臺灣博碩士論文加值系統

酚酸為常見之自毒/毒他物質，並被認為是多種作物連作障礙主要成因之一。酚酸可能影響植物的細胞分裂、水分及離子的吸收、抑制光合作用、干擾ATP的合成等，也可能刺激病原菌之生長或改變土壤微生物結構。前人研究發現，活性炭的施用可改善水耕及土壤中作物的自毒性，但一般活性炭價格高昂，並不適用於大面積之田間操作。相較於活性炭，生物炭可利用各類農業廢棄物製造，使廢棄物轉為可用資源回歸土壤並改善土壤，有助於土地的永續利用。而生物炭多孔之特性使其具有吸附有機物之能力，且可經由材料選擇、改變裂解條件、或利用不同改質方式提升其孔隙率及表面積，當施用於土壤中，應有助於解決連作障礙問題。本研究目的為：(1) 利用不同農業廢棄物及裂解條件製備與篩選對酚酸具高吸附性之生物炭；(2) 利用芹菜連作盆栽試驗評估所製備生物炭對連作障礙改良之效益；(3) 分析連作芹菜時，目標酚酸於土壤中之濃度變化；(4) 評估生物炭對土壤中微生物之影響。結果顯示，以木屑加磷酸 (1:1.5，w/w) 在400°C下裂解製備的生物炭 (WP400) 具最高之比表面積 (1273 m2 g-1)，並且對測試酚酸 (包括苯甲酸衍伸物及肉桂酸衍伸物) 有最高之吸附。WP400之吸附能力可能與其有較高的比表面積和含氧官能基有關，其對酚酸之吸附隨pH上升而降低。WP400可降低土壤之水可萃取總酚濃度，可能為土壤尖孢鐮刀菌 (Fusarium oxysporum) 密度下降並改善連作病害之原因。在第一作以0.2%左右之用量施用WP400可增加第一作之芹菜乾重，並可減少連作時之罹病率及死亡率。但WP400可能影響植物對氮、磷、鈣及鎂之吸收，施用時須評估土壤元素之有效濃度及肥料之施用。利用LC-QTOF/MS對酚酸進行定量，結果顯示，p-coumaric acid是所定量的土壤酚酸中唯一有累積趨勢的酚酸，且WP400的施用增加了累積幅度，顯示了WP400對此酚酸具有的較高的親和力。利用Mass Profiler以及Metlin資料庫搜尋芹菜連作下其他可疑毒他物發現，連作下有明顯累積趨勢的疑似物多為脂肪酸相關之化合物，而脂肪酸為前人研究植物毒他物中的一個類群。土壤中的微生物亦可能受毒他物影響而轉為不利作物生長之族群結構。本研究發現，WP400除了可降低尖孢鐮刀菌在芹菜連作土中之族群密度，且其施用改變了微生物對碳源的利用模式 (對胺類的利用率降低)，顯示此生物炭改變了土壤中一些碳源的可利用性，並影響了土壤微生物族群結構。

Phenolic acids are common autotoxins/allelochemicals and are considered a cause of obstacles in continuous cropping for various crops. Phenolic acids may affect plant cell division, water and ion absorption, inhibit photosynthesis, interfere with ATP synthesis, stimulate the growth of pathogens, or alter soil microbial structure. Previous studies have found that the application of activated carbon can improve the autotoxicity of crops in hydroponic and soil systems. However, activated carbon is generally expensive and not suitable for large-scale field operations. In comparison to activated carbon, biochar can be produced from various agricultural waste materials, converting waste into a reusable resource for soil improvement, contributing to sustainable land use. The porous nature of biochar provides it with the ability to adsorb organic com-pounds, and its porosity and surface area can be enhanced through feedstock selection, modification methods, and changes in pyrolysis conditions. The objectives of this study are: (1) to prepare and select biochar with high adsorption capacity for phenolic acids using different agricultural waste materials and pyrolysis conditions; (2) to evaluate the benefits of the prepared biochar in alleviating continuous cropping obstacles through celery continuous cropping pot experiments; (3) to analyze the concentration changes of target phenolic acids in the soil; (4) to assess the impact of biochar on microorganisms. The results showed that biochar prepared by pyrolyzing wood soaked with phosphoric acid (1:1.5, w/w) at 400°C (WP400) had the highest specific surface area (1273 m2 g-1) and exhibited the highest adsorption for tested phenolic acids, including derivatives of benzoic acid and cinnamic acid). The adsorption capacity of WP400 may be attributed to its higher specific surface area and oxygen-containing functional groups. The adsorption of phenolic acids by WP400 decreased as pH in-creases. WP400 could reduce the water-extractable total phenol concentration in the soil, this could be the reason for the decrease in the density of Fusarium oxysporum in the soil and the improvement of issues related to continuous cropping. At an application rate of around 0.2% in the first crop, it increased celery dry weight and reduced disease incidence and mortality in continuous cropping of celery. However, WP400 may affect the plant's uptake of nitrogen, phosphorus, calcium, and magnesium, and soil element concentrations need to be evaluated during the application. Quantitative analysis of phenolic acids using LC-QTOF/MS revealed that an accumulating trend solely for p-coumaric acid in the soil upon the application of WP400, highlighting the specific adsorption capability of WP400 for these phenolic acids. Using Mass Profiler and the Metlin database, other suspected allelopathic substances were identified, most of which were fatty acid-related compounds, suggesting a potential role of fatty acids as allelopathic compounds. Microorganisms in the soil may be influenced by allelopathic substances and shift towards a community structure detrimental to crop growth. This study found that WP400 can reduce the population density of Fusarium oxysporum in continuous cropping soil and alter microbial utilization patterns of car-bon sources (reducing the utilization rates of amines), indicating that this biochar changed the availability of some carbon sources in the soil and affect the soil microbial community structure.

摘要 ⅰ
ABSTRACT ⅲ
目錄 ⅴ
表目錄 ⅸ
圖目錄 ⅹ

第一章 前言與文獻回顧 1
1.1研究背景與動機 1
1.2 連作障礙與其成因 3
1.3 自毒/毒他作用 4
1.4 微生物與連作障礙 5
1.5 生物炭 6
1.5.1 生物炭之原料 7
1.5.2 生物炭之裂解溫度 7
1.5.3 生物炭改質方式 8
1.6 酚酸與連作障礙 10
1.7研究目標 13
第二章 生物炭的製備與篩選 14
摘要 14
2.1 前言 15
2.2 材料與方法 16
2.2.1生物炭之製備 16
2.2.2 原料與生物炭特性檢定 17
2.2.3 酚酸吸附試驗 19
2.3 結果與討論 21
2.3.1 未改質生物炭之基本特性 21
2.3.2 改質生物炭之基本特性 27
2.3.3 生物炭吸附酚酸之能力 32
2.3.4 WP400對酚酸之等溫與動力吸附 33
2.3.5 WP400對酚酸之可能吸附機制 37
2.4 結論 39
第三章 盆栽試驗 40
摘要 40
3.1 前言 41
3.2 材料與方法 42
3.2.1 試驗作物 42
3.2.2 WP400之製備 42
3.2.3 生物炭特性檢定 42
3.2.4 盆栽試驗 43
3.2.5 土壤分析 44
3.2.6 植體分析 46
3.2.7 芹菜病原真菌鑑定 46
3.2.8 黃萎病罹病度計算 46
3.2.9 統計分析 47
3.3 結果與討論 47
3.3.1 第一次盆栽試驗 47
3.3.2 第二次盆栽試驗 56
3.4. 結論 61
第四章 酚酸之定量以及可疑毒他物之搜尋 62
摘要 62
4.1 前言 63
4.2 材料與方法 63
4.2.1 WP400與土壤對混合酚酸的吸附 63
4.2.2 土壤 (吸附態) 酚酸之萃取 (QuEChERS) 64
4.2.3 酚酸濃度分析 64
4.2.4 芹菜可疑毒他物之搜尋 (未知物分析) 66
4.2.5 統計分析 68
4.3 結果與討論 68
4.3.1 WP400與土壤對混合酚酸之吸附 68
4.3.2 土壤酚酸萃取與定量 69
4.3.3 可能之毒他物搜尋 71
4.4 結論 73
第五章 土壤微生物之變化 74
摘要 74
5.1 前言 75
5.2 材料與方法 76
5.2.1 土壤真菌鑑定 76
5.2.2 Ecoplates群落分析 76
5.2.3 統計分析 77
5.3 結果與討論 79
5.3.1 生物炭 (WP400) 對Fo及其他土壤真菌之影響 79
5.3.2 土壤微生物Ecoplates群落分析 80
5.4 結論 86
第六章 總結 87
第七章 參考文獻 90

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