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研究生: 張瓊云
Qiong-Yun Zhang
論文名稱: 調查經零價鐵與硫酸鹽處理之水田根系土 於稻作栽種期間主要最終電子接受程序
Investigation of the primary terminal electron accepting process in the paddy rhizosphere amended with zerovalent iron and sulfate during rice cultivation
指導教授: 林居慶
Chu-Ching Lin
口試委員:
學位類別: 碩士
Master
系所名稱: 工學院 - 環境工程研究所
Graduate Institute of Environmental Engineering
論文出版年: 2022
畢業學年度: 110
語文別: 中文
論文頁數: 87
中文關鍵詞: 水田根圈土壤鎘污染生物有效性硫酸鹽添加生態氧化序列含硝酸鹽肥料
外文關鍵詞: paddy rhizosphere, cadmium pollution, bioavailability, sulfate amendment, ecological redox sequence, nitrate-containing fertilizer
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  • 過往的文獻已證實藉由二價鐵與硫酸鹽(sulfate)的適度添加,可讓汞(Hg)與鎘(Cd)穩定於底泥跟土壤介質中,達到兩金屬生物有效性顯著降低之功效。然而,實驗室前期盆栽試驗的結果,卻發現僅有零價鐵可發揮降低水田根系土壤中鎘之生物有效性的功能,硫酸鹽的效果卻遠不如預期。由於後續菌種組成的調查顯示試驗土壤中的硫酸鹽還原菌佔比極低,故本研究從生態氧化序列(ecological redox sequence)的角度切入,試圖調查硫
    酸鹽無法發揮功效的原因,是否與前期試驗時所用的肥料含有比硫酸鹽更容易被現地微生物利用的最終電子受體有關。有鑑於此,本研究利用原有的污染土壤及定期加入與所測得的根系分泌物等量的有機碳(葡萄糖與醋酸鹽),並分成有無添加肥料的組別,進行為期兩個月的土壤縮模培養試驗,以探討(兩種)肥料、硫酸鹽及零價鐵三者於模擬稻田覆水時期根圈土壤達厭氧狀態時,彼此的兢爭關係,並以孔隙水中重金屬濃度的減少與否,做為該金屬在試驗期間於土壤介質中生物有效性降低的證據。研究結果發現未含肥料組別的土壤及孔隙水樣品,隨時間皆能順利觀察到硫化物與二價鐵存在的跡象,且鎘於孔隙水中的濃度得以有效降低。而在含有肥料的組別中,零價體與硫酸鹽的還原速度相較於未含肥料組則來得緩慢、甚至毫無反應,並在孔隙水中檢測到硝酸鹽,其濃度隨時間逐漸降低,過程中也一度發現亞硝酸鹽的蹤影,藉此可確定系統中正進行硝酸鹽還原(或脫硝)反應,也由此可推測該土壤中的硝酸鹽會與零價鐵及硫酸鹽競爭,並優先成為系統中微生物呼吸作用的電子受體,最後使得硫酸鹽所受的影響最大,因無法被有效還原,以至於無法顯著降低鎘在系統中的生物有效性。這些結果表明故當利用硫酸鹽進行受鎘或其他重金屬污染的稻田土整治時,必須優先檢測所用肥料是否含有一定濃度的硝酸鹽,因其最終效用會與此含有硝酸鹽的氮肥形成衝突,兩者在厭氧根圈中競爭的後果將造成硫酸鹽帶來的整治效果不彰;但假使環境中缺少充足硝酸鹽作為電子受體,硫酸鹽的添加仍具有良好的效果,可以有效降低稻田土孔隙水中的鎘濃度,且其價格低廉,是值得考慮的土壤改良劑。


    Previous literatures have confirmed that by moderate addition of ferrous iron and sulfate,
    mercury and cadmium can be stabilized in the sediment and soil medium, and the bioavailability
    of the two metals can be significantly reduced. However, the results of the previous pot
    experiments in the laboratory found that only zero-valent iron can play a role in reducing the
    bioavailability of cadmium in the root soil of paddy fields, while the effect of sulfate is far less
    than expected. Since the subsequent investigation of bacterial species composition showed that
    the proportion of sulfate-reducing bacteria in the test soil was extremely low, this study started
    from the perspective of ecological redox sequence, and tried to investigate whether the reason
    why sulfate could not exert its effect was the same as that in the previous period. Fertilizers
    used in the experiments contained final electron acceptors that were more readily available to
    local microorganisms than sulfate. In view of this, this study used the original contaminated
    soil and regularly added the same amount of organic carbon (glucose and acetate) as the
    measured root exudates, and divided them into groups with or without added fertilizers for a
    period of two months. Soil miniature model culture experiment to explore the relationship
    between (two) fertilizers, sulfate and zero-valent iron when the rhizosphere soil reaches
    anaerobic state in the simulated paddy water-covered period, and the reduction of heavy metal
    concentration in pore water Whether or not, as evidence of reduced bioavailability of the metal
    in soil media during the test period.The results of the study found that the presence of sulfide
    and ferrous iron could be successfully observed over time in soil and pore water samples
    without fertilizers, and the concentration of cadmium in pore water was effectively reduced. In
    the group containing fertilizer, the reduction rate of zerovalent body and sulfate was slower than
    that of the group without fertilizer, and there was no response. Nitrate was detected in pore
    water, and its concentration gradually decreased with time. During the process, traces of nitrite
    were also found, which can confirm that the nitrate reduction (or denitrification) reaction is
    going on in the system, and it can be speculated that the nitrate in the soil will compete with
    zero-valent iron and sulfate, and It preferentially becomes the electron acceptor for microbial respiration in the system, and finally makes the sulfate most affected, because it cannot be effectively reduced, so that the bioavailability of cadmium in the system cannot be significantly reduced.These results indicate that when using sulfate to remediate paddy soil contaminated with cadmium or other heavy metals, it is necessary to first detect whether the fertilizer used contains a certain concentration of nitrate, because its final effect will conflict with this nitrogen fertilizer containing nitrate, and the two The result of the competition between the two in the
    anaerobic rhizosphere will cause the ineffective remediation effect brought by sulfate; but if there is a lack of sufficient nitrate as an electron acceptor in the environment, the addition of sulfate still has a good effect, which can effectively reduce the amount of soil in paddy fields.Cadmium concentration in pore water, and its low price, is a soil conditioner worth considering.

    摘要 ........................................................................................................................................ i Abstract ................................................................................................................................. ii 第一章 前言 ................................................................................................................... 1 1.1 研究背景 ............................................................................................................ 1 1.1.1 重金屬污染農田帶來的影響 ................................................................. 1 1.1.2 農地重金屬污染整治技術 ..................................................................... 2 1.1.3 鎘在水稻田覆水期間時的型態 ............................................................. 2 1.1.4 利用硫酸鹽與零價鐵整治水稻土原因 .................................................. 3 1.1.5 土壤介質中硫酸鹽、零價鐵與鎘的相互關係 ...................................... 4 1.1.6 硫酸鹽、零價鐵、鎘對生物體和植作體的影響 ................................... 5 1.1.7 硫酸鹽與零價鐵植栽試驗結果 ............................................................. 6 1.1.8 生態氧化還原序列 ............................................................................... 14 1.2 研究目的 .......................................................................................................... 16 第二章 材料與方法 ...................................................................................................... 17 2.1 實驗設計與架構 .............................................................................................. 17 2.1.1 土壤配製 .............................................................................................. 17 2.1.2 土壤縮模實驗架構 ............................................................................... 20 2.1.3 土壤根系分泌物收集方式與添加 ........................................................ 24 2.2 孔隙水參數分析 .............................................................................................. 28 2.2.1 孔隙水採集 .......................................................................................... 28 2.2.2 孔隙水中DOC 濃度定量分析 ............................................................. 29 2.2.3 孔隙水中總氮濃度定量分析 ............................................................... 29 2.2.4 孔隙水中硫化物濃度定量分析 ........................................................... 29 2.2.5 孔隙水中亞鐵濃度定量分析 ............................................................... 30 2.2.6 孔隙水中硝酸鹽/亞硝酸鹽/硫酸鹽濃度定量分析 .............................. 30 2.2.7 孔隙水中重金屬(鎘、銅、鋅)濃度定量分析 ...................................... 30 2.3 土壤參數分析 .................................................................................................. 30 vi 2.3.1 土壤中可被稀鹽酸溶解萃取之總鐵/亞鐵分析 ................................... 30 2.3.2 土壤中揮發性硫化物(acid-volatile suifide, AVS)分析 ......................... 32 第三章 結果與討論 ...................................................................................................... 33 3.1 根系分泌物的收集與成分的衰減 ................................................................... 33 3.2 土壤背景與肥料分析 ...................................................................................... 35 3.3 縮模實驗中零價鐵與硫化物在土壤固相中的測值 ........................................ 39 3.4 縮模實驗中孔隙水中總碳及總氮的測值 ........................................................ 42 3.5 縮模實驗中孔隙水中硝酸鹽與亞硝酸鹽的測值 ............................................ 45 3.6 縮模實驗中零價鐵與硫酸鹽在孔隙水中的測值 ............................................ 48 3.7 縮模實驗中親硫金屬(Cd、Cu、Zn)於孔隙水中的測值 ................................ 53 3.8 NRB、IRB 與SRB 三者於生態圈中的相互關係 ........................................... 57 3.9 在開放系統中硝酸鹽還原菌與氮肥間於土壤中的關係 ................................. 58 第四章 結論與建議 ...................................................................................................... 60 4.1 結論 ................................................................................................................. 60 4.2 建議 ................................................................................................................. 61 參考文獻 ............................................................................................................................. 62 附錄 ..................................................................................................................................... 68

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