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研究生:彭查禮
研究生(外文):Chakkrit Poonpakdee
論文名稱:鉀於農業土壤及植體中之型態與生物可利用性之研究
論文名稱(外文):The Potassium Speciation and Bioavailabilityin Agricultural Soil and Plant
指導教授:林耀東林耀東引用關係
口試委員:劉雨庭賴鴻裕李得逵翁誌煌
口試日期:2018-07-25
學位類別:博士
校院名稱:國立中興大學
系所名稱:土壤環境科學系所
學門:農業科學學門
學類:農業化學類
論文種類:學術論文
論文出版年:2018
畢業學年度:107
語文別:英文
論文頁數:481
中文關鍵詞:鉀型態X光吸收光譜連續萃取法黏土礦物穿透式X光顯微攝影術
外文關鍵詞:Potassium speciationXASSequential extraction processClay mineralTXM
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Potassium (K) is a macro-nutrient for plant growth. The bioavailability of K depends on its speciation distribution in the soil. Wet chemical extractions are commonly used to estimate K speciation including traditional single leaching (TSL) and sequential extraction process (SEP). In wet chemical extraction, the soil requires pretreatment, chemical preparation, and the experiment needs to be conducted using specific methods and under specific conditions. The synchrotron light sources technique (X-ray absorption spectroscopy, XAS) has a number of advantages: It is non-destructive to the sample and gives a direct estimation of the component in the sample. Potassium speciations in soil exist in dynamic equilibrium. Moreover, clay mineral in soil is a factor that influences soil fertility. The change of the microstructure of clay minerals in various environmental conditions (such as swelling or shrinking) was characterized using Transmission X-Ray Microscopy (TXM). The objectives of this study were to 1) estimate K speciations 2) estimate soil K buffering power, and 3) investigate K transformation and translocation between soil K and plant K. The results showed that for the various SEP schemes, K speciation was found to be greatest in the residual fraction, with only 3% observed in the carbonate, exchangeable, metal organic complex, or amorphous hydroxides of Fe or Mn. After following the first two steps of the SEP schemes, the available K was similar to that of the TSL method. Distribution of non-exchangeable K using the TSL method was comparable with the five combined SEP extraction steps which were all affected by environmental conditions.
Direct method demonstrated that soil samples showed potassium K-edge XANES peak at 3615.2 eV. This peak represented excitation of 1s electrons as the K orbital. Five types of soil samples fitted well with an illite-smectite standard that related to the soil component. Furthermore, the 2 and 3-dimensions of soil flocculation structure were successfully deconstructed and showed variations in structure. Soil available K (exchangeable, and carbonate fraction) is the K bioavailability fraction in soil. Soil cation exchange capacity (CEC) and K desorption rate had a positive correlation with the amount of K translocation to plant and water leaching K. The ration between K transformation to plant and water leaching K found that K loss was at 1 A.U. per 5-15 A.U. to plant in soil applied K fertilizer and 9-44 A.U. in soil that was not treated with K fertilizer. Exchangeable K (24-30%), carbonate K (20-75%), and easily reducible metal oxide K (1.70%) were the sources for K translocation from soil to plant K and water leaching K. Plant growth in soil applied with K fertilizer was higher than that grown in soil that had no K fertilizer applied (shoot height 1.28-1.31 folds; dried weight 1.29-1.35 folds; total plant K 1.52-2.39 folds). Wet chemical extraction from SEP is highly advantageous to classify the soil K speciation that is correlated with K bioavailability as total plant dried weight (r2 = 0.71), plant shoot height (r2 = 0.65), and shoot dried weight (r2 = 0.71). Therefore, a combination of direct and indirect methods for measuring K speciation in soil is the most effective method to provide more information and the relationship between soil K speciation information in large and atomic scale.
Contents
Acknowledgements i
Abstract ii
Content of Tables ix
Content of Figures x
1. Introduction 1
1.1. Background of the study 1
1.2 Objectives 4
2. Literature review 6
2.1 Potassium cycle 6
2.2 Role of K on plant growth 7
2.3 The generation of traditional single leaching reagent 9
2.4 Traditional single leaching (TSL) 14
2.4.1 Water soluble K 14
2.4.2 Exchangeable K 15
2.4.3 Non-exchangeable K 15
2.4.4 Mineral K 17
2.4.5 Drawback of traditional single leaching 18
2.5 Sequence extraction process (SEP) 20
2.5.1 Tessier et al., (1979) scheme 20
2.5.2 Shuman (1985) scheme 22
2.5.3 Ure et al. (1993) scheme (BCR method) 23
2.5.4 Krishnamurti et al. (1995) scheme 24
2.5.5 The term definition of the speciation in the soil 26
2.6 The comparison between tradition method and sequential extraction process 30
2.7 Potassium availability 32
2.7.1 Clay mineral 32
2.7.2 Concentration of K in soil 34
2.7.3 Concentration of Calcium and Magnesium in soil 35
2.7.4 Wetting and Drying of soil 35
2.7.5 Soil pH 35
2.7.6 Soil organic matter 36
2.7.7 Soil nitrogen 36
2.7.8 Soil EC 37
2.8 Kinetic of K sorption and desorption in soil 37
2.9 Synchrotron radiation 40
2.9.1 X-Ray Absorption Near Edge structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) 42
2.9.2 Transmission X-ray microscopy (TXM) 45
2.10 The comparison between direct and indirect method for K speciation 46
3. Materials and Methods 48
3.1 X-ray absorption spectroscopy and sample preparation 50
3.2 Soil sampling and preparation 52
3.3 Physicochemical soil analyzesis 55
3.3.1 Soil pH and electric Conductivity (EC) 55
3.3.2 Cation exchange capacity (CEC) 55
3.3.4 Organic matter 55
3.3.5 Total nitrogen in soil 56
3.3.6 Available P 56
3.3.7 Exchangeable Ca and Mg 56
3.3.8 Soil particle 57
3.3.9 Clay mineral 58
3.4 Experiment 1: Assessment of potassium speciation in soil using traditional single leaching and modified sequential extraction processes 59
3.4.1 Traditional single leaching (TSL) 59
3.4.2 Sequential extraction process (SEP) 60
3.4.3 Data analysi 67
3.5 Experiment 2: Potassium sorption and desorption in soil. 67
3.5.1 K sorption in soil 68
3.5.2 K desorption in soil. 70
3.5.3 Data analysis 70
3.6 Experiment 3: Pot experiment 72
3.6.1 Plant growth indicator 73
3.6.2 Plant K analysis 73
3.6.3 K speciation in soil 73
3.6.4 Water leaching K 74
3.6.5 Data analysis 74
4. Results and discussion 75
4.1 Assessment of potassium speciation in soil using traditional single leaching and modified sequential extraction processes 75
4.2 Potassium speciation in soil by X-ray absorption spectroscopy (XANES and EXAFS) and wet-chemical fractionation 100
4.3 Potassium adsorption and transformation characteristic in soil 115
4.4 Available potassium reserve assessment using sodium tetraphenylboron in intensive ryegrass cropping 147
4.5 Speciation, transformation, and translocation of potassium in soil and plants 161
4.6 Applicability of the Sequential Extraction Process for Potassium Bioavailability Assessment 197
5. Conclusions and Suggestion 223
5.1 Conclusions 223
5.2 Suggession 225
References 227
Content of Appendix 237
Content of Appendix Table 239
Content of Appendix Figures 244
Appendix I Material and Method 250
I-1 Chemical list 250
I-2 Instrument 251
I-3 Statistic analysis 252
Appendix II Wet chemical extraction 253
II-1 Traditional single leaching 253
II-1-1 Water soluble K 253
II-1-2 Available K 253
II-1-3 Exchangeable K 253
II-1-4 HNO3-K 254
II-1-5 Non-exchangeable K 254
II-1-6 Total K 254
II-1-7 Mineral K 254
II-2 Sequential extraction processes 255
II-2-1 Tessier et al. (1979) scheme 255
II-2-2 Shuman (1983) scheme 255
II-2-3 BCR scheme (Ure et al. 1993) 255
II-2-4 Krishnamurti et al. (1995) scheme 256
Appendix III Standard K calibration curve 257
III-1 Potassium standard calibration curve 257
III-1-1 Soil K speciation 257
III-3 Potassium sorption 265
III-4 Potassium desorption 266
III-5 Potassium speciation in cultivation soil 269
III-2 Detection limit of K 273
Appendix IV Raw dara 274
IV-1 Potassium speciation by TSL, and SEP schemes 274
IV-1-1 Soil K speciation using TSL scheme 274
IV-1-2 Soil K speciation using SSL scheme 278
IV-1-3 Soil K speciation using Tessier et al., (1979) 282
IV-1-4 Soil K speciation using Shuman (1985) 287
IV-1-5 Soil K speciation using Ure et al., (1993) 292
IV-1-6 Soil K speciation using Kritinamuti et al., (1995) 296
IV-2 Potassium adsorption and desorption 304
IV-2-1 Potassium adsorption 304
IV-2-2 Potassium desorption 329
IV-3 Pot experiment 342
IV-5 Data calculation 365
IV-5-1 Soil K speciation 365
IV-5-2 Plant K 366
IV-5-3 Water leaching K 367
IV-6 Results 368
IV-6-1 The comparison of K speciation using various schemes 368
IV-6-2 Potassium adsorption 373
IV-6-3 Potassium adsorption 378
IV-6-4 Experiment 3 Potassium distribution in soil and plant 378
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