臺灣博碩士論文加值系統

五氯酚 (pentachlorophenol, PCP) 過去使用於木材保護劑與殺蟲劑，其為持久性之有機污染物 (persistent organic pollutants, POP) 且具致癌性。由於不適當儲存與廢棄這些持久性有機污染物，世界已有許多POP污染場址，台灣已發現PCP污染場址。而奈米零價鐵鈀 (palladium/iron, Pd0/Fe0) 顆粒之技術已發展於現地化學還原含鹵素有機污染物。
此研究以批次實驗系統應用自行合成之奈米Pd0/Fe0移除PCP，評估以供復育污染場址之潛力。由於增加奈米Pd0/Fe0劑量使其具較多之Pd0/Fe0表面以還原PCP，故其降解速率提高。奈米Pd0/Fe0顆粒之Pd重量百分比於0.02 wt %至0.054 wt %之間，則增加Pd重量百分比則會提高PCP之降解速率，但若增加Pd之重量百分比至 0.13 wt %，則會降低PCP之降解速率。PCP初始濃度之影響可以Langmuir-Hinshelwood模式描述，另外經計算求得之活化能為29 kJ/mol，此結果顯示利用奈米Pd0/Fe0降解PCP為一表面控制反應。
地下水中常見之陰離子會抑制PCP之降解效率，其抑制的順序依序為Cl- < HCO3- < SO42- < HPO42- < NO3-。除了NO3-與HCO3-之外，此抑制順序與這些陰離子與鐵氧化物產生複合物之親合力順序相符，抑制程度隨其濃度增加而增加。而NO3-會與PCP競爭電子而使其還原成其他含氮化合物，所以抑制PCP之降解效率最顯著。HCO3-因其具有pH緩衝能力而減少抑制PCP之降解效率。
在SO42-為背景陰離子之情況下，因如前所述，SO42-會抑制奈米Pd0/Fe0降解PCP，又因Na+之高還原電位，所以Na+應不影響奈米Pd0/Fe0降解PCP，可作為比較之基準。所以相較於相同濃度之下，Mg2+、Cu2+、Ni2+與Fe3+則可促進PCP之降解效率，其促進之順序依序為Cu2+ < Mg2+ < Fe3+ < Ni2+。此外，Ni2+即使未扣除SO42-之影響，其亦會促進PCP之降解效率。而在以Cl-為背景陰離子之情況下，相同地以Cl-為抑制奈米Pd0/Fe0降解PCP之原因，所以NaCl對利用奈米Pd0/Fe0降解PCP的影響作為比較基準。Mg2+、Ni2+與Fe3+則可促進PCP之降解效率，其促進之順序依序為Mg2+ < Fe3+ < Ni2+。但Cu2+會抑制PCP之降解效率。此外，Ni2+即使未扣除Cl-之影響，其亦會促進PCP之降解效率。
於土壤溶液方面，增加鹿港系土壤溶液之濃度則會降低PCP之降解速率。由於土壤溶液中含不同陰陽離子，土壤溶液中之陰離子會與鐵形成鐵複合物而於奈米Pd0/Fe0顆粒上產生礦物沉澱，進而降低其表面活性而降低反應奈米Pd0/Fe0之降解效率。
在反應過程中偵測到四氯酚、三氯酚、二氯酚、氯酚以及酚為其副產物，推測降解反應為多步降解過程。奈米Pd0/Fe0於PCP之鄰位(othro)及間位(meta)取代基之脫氯作用較對位(para)取代基多，原因為移除PCP之氯取代基位置取決於減少PCP之立體結構障礙。
本研究亦有效地降解鹿港系土壤與PCP污染土壤中之PCP，PCP於鹿港系土壤中之降解速率較於PCP污染土壤中之降解速率低。由於鹿港系土壤中之NO3-濃度較PCP污染土壤中高而抑制PCP之還原。土壤中之碳含量百分比亦會影響PCP之降解速率，因碳含量百分比高之土壤增加PCP於土壤之吸附作用而抑制奈米Pd0/Fe0降解PCP。而鹿港系土壤之碳含量百分比較PCP污染土壤高，故其會降低PCP降解速率。而另外，土壤膠體亦會影響奈米Pd0/Fe0於土壤中降解PCP之應用。
此結果可更加了解利用奈米Pd0/Fe0降解PCP污染場址復育之設計方式與預期其處理效果。由於奈米Pd0/Fe0具快速還原PCP之能力，故利用其降解PCP可作為整治PCP污染場址之有效方式。

Pentachlorophenol (PCP), one of persistent organic pollutant (POP) and also a carcinogenic compound, has been used widely as wood preservative and pesticides in the past. Due to the improper storage and disposal of these persistent organic pollutants, several POP contaminated sites were found in the world, especially a PCP contaminated site in Taiwan. Nanoscale zerovalent metal particles were developed to in-situ chemically degrade poly-halogenated aromatic contaminants.
Nanoscale Pd0/Fe0 particles we synthesized were used to evaluate the potential of Pd0/Fe0 nanoparticles for the remediation the PCP contaminated sites. The effects of nanoscale Pd0/Fe0 dosage, palladium loading, PCP concentrations, and aqueous parameters such as different concentration of various common cations and anions, temperature, and pH, on the degradation of PCP were performed. And the removal experiments of PCP in PCP contaminated soil and Lukang soil were investigated.
The increase of nanoscale Pd0/Fe0 dosage results in the increase in PCP degradation rate and efficiency due to more Pd0/Fe0 surface to reduce PCP. With the increase of the palladium loading percentage from 0.02 wt % to 0.054 wt %, PCP degradation rates increased but the degradation rate slightly decreased with the increase of the palladium loading percentage from 0.054 wt % to 0.13 wt %. It seems a common characteristic for catalyst. The effect of initial PCP concentrations on the removal rate can be described by a surface kinetic model, Langmuir-Hinshelwood model. The estimated activation energy of the dechlorination reactions of 29 kJ/mol indicates that the degradation of PCP on Pd0/Fe0 nanoparticle is a surface-control mechanism.
The effects of common cations and anions on the degradation of PCP with Pd0/Fe0 nanoparticles were needed to be studied. Common groundwater anions inhibited PCP reduction in increasing order of Cl- < HCO3- < SO42- < HPO42- < NO3-, which is generally consistent with their affinity to form complexes with iron oxide except NO3- and HCO3-. Generally, the inhibition effect increased with the increase of anion concentrations. Nitrate may compete electrons offered from iron with PCP to reduce other nitrogen species. The smallest pH variation before and after experiments indicates that HCO3- has pH buffer capacity.
In the presence of sulfate, which can cause for inhibition, cation Na+ was proposed to have no influence the degradation efficiencies of PCP and used as a reference. Cations Mg2+, Cu2+, Ni2+ and Fe3+ could facilitate the degradation efficiencies of PCP with nanoscale Pd0/Fe0 particles in increasing order of Cu2+ < Mg2+ < Fe3+ < Ni2+. With chloride ions, the smallest effect in our anions, the decrease trend of PCP degradation for these cations is similar, except Cu2+. Moreover, Ni2+ could increase the degradation kinetics and efficiency of PCP with Pd0/Fe0 nano-particles although either sulfate or chloride ions inhibit the degradation behaviors.
The increase of concentration of soil solution showed a negative effect on the degradation rate constants of PCP by nanoscale Pd0/Fe0 particles. Soil solution containing common anions may inhibit the degradation. The anions in soil solutions would form iron-complex or metal oxides precipitation on nanoscale Pd0/Fe0 particles to decrease the surface reactivity.
According to the instant occurrence of degraded byproducts, tetrachlorophenols, trichlorophenols, dichlorophenols, chlorophenols, and phenol during the reaction, multiple dechlorination process is proposed for the PCP degradation reaction on the nanoscale Pd0/Fe0 particles. The chlorine atom at the ortho and meta positions can be more easily dechlorinated than that at para position on PCP. It results from the steric effect of chloride on PCP structure.
An efficient degradation of the PCP with nanoscale Pd0/Fe0 particles in soils was performed in this study. The degradation efficiency and kinetics of PCP in Lukang soil are less than these in PCP contaminated soil due to the higher nitrate concentration and higher soil organic carbon in Lukang soil than PCP contaminated soil. Nitrate ions inhibit the reduction of PCP. The low degradation efficiency could also result from larger adsorption of PCP in Lukang soil. The colloids in soils may also decrease the degradation efficiency in the application of removal of PCP with nanoscale Pd0/Fe0 particles so a higher amount of Pd/Fe nanoparticles was used in soil than in solution.
These better understandings can facilitate the remediation design and the prediction of treatment efficiency of PCP with nanoscale Pd0/Fe0 particles. Nanoscale Pd0/Fe0 particles could be a potential remediation agent for PCP contaminated sites because their rapid removal reactions of PCP occur in soils and groundwater and an excess of the nanoscale Pd0/Fe0 particles in the soils can provide an extra reducing power to reduce the target polyhalogenated aromatic compounds of PCP.

Abstract i
摘要 iii
Tables of Contents v

Abstract i
摘要 iii
Tables of Contents v
List of Tables ix
List of Figures xi
Chapter 1 Introduction 1
1.1 Background 1
1.2 Scope and Objectives 2
Chapter 2 Literatures Review 4
2.1 Introduction of pentachlorophenol 4
2.2 Human toxicology of pentachlorophenol 7
2.3 The fate of pentachlorophenol in the environment 8
2.4 The cases of organic compounds contaminated sites in Taiwan 9
2.5 The zero-valent iron 13
2.6 The Pd0/Fe0 bimetallic particles 18
2.7 Application of nanoscale zero-valent iron and nanoscale Pd0/Fe0 particles on soil and groundwater environment 24
2.8 The factors that could affect removal of chlorinated organic compounds with zero-valent iron and Pd0/Fe0 particles 25
2.8.1 Temperature 25
2.8.2 pH value 26
2.8.3 structure 27
2.8.4 ions 27
Chapter 3 Materials and Methods 29
3.1 Chemicals and standards 29
3.2 Extraction and analysis methods of pentachlorophenol 30
3.3 Synthesis of nanoscale palladium/iron particles 31
3.4 Characterization of the synthesized nanoscale Pd/Fe particles 32
3.4.1 Field-emission scanning electron microscope, FE-SEM 32
3.4.2 Transmission electron microscope, TEM 33
3.4.3 Photon correlation spectroscopy, PCS 33
3.4.4 X-ray Diffraction, XRD 33
3.4.5 BET (Brunauer-Emmett-Teuller) surface area 34
3.5 Batch PCP degradation experiments 35
3.6 Effect of environmental factors on degradation of PCP with nanoscale Pd0/Fe0 particles 35
3.7 Analysis of soils and soil solutions 37
3.8 Extraction efficiency of PCP in soils with microwave-assisted extraction 37
3.9 Batch PCP degradation experiments in soils 38
3.10 Chemical reduction rate constants 38
Chapter 4 Results and Discussion 39
4.1 Characterization of nanoscale Pd0/Fe0 particles 39
4.2 The XRD patterns of nanoscale Pd0/Fe0 particles before and after reactions. 43
4.3 Extraction efficiency of PCP in aqueous solutions, soil solutions, and soils. 45
4.3.1 Extraction efficiency of PCP in aqueous and soil solutions. 45
4.3.2 Extraction efficiency of PCP in soils with microwave-assisted extraction. 46
4.4 Effect of palladium percentage on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 48
4.5 Effect of the dosage of nanoscale Pd0/Fe0 particles on the degradation kinetics of PCP by nanoscale Pd0/Fe0. 51
4.6 Effect of initial concentrations of PCP on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 53
4.7 Effect of temperature on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 57
4.8 Effect of pH on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 61
4.9 Effect of oxygen on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 63
4.10 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles in aerobic and anaerobic conditions 64
4.11 Effect of various anions (NO3-, Cl-, HCO3-, SO42- and HPO42-) on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 68
4.11.1 Effect of nitrate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 68
4.11.2 Effect of chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 72
4.11.3 Effect of hydrogen carbonate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 76
4.11.4 Effect of hydrogen phosphate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 80
4.11.5 Effect of sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 84
4.12 Effect of various cations (Fe3+, Cu2+, Ni2+, Mg2+ and Na+) on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 91
4.12.1 Effect of sodium sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 91
4.12.2 Effect of magnesium sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 94
4.12.3 Effect of copper sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 98
4.12.4 Effect of nickel sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 102
4.12.5 Effect of ferric sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 106
4.12.6 Effect of sodium chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 113
4.12.7 Effect of magnesium chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 116
4.12.8 Effect of copper chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 119
4.12.9 Effect of nickel chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 123
4.12.10 Effect of ferric chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles 127
4.13 Degradation of PCP with nanoscale Pd0/Fe0 in soil solutions 134
4-16 The proposed dechlorination pathways of PCP by nanoscale Pd0/Fe0 particles 139
4.15 Degradation of PCP with nanoscale Pd0/Fe0 in soils 141
Chapter 5 Conclusions 144
Chapter 6 Reference 146
Appendix 153

List of Tables
Table 2-1 Selected physicochemical properties of phenol and chlorophenols. 10
Table 2-1 Selected physicochemical properties of phenol and chlorophenols (continuous). 11
Table 2-2 The pollution sites of soil and groundwater that have been announced. 12
Table 2-3 The standard reduction potentials of various elements for aqueous solutions at 25℃ (Speight, 2005) 21
Table 3-1 Composition and the content of the standard solution DIN EN 12673 Chlorophenols. 30
Table 3-2 Operation condition of Agilent 6890 GC-μECD. 31
Table 4-1 Dechlorination rate constants of PCP by nanoscale Pd0/Fe0 at various percentages of palladium. 49
Table 4-2 Dechlorination rate constants of PCP by various amounts of nanoscale Pd0/Fe0 52
Table 4-3 Dechlorination rate constants of PCP and the pH variation before and after reaction in various initial concentrations of PCP. 56
Table 4-4 Dechlorination rate constants of PCP by nanoscale Pd0/Fe0 at 5℃, 15℃, 25℃, 35℃ and 45℃. 60
Table 4-5 Dechlorination rate constants of PCP and the pH variation in various pH conditions. 62
Table 4-6 Dechlorination rate constants and degradation efficiency of PCP by nanoscale Pd0/Fe0 particles containing various anions. 89
Table 4-7 Stability constants for formation of complexes from metals and ligands (Morel and Hering, 1993; Benjamin, 2000). 89
Table 4-8 The pH variation before and after dechlorination of PCP with nanoscale Pd0/Fe0 particles containing various anions. 90
Table 4-9 Dechlorination rate constants of PCP by nanoscale Pd0/Fe0 containing various cations in the presence of sulfate. 112
Table 4-10 The pH variation before and after reaction of PCP with nanoscale Pd0/Fe0 containing various cations in the presence sulfate. 112
Table 4-11 Dechlorination rate constants of PCP by nanoscale Pd0/Fe0 containing various cations in the presence of chloride. 133
Table 4-12 The pH variation before and after reaction of PCP with nanoscale Pd0/Fe0 containing various cations in the presence of chloride. 133
Table 4-13 The dechlorination rate constants of PCP with nanoscale Pd0/Fe0 and the pH variation before and after reactions in soil solutions 135
Table 4-14 The ion concentrations and carbon contents in soils (2000 g/L) 136
Table 4-15 Dechlorination rate constants of PCP with nanoscale Pd0/Fe0 particles and the pH variation before and after reaction in soils. 143

List of Figures
Figure 2-1 The structure of pentachlorophenol. 4
Figure 2-2 Effect of pH on the solubility of pentachlorophenol at 25℃. (Huang et al., 2000). 5
Figure 2-3 The species distribution for pentachlorophenol system as a function of pH (Fein, 1996). 6
Figure 2-4 Proposed pathways for reductive dehalogenation in anoxic Fe0-H2O system (Matheson and Tratnyek, 1994). 15
Figure 2-5 pe-PH stability diagram for iron oxides and hydroxides at 25℃ (Stumm and Morgan, 1981). 16
Figure 2-6 A conceptual model for the hydrodechlorination of chlorinated organic compounds. Atomic hydrogen is expressed as H*. 20
Figure 2-7 Nanoscale iron particles for in situ remediation (Zhang, 2003). 25
Figure 4-1 The particle size analysis of nanoscale Pd0/Fe0 by photon correlation spectroscopy (PCS). 40
Figure 4-2 Scanning electron microscopy (SEM) image of nanoscale Pd0/Fe0 particles. 40
Figure 4-3 Transmission electron microscopy (TEM) image of nanoscale Pd0/Fe0 particles. 41
Figure 4-4 Scanning electron microscopy energy-dispersive spectroscopy (SEM-EDS) spectrum for nanoscale Pd0/Fe0 particles. 41
Figure 4-5 The adsorption and desorption isotherms of nitrogen on nanoscale Pd0/Fe0 particles. 42
Figure 4-6 X-ray diffraction spectrum of nanoscale Pd0/Fe0 with 0.054% palladium before reactions with PCP. 44
Figure 4-7 X-ray diffraction spectrum of nanoscale Pd0/Fe0 with 0.054% palladium after reactions with PCP. 44
Figure 4-8 Extraction recovery of PCP in water in different extraction time. 45
Figure 4-9 Extraction recovery of PCP in Lukang soil solution in different extraction time. 46
Figure 4-10 Effect of solvent volumes on the extraction efficiency of PCP with microwave-assisted extraction. 47
Figure 4-11 Effect of PCP concentrations on the extraction efficiency of PCP with microwave-assisted extraction. 47
Figure 4-12 Effect of palladium percentage on the degradation kinetics of PCP by nanoscale Pd0/Fe0. 49
Figure 4-13 Rate constant for the reduction of PCP by Pd0/Fe0 bimetallic particles as a function of the palladium content. 50
Figure 4-14 Effect of nanoscale Pd0/Fe0 dosage on the degradation kinetics of PCP by nanoscale Pd0/Fe0. 52
Figure 4-15 Effect of initial concentrations of PCP on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 55
Figure 4-16 Linear transform plot of 1/r0 vs. 1/C0. 56
Figure 4-17 Evolution of chloride during dechlorination of PCP by nanoscale Pd0/Fe0 particles. 57
Figure 4-18 Effect of temperature (5℃, 15℃, 25℃, 35℃ and 45℃) on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 59
Figure 4-19 The plot of 1/T versus ln(kobs). 60
Figure 4-20 Effect of pH on the on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 62
Figure 4-21 Effect of oxygen on the on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 64
Figure 4-22 Byproduct distribution during dechlorination of 5 mg/L PCP by 12.5 g/L nanoscale Pd0/Fe0 particles (A) TeCP and PCP; (B) Phenol, CP, DCP and TCP. 65
Figure 4-23 Byproduct distribution during dechlorination of 10 mg/L PCP by 12.5 g/L nanoscale Pd0/Fe0 particles (A) TeCP and PCP; (B) Phenol, CP, DCP and TCP.. 66
Figure 4-24 Byproduct distribution during dechlorination of 5 mg/L PCP by 12.5 g/L nanoscale Pd0/Fe0 particles in anaerobic condition (A) TeCP and PCP; (B) Phenol, CP, DCP and TCP.. 67
Figure 4-25 Effect of different concentration of nitrate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 69
Figure 4-26 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM nitrate ion (A) TeCP and PCP; (B) CP, DCP and TCP. 70
Figure 4-27 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM nitrate ion (A) TeCP and PCP; (B) CP, DCP and TCP. 71
Figure 4-28 Effect of different concentration of chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 73
Figure 4-29 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM chloride ion (A) TeCP and PCP; (B) CP, DCP and TCP. 74
Figure 4-30 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM chloride ion (A) TeCP and PCP; (B) CP, DCP and TCP. 75
Figure 4-31 Effect of different concentration of hydrogen carbonate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 77
Figure 4-32 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM bicarbonate ion (A) TeCP and PCP; (B) CP, DCP and TCP. 78
Figure 4-33 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM bicarbonate ion (A) TeCP and PCP; (B) CP, DCP and TCP. 79
Figure 4-34 Effect of different concentration of hydrogen phosphate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 81
Figure 4-35 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM hydrogen phosphate ion (A) TeCP and PCP; (B) CP, DCP and TCP. 82
Figure 4-36 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM hydrogen phosphate ion (A) TeCP and PCP; (B) CP, DCP and TCP. 83
Figure 4-37 Effect of different concentration of sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0. 85
Figure 4-38 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM sulfate ion (A) TeCP and PCP; (B) CP, DCP and TCP. 86
Figure 4-39 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM sulfate ion (A) TeCP and PCP; (B) CP, DCP and TCP. 87
Figure 4-40 Effect of 10 mN various anions (HPO42-, SO42-, HCO3- , NO3- and Cl-) on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 88
Figure 4-41 Effect of different concentration of sodium sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 91
Figure 4-42 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM sodium sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 92
Figure 4-43 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM sodium sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 93
Figure 4-44 Effect of different concentration of magnesium sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 95
Figure 4-45 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM magnesium sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 96
Figure 4-46 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM magnesium sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 97
Figure 4-47 Effect of different concentration of copper sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 99
Figure 4-48 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM cupper sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 100
Figure 4-49 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM cupper sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 101
Figure 4-50 Effect of different concentration of nickel sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 103
Figure 4-51 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM nickel sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 104
Figure 4-52 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM nickel sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 105
Figure 4-53 Effect of different concentration of ferric sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 107
Figure 4-54 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 3.33 mM ferric sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 108
Figure 4-55 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM ferric sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 109
Figure 4-56 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM ferric sulfate (A) TeCP and PCP; (B) CP, DCP and TCP. 110
Figure 4-57 Effect of 10 mN various caions (Na+, Mg2+, Cu2+, Ni2+ and Fe3+) in the presence of sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 111
Figure 4-58 Effect of different concentration of sodium sulfate on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 113
Figure 4-59 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM sodium chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 114
Figure 4-60 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM sodium chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 115
Figure 4-61 The effect of different concentration of magnesium chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 116
Figure 4-62 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM magnesium chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 117
Figure 4-63 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM magnesium chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 118
Figure 4-64 The effect of different concentration of copper chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 120
Figure 4-65 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM copper chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 121
Figure 4-66 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM copper chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 122
Figure 4-67 The effect of different concentration of nickel chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 124
Figure 4-68 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM nickel chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 125
Figure 4-69 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM nickel chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 126
Figure 4-70 The effect of different concentration of ferric chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles. 128
Figure 4-71 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 3.33 mM ferric chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 129
Figure 4-72 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 5 mM ferric chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 130
Figure 4-73 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles under the existence of 10 mM ferric chloride (A) TeCP and PCP; (B) CP, DCP and TCP. 131
Figure 4-74 Effect of various cations (Fe3+, Cu2+, Ni2+, Mg2+, and Na+) in the presence of chloride on the degradation kinetics of PCP by nanoscale Pd0/Fe0 particles at 10 mN. 132
Figure 4-75 Degradation of PCP with nanoscale Pd0/Fe0 in Lukang soil solution. 135
Figure 4-76 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles in 25 g/L Lukang soil solution. 137
Figure 4-77 Byproduct distribution during dechlorination of PCP by nanoscale Pd0/Fe0 particles in 50 g/L Lukang soil solution. 138
Figure 4-78 The proposed dechlorination pathways of PCP by nanoscale Pd0/Fe0 particles. 140
Figure 4-79 Degradation of PCP with nanoscale Pd0/Fe0 in PCP contaminated soil and Lukang soil. 142

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