臺灣博碩士論文加值系統

腐植物質之研究大多數採用氫氧化鈉作為萃取溶液，也就是國際腐植質學會(IHSS)普遍選用的方法。然而，腐植素不溶於鹼液之特性難以用上述方法所萃取。近年來以連續消耗性抽出方法(SEE)進行腐植素的抽出已經被應用於與熱帶亞馬遜與溫帶愛爾蘭高緯度地區。實驗選用 SEE 萃取方法對台灣的火山土壤加以分離腐植酸、黃酸以及腐植素。結果顯示，各 pH 階段所萃取出的腐植酸及黃酸，隨著萃取 pH 值的升高，其所抽出的脂肪族碳含量相對性增加。而 SEE 所萃取出的腐植酸/黃酸與用 IHSS 方法有相似的結果，各萃取流程的組成份在效率和產量上雖有所不同，其累積萃取效率在 SEE(65%)方法較 IHSS(33%)為高，但不會改變各組分的化學結構。此外，將殘餘的土壤以鹼液連續性進行一次、三次以及八次的抽出後，再以 SEE 方法的最後一個步驟利用 DMSO 加以萃取腐植素，結果顯示隨著萃取次數的增加，其結晶性 polymethylene hydrocarbon 亦有增加之趨勢，說明晶性佳的烴結構與礦物膠體之鍵結將增加萃取的困難度。土壤中普遍存在的腐植物質與黏土礦物促成土壤團粒結構，即一種有機-黏土基質。醌類化合物是經由二氧化錳之非生物性催化作用氧化聚合多酚類化合物所形成，此多酚類的反應被認為是腐植化作用之前趨物之一。釐清醌類及腐植物質與廣泛分布於土壤環境中的鐵(氫)氧化物之反應機制有助於瞭解無機礦物在土壤中腐植化作用及其對環境中的物理及化學作用之影響。鐵(氫)氧化物吸附腐植酸及醌類化合物有 HA>HQ-20>HQ-7>HQ-1 之趨勢。在較低的 pH 值(pH 4)，土壤礦物對腐植酸/黃酸有較高之吸附量;隨著 pH 值的增加，當礦物膠體的 ZPC 值大於溶液 pH，
將顯著地降低其吸附量。鐵(氫)氧化物與土壤礦物對於腐植酸/黃酸在吸附量上為水合鐵礦>針鐵礦>高嶺土≒蒙特石。經由傅立葉紅外光譜結果顯示，波數 1720的消失以及 1609、1575 的變寬及強度增加，顯示腐植酸/醌類化合物之羧基與鐵(氫)氧化物表面的氫氧基進行配位基交換，形成強的內圈錯合物。利用中空管柱過濾系統(hollow-fiber filtration)將腐植酸分為>100 kD、50-100 kD 以及<50 kD 三個不同分子量範圍的腐植酸分布。動力吸附結果顯示大分子腐植酸(> 100 KD)被固定在礦物表面比小分子腐植酸上有較高的偏好。而優先吸附的原因包含一、芳香性碳結構(增加疏水性交互作用)，二、羧基官能基(主要的吸附位置)，三、含碳量。

關鍵字：
腐植素萃取; 連續消耗性抽出方法; 醌; 氧化聚合; 鐵(氫)氧化物; 吸附

Most studies of humic substances (HSs) been carried out on extracts of soils in dilute sodium hydroxide solutions, i.e., the isolation of the International Humic Substances Society (IHSS). However, humin, is insoluble in aqueous base. Recently, a sequential exhaustive extraction (SEE) process has been shown to be capable of isolating and separating the major components of the classically defined HSs from soils of the temperate and tropical regions. The SEE system was used to isolate the HA/FA and humin fractions from a subtropical volcanic Taiwanese soil. Increases in
the aliphatic relative to aromatic carbon contents were observed for both the HA and FA fractions when the pH values of the extraction media were increased. HAs and FAs isolated using the SEE method have spectroscopic profiles similar to those from the IHSS isolate; however, the cumulative extraction efficiency (%) of the SEE method (65%) for the volcanic soil was much higher than for the traditional IHSS
method (33%). When the residual volcanic soil, following extractions once, three, and eight times with 0.1 M NaOH were then extracted with dimethylsulphoxide (DMSO) plus concentrated sulphuric acid (the final solvent in the SEE sequence), it was seen that the content of crystalline polymethylene hydrocarbon (33 ppm 13 C NMR resonance in the humin (or DMSO-acid)) extract increased relative to the amorphous methylene (30 ppm). That highlights the difficulty in dissolving the more highly ordered hydrocarbon structures that would be expected to have closer associations with the
mineral colloids.In addition,the interactions of HSs with
clay minerals commonly occur in soil which may lead to the formations of soil aggregates, forming an organo-clay matrix. Quinones, naturally abiotic polyphenol polymerization reaction catalyzed by MnO2, have been considered as precursor of humification in soil. Clarifying the reactive mechanisms of quinones (HQs) and HSs with widely distributed Fe(oxy)hydroxides can provide insight into the effects of the inorganic minerals on the humification of organic components in soil and the
important physico-chemical reactions of environmental processes. The organo-clay of HA and HQs adsorbed on Fe(oxy)hydroxides followed the order of HA > HQ-20 > HQ-7 > HQ-1. Adsorption results indicated that low pH was favorable for sorption of HA/FA on soil minerals, and OH-concentrations affected dramatically the sorption behaviors of the organic acids with a pH larger than the ZPC of the colloid adsorbents.Sorption of HA/FA on soil minerals followed generally the orderof ferrihydrite > goethite > kaolinite ≒ montmorillonite. The FTIR absorption band at 1720 cm-1 disappeared while the bands at 1609 and 1575 cm-1 broaden and increased in intensity, demonstrating that the formation of a strong complex through a ligand exchange of the carboxylic groups of HA and quinones with OH on the
surfaces of Fe(oxy)hydroxides was the major reaction involved in the sorption process. The hollow-fiber filtration system could further fractionate efficiently HA into three categories of < 50, 50-100, and >100 kD HA, and high molecular weight (MWs) (i.e., > 100 kD HA) of HA exhibited a preferential sorption behavior on Fe(oxy)hydroxides. The preferential sorption of larger HA molecules may be attributed to the presence of higher contents of (1) aromatic carbon (helpful for increasing the hydrophobic interactions); (2) carboxylic group (the major reactive sites); and (3) carbon mass in their structures.
Key Words:
humin extraction; sequential exhaustive extraction; quinones; polyphenol polymerization; Fe(oxy)hydroxides; adsorption

中文摘要.................................................. I
ABSTRACT ............................................... III
TABLE OF CONTENTS ........................................ V
LIST OF TABLES......................................... VIII
LIST OF FIGURES ......................................... IX
CHAPTER 1 ................................................ 1
INTRODUCTION AND LITERATURE REVIEW ....................... 1
1.1. The Concepts and Importance of Humic Substances ... 1
1.2. Isolation and Fractionation of HSs................. 3
1.3. The Concepts of Humic Substances-like Materials ... 5
1.4. The Interactions of Humic Substances and Short-Ranged Ordered (SRO) Fe (oxy)hydroxide/mineral .................. 7
CHAPTER 2 ............................................... 12
A Comparison of the Compositional Differences Between Humic Fractions Isolated by the IHSS and Exhaustive Extraction Procedures............................................... 12
2.1. INTRODUCTION...................................... 12
2.2. MATERIALS AND METHODS ............................ 16
2.2.1. Sampling Site ............................... 16
2.2.2. Extraction of HAs and FAs ................... 17
2.2.3. Extraction of Humin .............................. 18
2.2.4. Sample Characterizations.......................... 22
2.2.4.1. UV-Vis Spectroscopy ......................... 22
2.2.4.2. Elemental Compositions ...................... 22
2.2.4.3. FT-IR Spectroscopy........................... 22
2.2.4.4. CPMAS 13C-NMR Spectroscopy................... 23
2.3. RESULTS AND DISCUSSION ............................. 23
2.3.1. Characteristics of HA and FA Extracted by IHSS Method .................................................. 23
2.3.2. Characteristics of HA and FA Fractions Extracted by SEE Method .............................................. 27
2.3.2.1. Isolation of Components with Base/Urea .... 33
2.3.3. Characteristics of Humins Isolated by IHSS and SEE Methods.................................................. 35
2.3.4. Cumulative Extraction Efficiency of SEE and IHSS Methods for the Volcanic Soil ........................... 39
2.3.5. Evaluation of the Suitability of the SEE Method for Isolations of Organic Matter from Soils in Different Climate Regions.................................................. 41
2.4. CONCLUSIONS ........................................ 44
CHAPTER 3................................................ 46
The Interactions of Humic Substances onto Clay and Fe-(oxy)hydroxide Colloid and Prolong the Quinones as Influenced by Chemical Structure and Molecular Size..................................................... 46
3.1. INTRODUCTION...................................... 46
3.2. MATERIALS AND METHODS ............................ 50
3.2.1. Sample Preparations.......................... 50
3.2.1.1. Clay Minerals ......................... 50
3.2.1.2. Syntheses of Fe(oxy)hydroxides .........51
3.2.2. Humic Substances ............................ 51
3.2.2.1. Extraction and Fractionation of HA and FA ......................................................... 51
3.2.3. Polymerization of Quinone ................... 52
3.2.4. Sorption of Humic Substances on Clay Minerals 53
3.2.4.1. Preparation of Stock Solution ......... 53
3.2.4.2. Sorption Kinetics ..................... 53
3.2.4.3. Sorption Kinetics of HA and FA on Goethite and Ferrihydrite at pH 4, 6 and 8 ....................... 54
3.2.4.4. Sorption Envelopes .................... 54
3.2.4.5. Sorption Isotherm...................... 54
3.2.5. Sample Characterization ..................... 55
3.2.5.1. Total Organic Carbon (TOC) ............ 55
3.2.5.2. Elemental Composition.................. 55
3.2.5.3. Fourier Transform Infrared Spectroscopy (FT-IR spectroscopy) .................................... 55
3.2.5.4. Carbon-13 Nuclear Magnetic Resonance (13C-NMR spectroscopy) ....................................... 56
3.2.5.5. High Performance Size Exclusion Chromatography (HPSEC) ................................................. 56
3.2.5.6. Gas Chromatography-Mass Spectrometry (GC-MS)...................................................... 56
3.2.6. Kinetic Models and Isotherm Models ............... 57
3.2.6.1. Kinetic Models .............................. 57
3.2.6.2. Isotherm Models ............................. 57
3.3. RESULTS AND DISCUSSION ............................. 58
3.3.1. Adsorption Kinetics of HA/FA on Goethite and Ferrihydrite ............................................ 58
3.3.2. Adsorption Envelopes of HA/FA on Goethite and Ferrihydrite............................................. 62
3.3.3. Adsorption Isotherm of HA/FA on Goethite and Ferrihydrite ............................................ 66
3.3.4. Prolonged Time to Oxidative Polymerization of Quinones in the Presence of Birnessite .................. 71
3.3.5. Comparisons of the Characteristics and Sorption of HA, FA and Quinones onto Goethite and Ferrihydrite and Discuss of Time-dependent Change in the MWs Distribution ......................................................... 81
3.3.6. The Possible Fates of Quinones into Soil Environment ......................................................... 95
3.4. CONCLUSIONS ........................................ 97
3.5. APPENDIX ........................................... 99
CHAPTER 4 .............................................. 102
CONCLUSIONS ............................................ 102
REFERENCE .............................................. 106

LIST OF TABLES
Table 2.1. The physical/chemical properties of volcanic Yamgming Mountain soil .................................. 17
Table 2.2. Elemental compositions (on ash-free basis), H/C, O/C and E4/E6 ratios of humic substances isolated by the IHSS and SEE method ..................................... 28
Table 2.3. Comparison of extracts from the Taiwanese volcanic soil and selected soils from Brazil, the USA, and Ireland ................................................. 43
Table 3.1. Kinetic parameters for the sorption of HA/FA on goethite and ferrihydrite ............................... 61
Table 3.2. Parameters of Langmuir and Freundlich isotherm models of HA onto goethite and ferrihydrite at pH 4, 6 and 8, respectively ......................................... 70
Table 3.3. Elemental composition (%) of HQ samples and comparisons with HA...................................... 75
Table 3.4. GC-MS peaks of HQ samples and HA identified by NIST Library ............................................ 80
Table 3.5. Integration of 13C-NMR spectra of HA and FA .. 84
Table 3.6. First and second order regressions for adsorption kinetics ................................................ 90

LIST OF FIGURES
Figure 2.1. Flow chart for organic matter extractions by (a) the IHSS and (b) sequential exhaustive extraction (SEE) procedures ............................................. 21
Figure 2.2. (a) Infrared and (b) 13C-NMR spectra of HAs and FAs isolated from extracts by the IHSS method ........... 26
Figure 2.3. Infrared spectra of (a) HAs, and of (b) FAs isolated by the exhaustive extraction (SEE) method (pH7,0.1 M NaOH + 6 M urea following the exhaustive extraction method. HA and FA samples isolated by the IHSS method are used for comparison. .................................... 30
Figure 2.4. 13C-NMR spectra of (a) HAs, and of (b) FAs isolated from the exhaustive extraction (SEE) method (pH7,M NaOH + 6 M urea following the exhaustive extractions. Spectra for the IHSS-HAs and FAs (isolated by the IHSS method) are used for comparison.......................... 32
Figure 2.5. Comparison of (a) Infrared and (b) 13C-NMR spectra of DMSO humin isolated from the residue of the SEE exhaustive extract, and of humin-1, humin-3,humin-8 isolated after 1, 3, and 8 extractions using the IHSS method and of the humin in the residual soil following the DMSO/H2SO4 extraction. ............................................. 38
Figure 2.6. A comparison of the organic carbon (OC) contents (%) isolated by the IHSS extraction method with the cumulative extraction percentage of the OC in the different extracts and in the residual materials following each stage of the SEE isolation. ................................... 40
Figure 3.1. Adsorption kinetics of HA on (a) goethite with initial of concentration (Ci) of 26 mg L-1 and solid solution ratio (SSR) of 0.51 g L-1 and (b) ferrihydrite with Ci of 105 mg L-1 and SSR of 0.46 g L-1 at pH 4, 6, and 8. ......................................................... 59
Figure 3.2. Adsorption kinetics of FA on goethite (SSR 0.52 g L-1) and ferrihydrite (SSR 0.24 g L-1) with initial of concentration of 18 and 35 mg L-1 at pH 4. .............. 60
Figure 3.3. Adsorption envelopes for (a) HA and (b) FA with clay and Fe(oxy)hydroxides (SSR approximately 0.5 g L-1 except ferrifydrite with FA)..............................65
Figure 3.4. Adsorption isotherm for HA adsorption onto goethite and ferrihydrite at pH 4, 6, and8 (initial of HA conc. 6-53 mg L-1 for goethite and initial HA conc.60-180 mg L-1 for ferrihydrite, SSR=0.5-0.55) (right Y axis represents adsorption normalize by surface area).................... 69
Figure 3.5. Effect of incubation time on absorbance (400-700 nm) of filtrates from reaction of hydroquinone (a) without and (b) with birnessite at pH 6. ........................ 71
Figure 3.6. (a) FT-IR spectra of HQ samples within 1, 7 and 20 days polymerization,denoted as HQ-1, HQ-7 and HQ-20, respectively. HA from Yangming volcanic mountain is provided for comparison. (b) Enlargement of 600-2000 cm-1 region.. 74
Figure 3.7. HPSEC spectra of HQ-1, HQ-7, HQ-20 and HA ... 76
Figure 3.8. Total ion chromatogram of GC-MS spectra of hydroquinone and HQ samples at 1 and 20 days, denoted as HQ-1 and HQ-20, respectively. HA is shown for comparison. .. 78
Figure 3.9. 3D profile of GC-MS spectra of hydroquinone and HQ samples at 1 and 20 days, denoted as HQ-1 and HQ-20, respectively. HA is shown for comparison. ............... 79
Figure 3.10. Comparison of adsorption isotherm for HA and FA onto goethite and ferrihydrite at pH 4 (initial of HA and FA conc. 6-53 mg L-1 for goethite and initial HA and FA conc. 60-180 mg L-1 for ferrihydrite, SSR=0.51-0.55). ........ 83
Figure 3.11. 13C-NMR spectra of HA and FA. .............. 84
Figure 3.12. Size distributions of fractionated humic acids analyzed by HPSEC. ...................................... 85
Figure 3.13. Sorption kinetics of HAs with different molecular weights onto ferrihydrite at pH 4 (with initial HA conc. of 8.7-9.94 mg L-1 and SSR of 0.05 g L-1). ........ 85
Figure 3.14. The HPSEC fractionation MWs of HA from the reaction solution (a) bulk (b) >100 kD (c) 50-100 kD and (d) <50 kD eliminated by ferrihydrite depending of time (0.05 g L-1, pH 4). ............................................. 86
Figure 3.15. Adsorption kinetics of HA, HQ-20, HQ-7, and HQ-1 on (a) ferrihydrite and (b) goethite at pH 4 and 25 oC with a suspension density of 0.25 and 0.62 g L-1, respectively ........................................... 89
Figure 3.16. Time-dependent changes for MW distribution of HQ-20 upon interaction with ferrihydrite. ............... 91
Figure 3.17. FTIR spectra of HA and FA. ................. 92
Figure 3.18. FTIR spectra of HA before and after interaction with (a) ferrihydrite and (b) goethite and spectra of HQ-20 before and after interaction with (c) ferrihydrite. ..... 94
Figure 3.19. The possible fate of hydroquinone into soil environment. ............................................ 96
Figure A3.1. XRD patterns of the solids residue separated from suspension by centrifugation after different reaction time between hydroquinone and birnessite................. 99
Figure A3.2. (a) FTIR spectra of the solids residue separated from suspension by centrifugation after different reaction time between hydroquinone and birnessite (b) comparison FTIR spectra of original birnessite and hydroquinone-birnessite system after 360 min. .......... 100
Fig. A3.3. Oxidative polymerization of hydroquinone with MnO2 by HPSEC. ......................................... 101

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