單等特點(diǎn),特別在修復(fù)重金屬?gòu)?fù)合污染土壤方面具有明顯優(yōu)勢(shì)。本文以環(huán)境友好的腐殖質(zhì)類物質(zhì)-胡敏素為基質(zhì),開發(fā)經(jīng)濟(jì)高效環(huán)保的土壤鈍化劑材料,并對(duì)其用于土壤重金屬污染修復(fù)開展了基礎(chǔ)性的理論和技術(shù)研究。主要包括下列內(nèi)容：1.采用堿提法從泥炭土中分離出來性質(zhì)穩(wěn)定的胡敏素,并通過吸附平衡實(shí)驗(yàn)研究了胡敏素對(duì)模擬土壤溶液中的重金屬Cd(Ⅱ)、Pb(Ⅱ)、Cu(Ⅱ)的吸附動(dòng)力學(xué)和熱力學(xué)特性,并研究了pH、溶液電解質(zhì)濃度、土壤溶液中小分子有機(jī)酸濃度等條件對(duì)胡敏素吸附重金屬效果的影響。結(jié)果表明,胡敏素表面含有大量含氧活性官能團(tuán)；其對(duì)三種重金屬的吸附能力順序?yàn)镃d(Ⅱ) Cu(Ⅱ)Cd(Ⅱ),且對(duì)Cd(Ⅱ)、Cu(Ⅱ)的吸附符合Freundlich模型,對(duì)Pb(Ⅱ)的吸附符合Langmuir模型；胡敏素對(duì)重金屬的吸附動(dòng)力學(xué)符合二級(jí)動(dòng)力學(xué)方程；隨著pH的升高,胡敏素對(duì)重金屬的吸附量迅速增加；溶液中的電解質(zhì)離子和酒石酸都能夠抑制胡敏素對(duì)重金屬的吸附；胡敏素對(duì)實(shí)際農(nóng)田土壤溶液中重金屬的鈍化能力優(yōu)于對(duì)模擬溶液的鈍化能力。2.通過土壤鈍化實(shí)驗(yàn),研究了添加胡敏素對(duì)污染土壤中銅和鉛的生物有效性的影響和重金屬賦存形態(tài)的轉(zhuǎn)化。結(jié)果表明,添加胡敏素可顯著降低重金屬的浸出濃度。當(dāng)投加2%的胡敏素5天后,土壤中重金屬銅和鉛的浸出濃度分別下降45.16%和56.97%。投加胡敏素后能迅速鈍化土壤中的重金屬,進(jìn)一步延長(zhǎng)鈍化時(shí)間對(duì)鈍化效果影響不大。尿素、硫酸銨、磷酸二氫鉀可顯著提高胡敏酸對(duì)鉛的鈍化效果,浸出濃度分別下降了29.36%、23.57%、28.69%,但對(duì)銅的影響不明顯。進(jìn)一步的研究表明投加2%的胡敏素鈍化處理30天后土壤中交換態(tài)銅和鉛的所占的比例由原來的15.68%和15.79%下降到了0.48%和1.22%,而有機(jī)態(tài)銅和鉛的比例則由5.35%和10.93%上升到了13.24%和27.32%,表明胡敏素可以促進(jìn)可交換態(tài)重金屬向有機(jī)態(tài)和殘?jiān)鼞B(tài)轉(zhuǎn)化。3.用巰基乙酸和乙酸酐對(duì)胡敏素進(jìn)行巰基化改性,從而獲得巰基胡敏素。通過傅里葉紅外和熱重分析研究了巰基化胡敏素的化學(xué)結(jié)構(gòu)特點(diǎn)。通過吸附平衡實(shí)驗(yàn)研究了巰基化胡敏素對(duì)土壤溶液中重金屬Cd(Ⅱ)的吸附熱力學(xué)特性。最后通過土壤鈍化實(shí)驗(yàn)比較了巰基胡敏素和胡敏素對(duì)重金屬?gòu)?fù)合污染土壤的修復(fù)效果。結(jié)果表明：改性后胡敏素表面具有較多的羧基官能團(tuán)。與胡敏素相比,巰基化胡敏素在2578cm-1處出現(xiàn)了典型的巰基官能團(tuán)(S-H)的吸收峰,表明胡敏素表面巰基官能團(tuán)的存在；在不同溫度下巰基胡敏素對(duì)Cd(Ⅱ)的吸附等溫線更符合Langmuir方程,在298K條件下,巰基胡敏素對(duì)Cd的理論飽和吸附量為8.9081 mg·g-1,而胡敏素的理論飽和吸附量為6.5335mg·g-1,表明在胡敏素表面增加巰基數(shù)量顯著提高了其對(duì)鎘的吸附能力；吸附熱力學(xué)參數(shù)表明巰基胡敏素對(duì)Cd(Ⅱ)的吸附為自發(fā)吸熱反應(yīng)。隨著溫度升高,△G的絕對(duì)值增加,吸附劑的飽和吸附量也相應(yīng)增大。在鈍化劑投加量為2.5%的情況下,鈍化處理十天后,巰基胡敏素對(duì)土壤中鎘、鉛、銅三種重金屬的鈍化率分別為44%、65%、50%。對(duì)鎘的鈍化率顯著提高了12%,而對(duì)鉛和銅的鈍化效果沒有明顯變化胡敏素是一種優(yōu)良的土壤重金屬鈍化劑,巰基化胡敏素對(duì)重金屬Cd的吸附效果明顯提高。巰基胡敏素適用于對(duì)受中低濃度重金屬?gòu)?fù)合污染農(nóng)田的修復(fù),具有廣闊的應(yīng)用前景。
[Abstract]:Heavy metal pollution in soil has the characteristics of concealment, difficult degradation and bioaccumulation. The heavy metals in soil can not only destroy the soil microbial community structure, inhibit the growth of crops, cause grain production, but also can be continuously spread through the food chain and enriched in the organism, eventually threatening the human beings. The situation of heavy metal pollution in soil is serious in our country. Heavy metal pollution in farmland has seriously threatened the food safety of our country and the life and health of the people. In situ passivation technology is one of the important means to repair heavy metal contaminated soil. In situ passivation technology is to apply some organic or inorganic chemicals into the soil. To change the physical and chemical properties of soil, or to change the physical and chemical reactions between the chemicals added and the heavy metals in the soil, to change the form of the heavy metal in the soil, to reduce its bioavailability and mobility in the soil environment, to achieve the remediation of contaminated soil. The effect is good, the repair cycle is short, the cost is low, and the operation is simple, especially in the restoration of heavy metal compound contaminated soil. This paper uses the environmentally friendly humus material Hu Minsu as the matrix to develop the economically efficient and environmentally friendly soil passivating agent, and carries out the foundation for the remediation of soil heavy metal pollution. The main contents of the study are as follows: 1. the stability of Hu Minsu was separated from peat soil by alkali extraction, and the adsorption kinetics and thermodynamic properties of the heavy metals Cd (II), Pb (II), Cu (II) in the simulated soil solution were studied by adsorption equilibrium experiment, and the concentration of pH and electrolyte concentration was studied. The effects of the concentration of medium and small molecular organic acids on the adsorption of heavy metals on the adsorption of heavy metals on the Hu Minsu surface show that the Hu Minsu surface contains a large number of oxygen active functional groups, and the adsorption capacity of the three heavy metals is Cd (II) Cu (II) Cd (II), and the adsorption of Cd (II), Cu (II) conforms to the Freundlich model, and the adsorption of Pb (II). The adsorption kinetics of heavy metals conforms to the Langmuir model, and the adsorption kinetics of heavy metals conforms to the two stage kinetic equation; with the increase of pH, the adsorption of heavy metals by Hu Minsu increases rapidly; both the electrolyte ions and tartaric acid in the solution can inhibit the adsorption of heavy metals by the huminin and the blunt of the heavy metals in the actual farmland soil solution by Hu Min. The ability of chemical passivation.2. is better than the passivation ability of simulated solution. The effect of adding Hu min Su on the bioavailability of copper and lead in contaminated soil and the transformation of heavy metal forms are studied. The results show that the leaching concentration of heavy metals can be significantly reduced by adding Hu Minsu. The heavy gold in the soil when adding 2% of the humin 5 days later. The leaching concentration of copper and lead decreased by 45.16% and 56.97%. added humin to passivate the heavy metals in the soil quickly. Further prolonging the passivation time had little effect on the passivation effect. Urea, ammonium sulfate and potassium dihydrogen phosphate could significantly increase the passivation effect of Hu Min acid on lead, and the leaching concentration decreased by 29.36%, 23.57%, 28.69% respectively. The effect of copper was not obvious. Further studies showed that the proportion of exchangeable copper and lead in soil dropped from 15.68% and 15.79% to 0.48% and 1.22% after 30 days of passivation treatment, while the proportion of organic copper and lead increased from 5.35% and 10.93% to 13.24% and 27.32%, indicating that humin could promote exchangeable. The sulfhydryl thioacetic acid and acetic anhydride were modified by mercapto acetic acid and acetic anhydride to obtain mercapto thiothiothiothiothiothiothiothiothiothiothiothiothiothiothiothiothiothiothiothiothiohydrin (.3.). The chemical structure of thimercapmeryl humin was studied by Fourier transform infrared and thermogravimetric analysis. The heavy metal Cd in soil solution was studied by adsorption equilibrium experiment. The effect of sulfhydryl huminin and huminin on the remediation of heavy metal contaminated soil was compared with the soil passivation experiment. The results showed that the surface of Hu Minsu had more carboxyl functional groups after the modification. Compared with humin, the mercapto Hu Minsu had a typical sulfhydryl group (S-) at 2578cm-1. The absorption peak of H shows the existence of the Hu Minsu surface sulfhydryl functional group; the adsorption isotherm of thiol humin to Cd (II) at different temperatures is more consistent with the Langmuir equation. Under the 298K condition, the theoretical saturation adsorption of thiol humin to Cd is 8.9081 mg. G-1, while Hu Minsu's theoretical saturated adsorption amount is 6.5335mg. G-1, indicating that in Hu Minsu The adsorption capacity of cadmium was significantly increased by the increase of the number of sulfhydryl groups on the surface. Adsorption thermodynamic parameters showed that the adsorption of thiol huminin to Cd (II) was spontaneous endothermic reaction. With the increase of temperature, the absolute value of delta G increased and the adsorption capacity of adsorbents increased correspondingly. Under the condition of passivating agent 2.5%, the passivation treatment was treated after ten days, The passivation rate of three heavy metals of cadmium, lead and copper in soil was 44%, 65%, respectively, and the passivation rate of cadmium was increased by 12%, while the passivation effect of 50%. on lead and copper had no obvious change. The effect of huminin was a good heavy metal passivating agent. The adsorption effect of mercapto Hu Minsu on heavy metal Cd was obviously improved. It is suitable for remediation of farmland contaminated by low and heavy metals and has broad application prospects.

【學(xué)位授予單位】：廣東工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X53

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