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Removal of polycyclic aromatic hydrocarbons from deionized water and landfill leachate by using modified… Hedayati, Monirehsadat 2018

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REMOVAL OF POLYCYCLIC AROMATIC HYDROCARBON FROM DEIONIZED WATER & LANDFILL LEACHATE BY USING MODIFIED CLINOPTILOLITES  by  Monirehsadat Hedayati  M.Eng, The University of British Columbia, 2012  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF  MASTER OF APPLIED SCIENCE  in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Civil Engineering)  THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver)  June 2018  © Monirehsadat Hedayati, 2018  The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, a thesis/dissertation entitled:  REMOVAL OF POLYCYCLIC AROMATIC HYDROCARBON FROM DEIONIZED WATER & LANDFILL LEACHATE BY USING MODIFIED CLINOPTILOLITES  submitted by Monirehsadat Hedayati in partial fulfillment of the requirements for the degree of Master of Applied Science in Department of Civil Engineering (Geo-Environmental Engineering)  Examining Committee: Professor Loretta Li Supervisor  Dr. Jongho Lee Supervisory Committee Member   Supervisory Committee Member  Additional Examiner   Additional Supervisory Committee Members:  Supervisory Committee Member  Supervisory Committee Member ii  Abstract Polycyclic aromatic hydrocarbons (PAHs) are toxic, carcinogenic, and persistent in the environment. Clinoptilolite, a type of natural zeolite, was modified with cetylpridinium chloride (CPC), didodecyldimethylammonium bromide (DDAB), hexadecyltrimethylammonium bromide (HDTMA-Br), and tetramethylammonium chloride (TMA) separately as potential adsorbents for removal of PAHs. Leachability and thermal stability of modified clinoptilolites were investigated. Adsorption capacity, kinetics, sorbent dosage, pH, temperature, and competition effects were studied adopting batch adsorption tests using deionized water spiked with five PAHs (anthracene (50 µg/L), fluoranthene (100 µg/L), fluorene (100 µg/L), phenanthrene (100 µg/L), and pyrene (100 µg/L)). The leachability and thermal stability results indicated that CPC and DDAB modified clinoptilolites were less leachable and more stable compared to HDTMA modified clinoptilolites. The non-modified clinoptilolite, and TMA modified clinoptilolite exhibited <66 % PAH removals from water solution. However, CPC, DDAB, and HDTMA modified clinoptilolites retained >93 % of five PAHs after 24 hours at 1:100 solid: liquid ratio and met the local water quality criteria, except for fluorene on HDTMA modified clinoptilolite which retained >83%. For CPC and DDAB modified clinoptilolites, more than 80% of all PAHs were retained within 15 minutes and maximum adsorption was reached in < 2 hours. Three kinetic models were applied using pseudo-first, pseudo-second-order, and intra particle equations, and the results are well represented by the pseudo-second-order equation. With a 1:200 solid: liquid ratio, the removal of anthracene, fluoranthene, and pyrene were above 90, 80, and 70 % on CPC, DDAB, and HDTMA modified clinoptilolites, respectively. After performing 21 successive batch adsorption tests on CPC, DDAB, and HDTMA modified clinoptilolites, the PAHs had accumulated about 0.7 to 1.5 mg per gram of clinoptilolite. PAH leachabilities from iii  these loaded PAHs were less than 5% after conducting a stability test. Different pH values and temperatures have insignificant effects on adsorption of PAHs, except for fluorene. Different pH values changed the adsorption of fluorene only slightly on HDTMA modified clinoptilolite. When temperature was increased, fluorene adsorption was decreased by <13% on modified clinoptilolites. CPC and DDAB modified clinoptilolites, were able to remove all five PAHs efficiently (>95%) from landfill leachate spiked with PAHs.    iv  Lay Summary  Polycyclic aromatic hydrocarbons (PAHs) are toxic, mutagenic and carcinogenic. These PAHs can be detected in wastewater, stormwater, groundwater, and water that comes from landfills called leachate. One of methods to remove these compounds from water is an adsorption method that is efficient and inexpensive to conduct. To perform the adsorption test, an adsorbent that is capable of removing of PAHs is needed. The clinoptilolite mineral has been used to remove the metals from water. However, clinoptilolite is not able to remove the PAHs efficiently. Therefore, clinoptilolite was modified with cationic surfactants, an organic compound, to improve its surface properties. These modified clinoptilolites have been used to uptake PAHs from aqueous solutions including from deionized water and landfill leachate very effectively (more than 90%). The PAHs were accumulated significantly on modified clinoptilolites. Changing in temperature and pH values did not affect the PAHs adsorption very significantly.   v  Preface This thesis is original, unpublished, and independent work by the author, Monirehsadat Hedayati. The author designed the research plan and performed all experiments under the supervision of Professor Loretta Y. Li The author contribution for this study is as follows: • Conducted modification of clinoptilolite  • Performed all batch adsorption tests to remove PAHs  • Carried out all sample liquid –liquid extraction, solvent evaporation, and clean-up  • Chemically analyzed all surfactants using a TOC analyzer and UV/Vis, and PAHs using a GC/MS • Processed, analyzed, graphed, and interpreted results of all data All experiments and analysis were carried out at the Environmental Lab at Civil Engineering Department at UBC in Vancouver, British Columbia. Abstracts and presentation arising from this research: 1) Monireh S. Hedayati, Loretta Y. Li, 2017, “Removal of PAHs Compounds from Aqueous Solution by Modified clinoptilolites”, the Bettering Environmental Stewardship & Technology Conference (The Best 2017), British Columbia Environment Industry Association (BCEIA), May 10- 12, abstract & presentation, Whistler, British Columbia.   2) Loretta Y. Li, Monireh S. Hedayati, Chris Johnston, 2017, “Exploratory Study of modified –Zeolites as Sorbents for Poly- and Perfluoroalkyl Substances and Polycyclic Aromatic Hydrocarbons in Stormwater Runoff”, 16th International Clay Conference (16th ICC), July 17-21, abstract, Granada, Spain.  vi  Table of Contents  Abstract ......................................................................................................................................... iii Lay Summary .................................................................................................................................v Preface ........................................................................................................................................... vi Table of Contents ........................................................................................................................ vii List of Tables ................................................................................................................................ xi List of Figures ............................................................................................................................. xiii List of Symbols ......................................................................................................................... xviii List of Abbreviations ...................................................................................................................xx Acknowledgements ................................................................................................................... xxii Chapter 1: Introduction ................................................................................................................1 1.1 Problem Statement .......................................................................................................... 1 1.2 Research Objectives and Work Plan ............................................................................... 4 Chapter 2: Literature Review .......................................................................................................7 2.1 Polycyclic Aromatic Hydrocarbons (PAHs) in the Environment ................................... 7 2.2 Natural Zeolite .............................................................................................................. 13 2.3 Application of Zeolite ................................................................................................... 14 2.4 Cationic Surfactants Modified Zeolite .......................................................................... 15 2.4.1 Adsorption Models of Surfactant on Solids Surface ................................................. 17 2.4.2 Environmental Impacts of Cationic Surfactants ....................................................... 19 2.4.3 Contaminants Removal from Aqueous Solution by Using Modified Minerals ........ 20 2.5 Removal Methods of PAHs from Aqueous Solution .................................................... 22 vii  Chapter 3: Materials and Methodologies ..................................................................................28 3.1 Materials & Instruments ............................................................................................... 28 3.2 Na-Pre-treatment of Clinoptilolite ................................................................................ 29 3.3 Modification of Clinoptilolite ....................................................................................... 30 3.4 Thermal Effect on Stability of the Surfactants on Modified Clinoptilolites ................. 34 3.5 Batch Adsorption Test Procedure ................................................................................. 35 3.6 Factors Affecting the Removal Capacity of Modified Clinoptilolites .......................... 36 3.6.1 Adsorption Kinetics .................................................................................................. 37 3.6.2 Effect of Different Adsorbent Dosage ...................................................................... 38 3.6.3 Adsorption Capacity of Adsorbents to Remove the PAHs ....................................... 38 3.6.4 Leachability of Adsorbed PAHs from Modified Clinoptilolites............................... 39 3.6.5 Adsorption Competition of Single Vs Mixture PAHs .............................................. 40 3.6.6 Effect of pH............................................................................................................... 40 3.6.7 Effect of Temperature ............................................................................................... 41 3.6.8 PAH Removals from Landfill Leachate Using Modified Clinoptilolites ................. 41 3.7 QC/QA .......................................................................................................................... 42 3.8 Data Analysis & Interpretation ..................................................................................... 42 Chapter 4: Results and Discussions............................................................................................46 4.1 Modification and Leachability of Surfactant from Modified Clinoptilolites................ 46 4.2 Temperature Effect on Modified Clinoptilolite Stability .............................................. 53 4.3 PAH Removals by Using Different Adsorbents ........................................................... 55 4.4 Adsorption Kinetics of PAHs ....................................................................................... 60 4.5 Effect of Dosage Adsorbent Optimization for Treatment Process ............................... 70 viii  4.6 Adsorption Capacity of Adsorbent for PAH Adsorption .............................................. 73 4.7 Stability of Adsorbed PAHs on Modified Clinoptilolites ............................................. 79 4.8 Competition Effect of Single versus Mixture PAH Adsorptions.................................. 85 4.9 Effect of pH on PAH Removals.................................................................................... 88 4.10 Effect of Temperature on PAH Removals .................................................................... 93 4.11 Removal of PAHs from Landfill Leachate Using Modified Clinoptilolites ................. 98 Chapter 5: Conclusion & Recommendations ..........................................................................105 5.1 Conclusion .................................................................................................................. 105 5.2 Recommendations ....................................................................................................... 107 References ...................................................................................................................................109 Appendices ..................................................................................................................................126 Appendix A Surfactants & PAHs ........................................................................................... 126 A.1 US- EPA’s 16 Priority Pollutant PAHs .................................................................. 126 A.2 Occurrence of PAHs in the Environment ............................................................... 128 A.3 Water Quality Criteria............................................................................................. 129 Appendix B Modification of Clinoptilolite............................................................................. 131 B.1 Main Properties of Bear River Zeolite .................................................................... 131 B.2 Chemical Structure of Cationic Surfactants ............................................................ 132 B.3 Properties of Cationic Surfactants .......................................................................... 133 B.4 Preparation of Pretreated Clinoptilolite .................................................................. 133 B.5 Modification of Clinoptilolite with CPC ................................................................ 134 B.6 Modification of Clinoptilolite with DDAB............................................................. 134 B.7 Modification of Clinoptilolite with HDTMA-Br .................................................... 134 ix  B.8 Modification of Clinoptilolite with TMA-Cl .......................................................... 135 B.9 Residual Concentration of CPC in Supernatant after Modification and Washes ... 136 B.10 Residual Concentration of DDAB in Supernatant after Modification and Washes 138 B.11 Residual Concentration of HDTAM in Supernatant after Modification and Washes ..   ................................................................................................................................. 140 B.12 Residual Concentration of TMA in Supernatant after Modification and Washes .. 142 B.13 Thermal Stability of CPC on CPC-MC at Different Temperatures ........................ 144 B.14 Thermal Stability of DDAB on DDAB-MC at Different Temperatures ................ 145 B.15 Thermal Stability of HDTMA on HDTMA-MC at Different Temperatures .......... 146 Appendix C Batch Adsorption Test ........................................................................................ 147 C.1 Batch Adsorption Test Procedure ........................................................................... 147 C.2 Removal of PAHs by Using Different Adsorbents ................................................. 148 C.3 PAH Adsorption Kinetics ....................................................................................... 151 C.4 Adsorbent Dosage Effect ........................................................................................ 165 C.5 PAH Adsorption Capacity of Adsorbents ............................................................... 175 C.6 Stability of Loaded PAHs from Adsorbents ........................................................... 191 C.7 Competition Effect of Fluoranthene ....................................................................... 192 C.8 Effect of pH on PAH Adsorptions .......................................................................... 193 C.9 Effect of Temperatures on PAH Adsorptions ......................................................... 199 C.10 Removal of PAHs from Landfill Leachate ............................................................. 207 Appendix D Equations ............................................................................................................ 210 D.1 Coulomb's Law ....................................................................................................... 210 D.2 Thermodynamic Sorption Properties ...................................................................... 210 x  List of Tables Table 2.1 Concentrations of PAHs in the rivers, and groundwater .............................................. 10 Table 2.2 Environmental impact of cation surfactants ................................................................. 20 Table 2.3 List of adsorbents, modification agents, and removal contaminants ............................ 22 Table 2.4 Summary of PAHs removal from various aqueous media by minerals and modified minerals ............................................................................................................................... 27 Table 3.1 Summary of parameters for PAH removal by using modified clinoptilolites .............. 37 Table 4.1 Summary of experimental conditions for modification of clinoptilolite with surfactants solution, shaken at 220 rpm, at room temperature (20 ± 2oC) for 24 h, and washed with 150 mL of deionized water ......................................................................................................... 48 Table 4.2 Summary of estimation of residual surfactant concentrations after modification and leachability concentration after number of washes at room temperature ............................ 48 Table 4.3 Summary of surfactant leachability (%) of modified clinoptilolites after number of washes, and at different temperatures ................................................................................. 54 Table 4.4 The comparison of BC water quality criterial and the residual concentration of PAHs in the solution by using different adsorbents at room temperature for 24 hours contact time ............................................................................................................................................. 59 Table 4.5 Coefficient of determination (R2) for pseudo-first, second-order, and intra-particle linear model plots, and second-order model parameters for adsorption onto CPC-MC, DDAB-MC and HDTMA-MC ............................................................................................ 66 Table 4.6 Estimation of PAHs accumulation and leachability from three modified clinoptilolites ............................................................................................................................................. 80 xi  Table 4.7 The comparison of water quality criteria of BC for PAHs with the PAH residual concentrations in the solution by using modified clinoptilolites at different pH values at room temperature for 24 hours contact time ....................................................................... 92 Table 4.8 The comparison of water quality criteria of BC for PAHs with the PAH residual concentrations in the solution by using modified clinoptilolites at different temperatures at pH 6.5 for 24 hours contact time ......................................................................................... 98 Table 4.9 Main chemical characteristics of landfill leachate ........................................................ 99 Table 4.10 Comparison of water quality criteria of BC with PAH removal percentage (R%) in aqueous solution by using modified clinoptilolites ........................................................... 103  xii  List of Figures  Figure 1.1 flowchart of research plan ............................................................................................. 6 Figure 3.1 Summary of modification of natural clinoptilolite ...................................................... 33 Figure 3.2 Pictorial description of clinoptilolite modification steps............................................. 34 Figure 4.1 Surfactant Leachability, (a) The leachability concentration of surfactants (CPC, DDAB, HDTMA, and TMA) from modified clinoptilolites after 10, 9, 11, and 7 washes of CPC-MC, DDAB-MC, HDTMA-MC, and TMA-MC, respectively with deionized water at room temperature. All samples were run in duplicate. Error bar represent the standard division (n=2), (b) surfactant % absorbed before washes and after washes on modified sorbents, and leached surfactant% from modified sorbents. .............................................. 49 Figure 4.2 Clinoptilolite and modified clinoptilolites’ pictures; (a) clinoptilolite, (b) CPC-MC, (c) DDAB-MC, (d) HDTMA-MC ...................................................................................... 52 Figure 4.3 Effect of temperatures on stability of surfactants on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). All samples were run in duplicate. Error bar represent the standard division (n=2). ................................................................................ 54 Figure 4.4 PAHs adsorption by using various adsorbents at room temperature for 24 hours contact time at pH value of 6.5: (a) residual PAH concentrations in the solution (µg/L), error bar represent the standard deviation of n=3 (b) removal percentage of PAHs from water by using different adsorbents, error bar represent the standard deviation of n=3. The initial PAH concentrations were 50 µg/L for anthracene and 100 µg/L for fluoranthene, fluorene, phenanthrene, and pyrene. .................................................................................. 58 xiii  Figure 4.5 PAH removal % versus log of contact time on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC with initial concentration of 50 µg/L for anthracene, and 100 µg/L for fluoranthene, fluorene, phenanthrene, and pyrene at room temperature at pH 6.5. ...................................................................................................................................... 62 Figure 4.6 Equilibrium concentrations of mixed PAH in the solution at different times (log t) on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) with initial concentration of 50 µg/L for anthracene, and 100 µg/L for fluoranthene, fluorene, phenanthrene, and pyrene. The error bars denote the standard deviation of duplicate on CPC-MC and HDTMA-MC and triplicate on DDAB-MC. ............................................... 64 Figure 4.7 Pseudo–second–order sorption kinetics model of PAHs, (a) anthracene, (b) fluoranthene, (c) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). The t/qe values versus contact time (t). The contact time (t) is in hours (h), and the PAH adsorption capacity (qe) of modified clinoptilolites is in µg/g. ..................................................................................... 67 Figure 4.8 Weber intraparticle diffusion model, adsorption capacity at equilibrium of PAHs mixture (a) anthracene, (b) fluoranthene, (c) fluorene, (d) phenanthrene, and (e) at different times on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). ................................................................................................................................... 69 Figure 4.9 Effect of modified clinoptilolite dosage (CPC-MC, DDAB-MC, and HDTMA-MC) on PAH removal at room temperature and pH value of 6.5 for 24 hours contact time.  The remaining PAH concentrations were compared to the BC, Canada, water quality criteria. The error bars denote the standard deviation of triplicate for CPC-MC and HDTMA-MC, and quadruplicates for DDAB-MC. ................................................................................... 72 xiv  Figure 4.10 The PAHs adsorption capacity (µg/g) on CPC-MC at room temperature and pH 6.5. The successive batch tests were run 21 times. The total volume of contaminated solution was 2100 mL for CPC-MC. The total amounts of 2100 µg/L of each PAHs (fluoranthene, fluorene, phenanthrene, and pyrene), and 1050 µg/L of anthracene were used. ................ 74 Figure 4.11 The PAHs adsorption capacity (µg/g) on DDAB-MC at room temperature and pH 6.5. The successive batch tests were run 21 times. All samples were run in duplicate. The total volume of contaminated solution was 2100 mL for DDAB-MC. The total amounts of 2100 µg/L of each PAHs (fluoranthene, fluorene, phenanthrene, and pyrene), and 1050 µg/L of anthracene were used. ........................................................................................... 75 Figure 4.12 The PAHs adsorption capacity (µg/g) on HDTMA-MC at room temperature and pH 6.5. The successive batch tests were run 21 times. The total volume of contaminated solution was 2100 mL for HDTMA-MC. The total amounts of 2100 µg/L of each PAHs (fluoranthene, fluorene, phenanthrene, and pyrene), and 1050 µg/L of anthracene were used. .................................................................................................................................... 76 Figure 4.13 The PAHs uptake after exposure of CPC-MC, DDAB-MC, and HDTMA-MC to 21 successive batch assays at room temperature and pH 6.5. The total volume of PAHs contaminated solution was 2100 mL. ................................................................................. 78 Figure 4.14 Comparison of total accumulated PAHs on CPC-MC after 21 successive batch tests with leached PAHs from CPC-MC after performing leachability test. .............................. 82 Figure 4.15 Comparison of total accumulated PAHs on DDAB-MC after 21 successive batch tests with leached PAHs from DDAB-MC after performing leachability test. .................. 83 Figure 4.16 Comparison of total accumulated PAHs on HDTMA-MC after 21 successive batch tests with leached PAHs from HDTMA-MC after performing leachability test. .............. 84 xv  Figure 4.17 The competition effect of fluoranthene in single versus mixture PAHs solution at room temperature and pH value of 6.5 after 24 hours contact time. (a) Removal % of fluoranthene from single PAH and mixture PAHs solution on modified clinoptilolites. (b) Adsorption capacity of fluoranthene in single PAH and mixture PAHs solution on modified clinoptilolites. All DDAB-MC samples were run in duplicate. .......................... 87 Figure 4.18 Effect of pH values on the PAHs removal (a) anthracene, (b) fluoranthene, (c) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) at room temperature. All DDAB-MC samples were run in duplicate. Error bar denote the standard deviation of duplicate for DDAB-MC. .............. 90 Figure 4.19 Effect of pH values on the PAHs adsorption capacity at equilibrium; (a) anthracene, (b) fluoranthene, (c) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) at room temperature. All DDAB-MC samples were run in duplicate. ....................................................................... 91 Figure 4.20 The effect of temperature on the PAHs adsorption, (a) anthracene, (b) fluoranthene, (C) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTNA-MC) from 4 to 35oC. All samples were run in duplicate. Error bar denote the standard deviation of duplicate for modified clinoptilolites. ............ 94 Figure 4.21 The effect of temperature on the PAHs equilibrium adsorption capacity (qe, µg/g),  (a) anthracene, (b) fluoranthene, (C) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) at 4, 20 and 35oC. All samples were in duplicate. .................................................................................................. 96 xvi  Figure 4.22 Comparison of removal% of PAHs from deionized water and landfill leachate solution on CPC and DDAB modified clinoptilolites (CPC-MC and DDAB-MC) at room temperature. Samples were run in duplicate at room temperature. .................................. 100 Figure 4.23 Comparison of adsorption capacity of PAHs from deionized water and landfill leachate solution on CPC and DDAB modified clinoptilolites (CPC-MC and DDAB-MC) at room temperature. Samples were run in duplicate and error bar denote the standard deviation of duplicate for modified clinoptilolites. .......................................................... 101 Figure 4.24 Comparison of BC water quality criteria with the residual PAH concentrations in deionized water and landfill leachate solution after adsorption on one gram of CPC-MC, and DDAB-MC at room temperature. .............................................................................. 103 Figure 4.25 The schematic of adsorption of anthracene on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). ...................................................................................... 104    xvii  List of Symbols µg   microgram µg/L   microgram per liter µg/g   microgram per gram g   gram L   liter mL   milliliter mg   milligram mg/L   milligram per liter mg/g   milligram per gram mg/kg   milligram per kilogram mmol/kg  millimoles per kilogram meq/g   milliequivalents per gram π-bond   two p-orbitals forming a π-bond ≥   greater than or equal to ˂   less than to qe   adsorption capacity at equilibrium qt   adsorption capacity at specific time  q1   charge on first molecule    q2   charge on second molecule    Co   initial concentration Ce   equilibrium concentration Ct   liquid-phase concentration at specific time xviii  D   dielectric constant E   electrostatic interaction energy e   1.602x10-19 c k1   pseudo-first-order equilibrium rate constant k2    pseudo-second-order equilibrium rate constant (gµmol−1 h−1) kid    intraparticle diffusion rate constant (µg/gh0.5) kd   adsorption-desorption distribution coefficient k   proportionality constant (kcal/mole or kJ/mole)  oC   degrees centigrade or degrees Celsius Pa   Pascal (kg/(m.s2)   R   universal gas constant (8.314 J/molK) R2   Pearson's correlation coefficient R%   percentage retention r   distance between two atoms (Ao) ΔG°   the free energy of adsorption (kJ/mol) ∆𝐻𝐻°    The enthalpy (kJ/mol) ΔS°   entropy change V   solution volume (L) ∑   summation $   dollar  xix  List of Abbreviations ANT   Anthracene BTEX   benzene, toluene, ethylbenzene and xylene CAN   acenaphthene CEC   cation exchange capacity CMC   Critical micelle concentration CPB   n-cetylpyridinium bromide CPC    Cetylpridinium chloride CPC-MC  Clinoptilolite modified with CPC DDAB   Didodecyldimethylammonium bromide DDAB-MC  Clinoptilolite modified with DDAB DOM   dissolved organic matter DTMA  dodecyltrimethylammonium EC50    Half maximal effective concentration ECEC    External cation exchange capacity FLA   Fluoranthene FLU   Fluorene GC/MS  Gas chromatography mass spectrometry HDTMA-Br  Hexadecyltrimethylammonium bromide  HDTMA-MC  Clinoptilolite modified with HDTMA-Br LAS   Linear alkylbenzene sulphonates  LC50    median lethal concentration  LD50   median lethal dose xx  LECA   Lightweight expanded clay aggregate  NAP   Naphthalene NC   Natural clinoptilolite rpm   Revolutions per minute PAHs   Polycyclic aromatic hydrocarbons PHN   Phenanthrene  PMO   periodic mesoporous organosilica  Pluronic P123  Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) PYR   Pyrene TMA-Cl   Tetramethylammonium chloride  TMA-MC  Clinoptilolite modified with TMA  TOC    Total Organic Carbon SDBAC   Stearyldimethylbenzylammoniumchloride STD   Standard deviation  US-EPA   Environmental Protection Agency in the US UV/VIS  Ultraviolet-visible spectrophotometry WWTP  Wastewater treatment plant Zn   zinc xxi  Acknowledgements I offer my gratitude to the faculty, staff and my fellow students at UBC, who have inspired me to continue my work in this field. I owe particular thanks to Professor Loretta Y. Li, whose penetrating questions taught me to question more profoundly.  I thank Professor Loretta Y. Li for expanding my vision of knowledge and providing comprehensive answers to my questions.  Special thanks are owed to my family, who has supported me throughout my years of education, both morally and financially.              xxii       This thesis is dedicated to my parents and my daughter Masomeh Taghipour Hesari, Seyed Asadollah Hedayati Hesari, and Viana Tebyanian for their love and support      xxiii  Chapter 1: Introduction 1.1 Problem Statement Polycyclic/ Polyarenes/ Polynuclear Aromatic Hydrocarbons (PAHs) are a group of organic compounds that are made of two or more fused aromatic rings. The sources of the PAHs chemicals are both natural and anthropogenic. Volcanoes and forest fires are the natural sources of PAHs (Forsgren 2015; Harvey 1997).  The anthropogenic sources form through the incomplete combustion of coal, oil, gasoline, diesel, wood, garbage or other organic compounds, and various industrial procedures (Abdel-Shafy and Mansour 2016).  PAH chemicals can typically be observed everywhere in air, water, terrestrial, and biological systems even at low concentrations because of their atmospheric emissions (Kaya et al. 2013). The PAHs have been reported to be in soil (Cao et al. 2017), sediments (Zhang et al. 2015b), rivers (Bai et al. 2014), air (Mohanraj et al. 2011), industrial wastewater (Sánchez-Avila et al. 2009), groundwater surrounding a municipal landfill leachate (Han et al. 2013), and runoff stormwater (Hwang and Foster 2006).   The Environmental Protection Agency in the US (US-EPA) priority pollutants list contains 16 PAH compounds, among a number of known PAHs, because of their toxicity, carcinogenic, teratogenic, persistent, and mutagenic properties (Forsgren 2015; Kaya et al. 2013; Luna et al. 2011; Pérez-Gregorio et al. 2010). Several organizations obtained guidelines for water quality criteria for PAHs to protect drinking water, fresh and marine water aquatic life, and food processing manufacturing. These organizations include US-EPA (U.S. EPA 1980), The European Union (EU) (The European Parliament and of the Council 2013), the Canadian Council of Ministers of the Environment (CCME 2010b), and the government of British Columbia, Canada (British Columbia 1993).  1  Due to moderately persistent properties of PAHs in the environment and bio-accumulation (Kumar et al. 2016), they have been accumulated in the soil, plant, sediment, animal and food chain (Abdel-Shafy and Mansour 2016; Albers 2002). They are found to be difficult to degrade or remove by microbes (Ghosal et al. 2016; Guieysse et al. 2004; Haritash and Kaushik 2009; Lafortune et al. 2009; Revathy et al. 2015). Removing PAHs from aqueous source to enter the environment will be the critical first step to prevent the PAH accumulative effect in marine environments, rivers, sediment and reduce the potential risk to human health.  PAHs, which have been discharged by combustion and petroleum sources, have been often observed in urban stormwater. The urban runoff is typically discharged directly into receiving water bodies without any treatment, which is a risk to water quality and aquatic life, the removal of PAHs from contaminated runoff is necessary (Björklund and Li 2015). PAHs found in leachate are an issue associated with management of landfills (Smol et al. 2016). Smol et al. (2016) reported the total concentration of 16 PAHs in raw municipal landfill leachates were from 23.64- 26.95 µg/L near the city Czestochowa (southern Poland) (Smol et al. 2016). The PAH concentration of 7,966 μg/L can be reached in landfill leachate based on the composition and level of industrial contamination in the landfill leachate (Smol et al. 2016). There is the lack of standards limit for PAHs in landfill leachate in Canada.  For the removal of PAHs from aquatic environments, the adsorption technique is also widely used in a batch method because of a low cost, high removal efficiency, and application at high temperatures (Luna et al. 2011; Pérez-Gregorio et al. 2010). Activated carbons have been often applied for the adsorption technique to remove PAHs from water (Valderrama et al. 2008; Yakout and Daifullah 2013), soil (Gong et al. 2007), sediments (Rakowska et al. 2013), and exhaust gases (Garcı́a et al. 2004; Mastral et al. 2003). However, activated carbon applications 2  are limited because of the high price of activated carbon; the price of activated carbon has reached $1399 per ton in 2017 (IBISWorld 2017).  Clay and modified clay minerals have been used as adsorbents for removing the PAHs (Nkansah et al. 2012). Bentonite clay was modified by sodium dodecyl sulfate to adsorb acenaphthene, acenaphthylene, anthracene, fluorene, phenanthrene, and naphthalene from aqueous solution, and some of the large PAHs were removed up to 76% (Unuabonah et al. 2017). Other minerals could be used as alternative adsorbents for removing the PAHs from water. Modified zeolites with cationic surfactant have been used to remove PAH compounds. Zeolite is modified with Stearyldimethylbenzylammoniumchloride (SDBAC) to remove benzo[a]anthracene, fluoranthene, fluorene, phenanthrene, and pyrene (Lemić et al. 2007) .  Among 39 types of naturally occurring zeolites in the environment, clinoptilolite is the most abundant (Bernal and Lopez-Real 1993). Clinoptilolites modified by surfactant could be a good potential adsorbent for removal of PAHs because of its low cost, and clinoptilolite is naturally occurring. Modified zeolite costs about $450/ton zeolite, and most of the price is accounted for by the surfactants (Bowman 2003). Since natural zeolite (e.g., clinoptilolite) is abundant in many countries, it can be used to remove the PAHs from aqueous solution. Because of the very low specific gravity of high porosity zeolites, surfactant modified natural zeolites could be a potential sorbent for PAH removal in aqueous media. In addition, surfactant modified natural zeolites ($450/ton (Bowman 2003)) are cheaper than granular activated carbon ($1399 per ton in 2017 (IBISWorld 2017)) to remove the As (V) from aqueous solution (Chutia et al. 2009). However, the types of surfactant to be used and the efficiency of these modified natural zeolites have not been fully explored.  3  1.2 Research Objectives and Work Plan The major objective of this research is to explore if modified clinoptilolite with specific types of surfactant are a good sorbent material for removal of PAHs from aqueous environment. The specific goals of this study are:  (1) Modify clinoptilolite adsorbent by using cationic surfactants to improve the PAH sorption from aqueous solution (2) Investigate the leachability and thermal stability of the modified clinoptilolites in order to estimate the efficiency of modified adsorbents to prevent potential environmental risk  (3) Investigate the potential PAH removal by using clinoptilolite and modified clinoptilolites (4) Study possible time dependent rate reaction of PAHs adsorption on the modified clinoptilolites  (5) Estimate the PAHs sorption capacity with the modified absorbents  (6) Investigate the potential effects of pH, adsorbent dosage, and temperature on the PAHs adsorption using modified clinoptilolites (7) Evaluate the competition effect of PAHs adsorption on modified clinoptilolites (8) Evaluate the potential removal of PAHs from a complex background matrix; use landfill leachate for adsorption test. Compare the adsorption results with simple solution (distilled water).  The scope and research plan are given in Figure 1.1. The Na+ homogenized clinoptilolite is studied. Four cationic surfactants with one or two long hydrocarbon chains: cetylpyridinium chloride (CPC), didodecyldimethylammonium bromide (DDAB), hexadecyltrimethylammonium bromide (HDTMA), and tetramethylammonium chloride (TMA), are selected to modify 4  clinoptilolite. The leachability and thermal stability of modified clinoptilolites with CPC, DDAB, HDTMA and TMA are determined.  Batch adsorption tests are performed on clinoptilolite and modified clinoptilolites (e.g., CPC-MC, DDAB-MC, HDTMA-MC, and TMA-MC). Five PAHs (e.g., anthracene (ANT, 3 rings), fluoranthene (FLA, 4 rings), fluorene (FLU, 3 rings), phenanthrene (PHN, 3 rings), and pyrene (PYR, 4 rings)) of three and four aromatic rings of the 16 PAH priority pollutants listed by the US-EPA that can be observed in river water (Luo et al. 2004), groundwater and stormwater (Selbig 2009) are selected for this study. Potential time dependent rate reactions of PAH adsorption on selected modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) are investigated. The PAH adsorption capacity has been carried out through 21 successive batch tests. The leachability test of loaded PAHs has been performed on modified clinoptilolites to precisely forecast sorption properties of modified clinoptilolites on the expected contamination scenarios. The effect of other different parameters on PAH adsorption on selected modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) has been investigated by using various amount of adsorbents, conducting the batch test at different temperatures and pH values.  PAH residuals are measured. PAH adsorption competition has been performed by using a single PAH solution versus a mixture of PAHs on selected modified clinoptilolites (e.g., CPC-MC, DDAB-MC, and HDTMA-MC), followed by evaluating the application of the modified clinoptilolite adsorbents to remove the PAHs from landfill leachate.   5   Figure 1.1 flowchart of research plan  6  Chapter 2: Literature Review  2.1 Polycyclic Aromatic Hydrocarbons (PAHs) in the Environment Polycyclic Aromatic Hydrocarbons (PAHs) are a large group of organic compounds that are made of two or more fused aromatic rings bonded in linear (e.g., as anthracene), angular (e.g., dibenzo (a, h) anthracene), or clustered (e.g., pyrene) arrangements (Abdel-Shafy and Mansour 2016). These compounds demonstrate persistence in the environment and have adverse health effects and these properties make them an important class of environmental pollutants (Kumar et al. 2016). They have low solubility in water and are less volatile with stable hydrophobic planar configuration because of the present of at least two aromatic rings (Duran and Cravo-Laureau 2016); Appendix A.1 presents some of physical-chemical properties of several PAHs. Sources of PAHs: The sources of the PAH chemicals are both natural and anthropogenic. Volcanoes, forest and brush fires, natural losses or discharge from petroleum or coal deposits, and open burning are the natural sources of PAHs, (Forsgren 2015; Harvey 1997). The PAHs anthropogenic sources form through residential heating, car exhaustion, coal gasification, production of asphalt, coke, and aluminum, petroleum refining, tobacco smoking, cooking at high temperature (e.g., charbroiling, grilling, and frying), and catalytic cracking, (Abdel-Shafy and Mansour 2016; Kumar et al. 2016; Srogi 2007; Wolska et al. 2012). The PAHs are used in pharmaceuticals and agricultural products, lubricating materials, manufacturing of pigments, pesticides, resins, dyes, plastics, and wood preserving (Abdel-Shafy and Mansour 2016). Atmospheric fallout, municipal litters, industrial effluents, urban surface runoff and spillage or leakage of oil are the mechanisms of releasing PAHs into natural water resources (Kaya et al. 2013; Srogi 2007). Because of atmospheric deposition or surface runoff, PAHs are observed 7  mostly in surface soils. The main source of PAHs in drinking water is related to coal-tar linings of the distribution pipes. The total consumption of PAHs from drinking water is an insignificant amount (Kumar et al. 2016). The main exposure route of the public to PAHs is via ambient and indoor air, and food ingestion. Inhalation and skin adsorption are the occupational exposure to PAHs (Kumar et al. 2016).  Occurrence of PAHs in the Environment:  PAHs can be released into the atmosphere in the form of gases or adsorbed onto particles and these chemical are removed by oxidation, photolysis, or wet and dry deposition reaction. The PAHs are dispersed and transported a long range distance by air current and wind and then deposit on soil, vegetation, and in water. PAHs are transferred by surface runoff to rivers and seas and enter into plants, fish and sedentary creatures by bioaccumulation. The PAHs have been reported to be in sediments, rivers, air, landfill leachate, wastewater, and runoff stormwater. For example, the PAHs occurrence was studies in a coking wastewater treatment plant (WWT) in Shaoguan, China. Although higher molecular weight PAHs were dominant in raw wastewater, 3-6 ring PAHs were predominant in the final effluent.  Phenanthrene, fluoranthene, pyrene were dominant in gas samples while dominant chemicals were fluoranthene, pyrene, chrysene and benzo[k]fluoranthene in sludge (Zhang et al. 2012). Table 2.1 provides the concentration of PAHs in the aqueous environment from previous studies. The mean concentration of six PAHs compounds dissolved in water including in the European Community  priority list of dangerous chemicals (fluoranthene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, benzo(g,h,i) perylene, and indeno(1,2,3-cd) pyrene) was 72 ng/L in the River Tiber, Italy (Patrolecco et al. 2010).  These chemicals were included in the European Commission priority list of hazardous chemicals (Patrolecco et al. 2010).  In the 8  Liaohe River Basin, China, the total concentrations of 16 US EPA priority PAHs was 111.9 to 2,931.6 ng/L with mean value of 454.7 ng/L in water and 92.2 to 295,635.2 ng/g dry weight in the sediments (Bai et al. 2014). The total concentration of 19 parent PAHs and alkylated PAHs (e.g., naphthalene, acenaphthene, acenaphthylene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, dibenzothiophene, benzo[a]anthracene, chrysene, benzo[a]pyrene, benzo[e]pyrene, perylene, benzo[b] fluoranthene, benzo[k]fluoranthene, dibenz [a, h]anthracene, benzo[g, h, i]perylene, indeno[1,2,3-cd]pyrene) in stormwater ranged from 1510 to12500 ng/L in the Anacostia River, Washington, DC, USA, (Hwang and Foster 2006).  Smol, et al. (2016) reported that the total concentrations of 16 PAHs, listed by EPA, are 23.64 - 26.95 μg/L in raw municipal landfill leachates in the city of Czestochowa (Southern Poland) (Smol and Włodarczyk-Makuła 2017; 2016; Smol and Włodarczyk-Makuła 2017; 2016).  The eleven detected PAHs including naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, and benzo(k)fluoranthene concentration in groundwater samples around the landfill ranged from not detected to 2.19 μg/L in  Zhoukou, China (Han et al. 2013). Table A.2 in Appendix A.2 provides the concentration of five PAHs (anthracene, fluoranthene, fluorene, phenanthrene, and pyrene) in other media as well.      9  Table 2.1 Concentrations of PAHs in the rivers, and groundwater  (Patrolecco et al. 2010) (Bai et al. 2014) (Hwang and Foster 2006) (Han et al. 2013) naphthalene  194.4 17.7-59 nd acenaphthene  26.8 3.68-28.8 380 acenaphthylene  13.3   fluorene  42.6 8.79-152 682 anthracene  6.8 5.43-119 168 phenanthrene  89.9 26.1-338 519 fluoranthene 8.9 30.5 86.5-1380 261 pyrene  21.6 65.6-774 158 benzo[a]anthracene  5.2 22.2-337 18.1 chrysene  7.3 48.6-519 nd benzo[a]pyrene 9.9 3.4 27.8-446  benzo[e]pyrene   45.8-498  perylene   6.84-122  benzo[b] fluoranthene 12.9 7 57.7-733 nd benzo[k]fluoranthene 9.4 nd* 32.4-404 nd dibenz[a, h]anthracene  0.4 6.94-134  indeno[1,2,3-cd]pyrene 26.5 2.2 37.1-505  benzo[g, h, i]perylene 5.3 2.4 15.0-548  dibenzothiophene   4.68-41.7  Total PAHs 72 454.7 1510-12500 2190 *nd: not detected The US-EPA (the Environmental Protection Agency in US) priority pollutants lists include the 16 PAHs (e.g., naphthalene, acenaphthene, acenaphthylene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[a]pyrene, benzo[b] 10  fluoranthene, benzo[k]fluoranthene, dibenz[a, h]anthracene, benzo[g, h, i]perylene, indeno[1,2,3-cd]pyrene), among more than a hundred numbers of known PAHs. Because of their toxic, carcinogenic, and mutagenic properties, they are actively monitored by the US and are considered environmentally persistent pollutants (Kaya et al. 2013; Luna et al. 2011; Pérez-Gregorio et al. 2010). Appendix A.1 presents the US-EPA priority pollutants list and their physical and chemical properties. In this list, with increasing the molecular weight of the PAHs, from 2 to 6, the Kow increases and the solubility and vapor pressure decreases.   PAHs Degradation &Bioaccumulation: Degradation and transport of PAHs in water occur by microorganism. The ability of microbes in water to transform the PAHs is limited. PAHs with higher molecular weight (four to seven aromatic rings) have greater resistance to biodegradation compared to PAHs with lower molecular weight (Wilcock et al. 1992). Non-degradable PAHs are accumulated in the bottom sediments where the process of biodegradation continues. The PAH bioaccumulations have been presented in phytoplankton (Duran and Cravo-Laureau 2016). If the sedimentation rate is high and sediments are not substantially disturbed, the PAHs could remain there for decades (Albers 2002). For example, all surface sediment samples from the Gulf of Gdansk site had a higher proportion of higher molecular weight of PAHs at the wreck of World War II German hospital ship (Wolska et al. 2012). Invertebrates and vertebrates ingest PAHs in addition to microbes. During feeding, grooming and respiration of mammals, birds, fish and invertebrates, PAHs are degraded and excreted (Albers 2002) . The polychacte Arenicola marina (invertebrates) was exposed to sediment that was contaminated with PAHs from oil spills. The polychacte Arenicola marina bio- accumulated fluoranthene, pyrene, bezo(b)fluoranthene, and benzo(k)fluoranthene whereas it accumulated phenanthrene and anthracene initially and then metabolized them (Morales-11  Caselles et al. 2008). Some zooplanktons do not have ability to metabolism the hydrocarbon; however, they have capability of bio-accumulating, transporting and storing them temporarily (Albers 2002) . The effects of crude oil exposure on the PAHs bioaccumulation in natural marine mesozooplankton communities were evaluated. Mesozooplankton and the copepod A. tonsa could selectively bio-accumulate five PAHs including fluoranthene, phenanthrene, pyrene, chrysene and benzo[b]fluoranthene (Almeda et al. 2013) . Organisms accumulate PAHs because of their poor PAHs metabolism, high lipid contents and activity or distribution that causes high concentration of PAHs (Albers 2002). Health Effect of PAHs: Metabolism and photo-oxidation affect the PAHs toxicity to aquatic environment. PAHs are more toxic in the present of ultraviolet light. Acute toxicity of PAHs to aquatic organisms and birds are moderate to high (Abdel-Shafy and Mansour 2016). A mammal can adsorb the PAHs through ingestion, inhalation and dermal contact. The main routes of human exposure to PAHs are inhalation of ambient and indoor air, eating contaminated food with PAHs, smoking cigarettes, or inhalation of smoke from fireplaces. Length and route of PAH exposure, exposed concentration, and toxicity of PAHs influence on human health.  PAHs can cause short- and long-term health impacts. In humans, the short term health effect is not clear. However, Eye irritation, nausea, vomiting, diarrhea and confusion are the short term health effect of occupational exposure to high concentration of PAHs (Abdel-Shafy and Mansour 2016). High volatility is characteristic of PAHs with low molecular weights (e.g., naphthalene) which result in short-term toxicity issues through inhalation without causing cancer. The long term exposure to PAHs can cause health effects including suppressed immune system, cataracts, damage to kidney and liver, inhalation difficulties, asthma symptoms, and 12  abnormalities in the lung system (Abdel-Shafy and Mansour 2016). PAHs with high molecular weight (e.g., benzo(a) pyrene) are identified as human carcinogens and can discharge into the environment (Lin et al. 2010). Due to the persistence of PAHs in the environment, it causes accumulation of them in the air, water, soil and foods. When PAHs enter the human body, they can simply pass across cell membranes and are easily adsorbed into cells. As a result, the immune system changes PAHs to diolepoxides and epoxide hydrolase, reacting with DNA and preventing its production (Chuang et al. 2010; Kaya et al. 2013). 2.2 Natural Zeolite From 39 types of zeolites that are naturally occurring in the environment, the clinoptilolite, [(Na, K)6-2x Cax].(Al6Si30O72).24 H2O, is the most abundant (Bernal and Lopez-Real 1993). Zeolites are crystalline, negatively charged, hydrated aluminosilicate with three dimensional structures and high internal and external surface areas (Lemic et al. 2006). Zeolites have large channels and cavities in their structures and negative charge sites are placed into those channels, which are referred to as zeolite exchange sites (Ming and Dixon 1987). Small molecules and ions can pass in and out via these channels, but larger molecules and ions can not enter (Ming and Dixon 1987). The pore size diameters of zeolite-clinoptilolite are 4-7 Å (0.4-0.7 nm) (Jha and Singh 2012). Zeolite has a high surface area and cation exchange capacity to retain contaminates from water and is free of swelling and shrinking behavior compared to clay because of zeolite’s rigid three-dimensional structure (Bowman 2003). Clinoptilolite demonstrates that various cation exchange capacities mostly depend on the Al content. Appendix B.1 presents the properties of clinoptilolite. The adsorption of cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide on the clinoptilolite provides more anion sorption sites (Pratap Chutia, 2009). 13  2.3 Application of Zeolite Zeolites have been used in many applications because of their unique chemical and physical properties (e.g. ion exchange, adsorption, molecular sieves, dehydration and rehydration). The zeolites have been used in pollution control, mining and metallurgy, petroleum refining, and energy conservation (Bernal and Lopez-Real 1993; Cui et al. 2006). Zeolites have many applications, and Rhodes (2010) indicates their application including (1) zeolites have been used in the construction industry to make a light-weight concrete (de Gennaro et al. 2008), (2) the synthesised zeolites have been used as a “builder” in detergents to soften water by removing Ca2+ and Mg2+ (Hui and Chao 2006) instead of using polyphosphates that promote algal bloom in rivers and lakes, (3) removal of heavy metal cations from the aqueous environment by cation-exchange phenomena (He et al. 2016), (4) synthetic zeolites are used as solid acid catalysts (H+ exchanged zeolites) in the petrochemical industry, (5) zeolite-loaded “catalytic converters” are used to reduce NOx emission (Berndt et al. 2003) from cars, (6) modified zeolite with surfactants are used to eliminate anions, such as chromate and organic contaminants (Leal et al. 2017) such as trichloroethylene, concurrently from aqueous solution, (7) silver and Ni2+ exchange zeolites can be used to remove radioactive iodine (Cheng et al. 2015) and sulfur compound (Mahmoudi and Falamaki 2016), (8) small pore zeolites can be used to adsorb traces of water from other solvents as a molecular sieves (Gounder and Davis 2013), (9) separation of linear n-alkanes from branched alkanes by preferential penetration of zeolite pores as hydrocarbon sieving, (10) Hemosorb and QuikClot based zeolites can be used to instantly stop wounds from bleeding, (11) oxygen of 90% purity is provided from air by using a zeolite to separate gases (Rao et al. 2014), (12)  zeolite has been enriched with K+ and NH4+ to supply these nutrients to plants from soils, and (13) zeolites have been used to decontaminate the 14  environment such as feeding zeolite to cattle to remove radioactive ions from milk, baking bread and biscuits for children with zeolite to reduce the radioactive pollution in humans, and cleaning up the Chernobyl nuclear plant after disaster (Rhodes 2010).  2.4 Cationic Surfactants Modified Zeolite Surfactants are compounds that contain parts with a hydrophobic tail and a hydrophilic head. Based on the head group, they are classified as cationic, anionic or zwitterionic (Durán-Álvarez et al. 2016). Because of this amphiphilic property, surfactants moieties can self-associate or aggregate in the solvent bulk. The term of “micellization” is the surfactant’s aggregation in the form of a cluster and “micelle” is the aggregate. The result of balanced forces between amphiphile and solvent is the micellization (Bijma et al. 1998).  The average size of cationic surfactant at CMC concentration is 126 nm (Esmaeilzadeh et al. 2011). These chemicals have been used to improve the surface properties of a solid surface (Choi et al. 2009) and to optimize hydrophobic binding sites for organic pollutants such as PAHs and recovery of pesticide (Clark and Keller 2012). Micelles could cross, or interact with the cell membrane because of having similar structure to lipids and hence could be employed in drug distribution systems (Taboada et al. 2001). The technological applications of surfactants include in the cleaning industry, emulsion polymerization, and pharmacology (García Daza and Mackie 2014).  Cationic surfactant compounds can substitute positively charged counterions on the zeolite surface (Altare et al. 2007) and could modify zeolite surface properties that could increase their use as an adsorbent for pollutants uptake from aqueous solutions. Cationic surfactants change the surface properties of zeolites with ion exchange.  Mineral typically have negative charge because of the isomorphous exchanges the alumina silica layers in natural clay, the charge is equalized by Na+, K+, and Ca2+. These cations can be 15  hydrated and form a hydrophilic nature on these surface of the mineral (Kaolinite, zeolite). The cations can be replaced by quaternary ammonium cations [(CH3)3NR]+at the exchangeable sites of the mineral with organophilic properties (Li et al. 2003). However, silica has the hydroxyl group (-OH) on its surface, which could adsorbs moisture and results in agglomeration (Ma et al. 2010), which make the silica unsuitable candidate for modification with surfactant.     Cationic surfactants such as HDTMA-Br have a long carbon chain that can not enter the zeolite pores; therefore, adsorption is limited to the external surface (Bowman 2003; Sullivan et al. 1998). Chemical structure of HDTMA is presented in Appendix B.2. This is because zeolite channel diameters are too small for the surfactant, but large enough for exchangeable cations (Pérez Cordoves et al. 2008). Depending on the Al content, nature zeolites show the different cation exchange capacity in different areas of the world (Chutia et al. 2009). Surfactant adsorption on zeolites is limited to external exchange sites only (Li et al. 1998). Therefore, the external cation exchange capacity (ECEC) typifies the exchange capacity of the zeolite surface for surfactants. The adsorption of surfactants onto zeolite surface is control by the initial concentration of surfactant (CMC) in the solution, and the zeolite’s ECEC. For the surfactant modified zeolite, the total cation exchange capacity (CEC) differs from 800-2200 meq/g, with an external cation exchange capacity (ECEC) in the variety of 70-110 meq/g (Apreutesei et al. 2008).   Various fractional organic carbon contents with various surface shapes of adsorbed surfactant elements are the results of surfactant modification by HDTMA (Bowman 2003; Ghiaci et al. 2004). HDTMA-Br is one of the constituents of the topical antiseptic cetrimide (Laemmli 1970)  and some buffers for DNA extraction (Clarke 2009). This surfactant is a successful antiseptic agent versus bacteria and fungi. The HDTMA has been used for synthesis of gold 16  nanoparticles (Biswal et al. 2010) and mesoporous silica nanoparticles (Pang et al. 2005), anti-corrosion (Arjmand et al. 2016)  and hair conditioning products. HDTMA has been used in many applications since 1970. In addition, it is well-known that clay modified with surfactant such as HDTMA can significantly increase the removal of non-ionic organic solutes from aqueous environments (Haggerty and Bowman 1994). The typical cationic surfactants, which are used for the modification, are HDTMA-Br and HDTMA-Cl to remove the PAHs from aqueous solution (Bansiwal et al. 2006; Bowman 2003; Chutia et al. 2009; Dong et al. 2010; Ghadiri et al. 2011; Ghiaci et al. 2004; Kuleyin 2007; Li and Bowman 1997; Rosales-Landeros et al. 2013; Seifi et al. 2011; Tashauoei et al. 2010; Vidal et al. 2012; Wingenfelder et al. 2006; Yu and Feng 2011).  2.4.1 Adsorption Models of Surfactant on Solids Surface  As Atkin et al. (2003) deliberate, there are two general models for the adsorption of cationic surfactants on the substrate surface: (1) the two-step model, and (2) the four-region model. A monolayer or “ hemimicelle” is formed through electrostatic interactions at the solid-aqueous interface until the surface charge is neutralized in both models except that in the two-step model the concentration of surfactant should be equal or less than its critical micelle concentration (CMC) (Gao et al. 1987; Somasundaran and Fuerstenau 1966). The CMC is the minimum amount of surfactant that forms a micelle and is called “critical micellization concentration” (CMC). Beyond the CMC, surfactants form micelles in well- defined geometric shapes and sizes and all further addition of surfactant to solution contributes to micelles (García Daza and Mackie 2014). CMC of several surfactants are presented in Table B.3 in Appendix B.3.  In the two-step model, a bi-layer (hemimicelle aggregates) through Coulomb’s forces is formed when the surfactant concentration exceeds the CMC which could have different shapes and sizes. However, in the four-region model, the surface morphology creates a bilayer with 17  head-groups that are face up to the solution (Atkin et al. 2003; Gao et al. 1987; Somasundaran and Fuerstenau 1966).  In the case of modification of zeolite, when the surfactant concentration is above the CMC in the solution, surfactants face a negative charge on the zeolite surface and form a bilayer or “admicelle” and surface charge of zeolite is reversed from negative to positive (Haggerty and Bowman 1994; Pérez Cordoves et al. 2008). The anionic counterions (e.g., Br-, or Cl-) balance the positive charge of head groups, which make surfactant modified natural zeolites a potential adsorbent to remove anionic pollutants (Haggerty and Bowman 1994; Pérez Cordoves et al. 2008).  Ersoy and Celik (2003) suggested that there are parameters that control the interaction between adsorbents with ion exchange capacity and the surfactant: (1) the adsorbent structure (e.g., surface charge, hydrophilicity or hydrophobicity, ion exchange capacity, porosity, and surface heterogeneity), (2) the surfactant structure (e.g., surfactant type, and length of carbon chain), and (3) the solution condition (temperature, pH, ionic strength, polarity and dielectric constant) (Ersoy and Celik 2003). Ersoy and Celik (2003) investigated the effect of hydrocarbon chain lengths on adsorptions of three cationic surfactants including hexadecyltrimethylammonium bromide (HDTMA, C16H33(CH3)3NBr), tetradecyltrimethylammonuim (TDTMA, C14H29(CH3)3NBr), and dodecyltrimethylammonim (DDTMA, C12H25(CH3)3NBr) on clinoptilolite. They found that longer carbon chains of cationic surfactants increased the ion exchange and hydrophobic interaction. HDTMA had the highest adsorption on clinoptilolite compared to the other two surfactants (Ersoy and Celik 2003). Li and Bowman (1997) investigated the effect of counterions of Cl-, Br-, and HSO4- on the adsorption of hexadecyltrimethylammonium (HDTMA) on clinoptilolite. The trend of adsorption of HDTMA on the clinoptilolite followed HDTMA-Br>HDTMA-Cl>HDTMA-HSO4 (208, 151,132 18  mmol/kg, respectively). The Br- counterion has more adsorption than Cl-, and HSO4-counterions on the HDTMA (Li and Bowman 1997).     2.4.2 Environmental Impacts of Cationic Surfactants  Studies indicate that the surfactants are a risk to the aquatic environment (Venhuis and Mehrvar 2004). Therefore, it is important to use a surfactant that has less leachability from zeolite and has a stronger bond on zeolite to ensure no risk to aquatic environment. The toxicity of a few cationic surfactants is presented in Table 2.2. This Table presents that the half maximal effective concentration (E50) value for the growth inhibition of the HDTMA and CPC were 3.27 ± 1.12 × 10−7 mol/L and 4.9 ± 1.3 × 10−7 mol/L for the  Acinetobacter junii (Hrenovic and Ivankovic 2007; Hrenovic et al. 2008).  Toxicity of HDTMA to the marine macroalga, Ulva lactuca, has been investigated and the results indicate the EC50 value of 2.4 mg/ L (Masakorala et al. 2011). Toxicity of DDAB-Br to the unicellar green alga Dunaliella sp. has been estimated and the results show the EC50 value of 18 mg/L. Concern has been raised regarding the toxicity of surfactants because of potential leaching into the environment from modified compounds, which would position the aquatic organisms at risk. When the modified clinoptilolites are used as an adsorbent to remove the organic pollutants, these surfactants could potentially leach into the water body depending on the bonding mechanism. Currently, there is not any water quality guideline or regulation related to toxicity of CPC, DDAB, HDTAM, and TMA to protect aquatic organisms in BC, Canada. However, regarding remediation technology precautionary principle must apply. The potential environmental impact of these surfactants could be a concern(s) despite lacking of environmental standard and guideline at the present time.   19  Table 2.2 Environmental impact of cation surfactants Species acute inhalation LC50 (mg/L) EC50 acute oral LD50 (mg/kg) References CPC Bombina orientalis embryos and tadpoles 0.697  (embryos, 168-h) 1.82   (tadpoles, 168-h) 0.531 mg/L  (embryos)  (Park et al. 2016) Male & female- rats 0.054 and 0.51    (European Commission 2015) Rats (sexes combined) 0.09   560.3 (female) (Lin et al. 1991) Acinetobacter junii    4.9±1.3 × 10−7 mol/L  (Hrenovic et al. 2008)   HDTMA-Br   Marine Macroalga, Ulva lactuca  2.4 mg/L  (Masakorala et al. 2011) Acinetobacter junii  (inhibition of CFUs)  3.27 ± 1.12 × 10−7 mol/L  (Hrenovic and Ivankovic 2007) Acinetobacter junii (inhibition of the P-uptake rates)   2.47 ± 0.51 × 10−6 mol/L  (Hrenovic and Ivankovic 2007) Daphnia magna  0.13 to 0.38 mg/L  (Zhang et al. 2015a)   DDAB-Br   Unicellar green alga Dunaliella sp.  18 mg/L  (Kaj et al. 2014) EC50: 50% reduction in growth of organisms under controlled conditions (Hasenbein et al. 2015) LC50 : the lethal concentration essential to kill 50% of the sample population (Hasenbein et al. 2015) LD50 : the amount of a consumed material that kills 50 percent of a test sample (Kreger 1992) 2.4.3 Contaminants Removal from Aqueous Solution by Using Modified Minerals   Adsorption is one of the efficient processes to remove contaminants from aqueous solutions. Organoclay and surfactant modified clinoptilolite have been studied to remove pollutants such as cadmium (Tashauoei et al. 2010), arsenate (V) (Chutia et al. 2009) and a synthetic textile dye (Reactive Blue 19 (RB19)) (Özcan et al. 2007) from aqueous environments via the adsorption process.  Modifications of clay and zeolite by quaternary ammonium cations have been investigated to remove organic pollutants. The modified clay, zeolite, and other sorbents have significant ability to remove pollutants such as antimonite (Wingenfelder et al. 2006), bisphenol A (Li et al. 2014), BTEX (benzene, toluene, ethylbenzene and xylene) (Altare et al. 2007; Janks and Cadena 20  1991; Vidal et al. 2012), chromate (Wibowo et al. 2011), and petroleum mono-aromatics (Seifi et al. 2011).  The list of adsorbents, modification agents, and removal pollutants from aqueous solution are provided in Table 2.3. Montmorillonite, natural clinoptilolite, synthetic zeolite Y, polymeric Al/Fe- montmorillonite, and bentonite were modified with HDTMA to remove Cr2O7-2, AS (v), nitrate, humic acid, and BTEX, respectively. KSF- type montmorillonites intercalated to polymeric aluminium and iron to adsorb heavy metals (Cd, Cu, Ni, Pb, and Zn) from portable water. The removal results indicated that polymeric Al modified montmorillonite had very low removal efficiency for heavy metals; however, polymeric iron and polymeric Al/Fe modified montmorillonite removed effectively all heavy metal from portable water (Cooper et al. 2002). KSF- type montmorillonites intercalated to polymeric aluminium and iron in the presence of HDTMA-Br to adsorb phenol from water. The adsorption results indicate that the polymeric Al/HDTMA and HDTMA modified montmorillonite had effective affinity to remove phenol from water (Jiang et al. 2002). Montmorillonite was modified by using HDTMA-Br to remove chromate, and the chromate was adsorbed at maximum amount at and below pH 1, and the adsorption of chromate reduced by half at pH 2 and 6 (Krishna et al. 2001). Krishna et al. (2001) used a commercial modified bentonite and modified bentonite with HDTMA-Cl to remove the toluene and xylene from water. The results of adsorption indicated that the modified bentonite with HDTMA had twice xylene adsorption compared to commercial bentonite (Vianna et al. 2005). Natural zeolite tuff was modified by HDTMA to remove the antimonite, and the modified zeolite removed up to 42% of antimonite (Wingenfelder et al. 2006). Natural zeolite was modified by cetylpridinium bromide (CPC) to remove the bisphenol A from aqueous solution (Li et al. 2014). Natural clinoptilolite was modified by HDTMA-Br to remove arsenic, As (V), from 21  aqueous solution. The high adsorption of As (V) by modified clinoptilolite results in reduction of As (V) to below WHO’s previous guideline values of 50 ppb in drinking water (Chutia et al. 2009). Vidal et al. (2012) modified synthetic Na Y zeolite with HDTMA-Br to remove the BTEX and the modified zeolite removed the BTEX by more than 80% from aqueous solution. Table 2.3 List of adsorbents, modification agents, and removal contaminants Adsorbent Modification agent Pollutants Removal References Fe & Fe/Al KSF- montmorillonite FeCl3, AlCl3  Cu, Pb, Zn, Cd, Ni  (Cooper et al. 2002) Bentonite,  HDTMA-Br1 Nitrate (Xi et al. 2010) Montmorillonite HDTMA-Br Cr2O7-2 (Krishna et al. 2001) Montmorillonite FeCl3, AlCl3, Organic Matter (Zohra et al. 2014) Polymeric Al-  KSF-montmorillonite HDTMA-Br Phenol (Jiang et al. 2002) Polymeric Al/Fe- montmorillonite HDTMA Humic Acid (Jiang and Cooper 2003) Kaolinite HDTMA, DDTMA2  (Li and Gallus 2007)  Montmorillonite HCl, NaOH Ni, Cu and Zn (Vengris et al. 2001) Bentonite (SVC) HDTMA BTEX3 (Vianna et al. 2005) Natural clinoptilolite (NC) HDTMA As(V) (Chutia et al. 2009) Synthetic zeolite Y HDTMA BTEX (Vidal et al. 2012) Modified clinoptilolites β-Cyclodextrin Nitrophenols (Li et al. 2011) Natural zeolite  CPB4 Bisphenol A (Li et al. 2014)     1HDTMA: (hexadecyltrimethylammonium bromide)    2DDTMA: Dodecyltrimethylammonium 3BTEX: benzene, toluene, ethylbenzene and xylene    4 CPB: cetylpridinium bromide (CPB)  2.5 Removal Methods of PAHs from Aqueous Solution PAHs have adverse health effect on human and aquatic life; therefore, they need to be removed from environment media. PAHs are removed from aqueous environment by several techniques including biodegradation (Hesham et al. 2012; Shao et al. 2015), oxidative photodegradation (Hussain et al. 2017), ozonation from sewage sludge (Carrère et al. 2006), and adsorption (Nkansah et al. 2012; Zhang et al. 2014). Exposing PAHs in air or water to sunlight can create polar oxidize chemicals (photooxidation). When oxygen is not enough for photooxidation, PAH degradations occur in water by photolysis. PAHs with high molecular weight are mostly changed by a photooxidation mechanism (Albers 2002). Photodegradation of 22  PAHs depends on few factors including dissolved organic matter (DOM), suspended particles, salinity, and ionic composition. Ionic composition is very different in estuary areas where there is a transition among freshwater and marine water (Shang et al. 2015). Although chemical methods are fast and destructive and are not sensitive to concentration and class of PAHs, they have benefits and drawbacks. For instance, the high solute concentration is essential for chemical participation and there is not an economically feasibility for reverse osmosis (Hall et al. 2009).  Biodegradation has been studied in an aerobic condition in petrochemical industry treatment plants (Sponza and Gök 2010) and anaerobic conditions with recirculating of ozonated sludge in municipal sewage sludge (Bernal-Martinez et al. 2009). As PAHs with high molecular weight resist to biological degradation and can prevent the process, the PAHs biodegradation is not a beneficial method (Hall et al. 2009). In addition, to break down the PAHs to acceptable level in the biological process, a significant extended time is required (El Khames Saad et al. 2014).  The water treatment cost for reverse osmotic, ion exchange, and elctro-dialysis ranges from 10-450 US$/m3 water, except adsorption technique. The water treatment cost by adsorption is 5-200 US$/m3 of water (Ali et al. 2012).  Adsorption method is an effective method to remove PAHs from aqueous environment because it has a low cost, simple design, is easy to operate and insensitive to toxic contaminants. The removal efficiency of adsorption technology could be up to 99.9 % (Ali et al. 2012). Therefore, there has been a growing interest to discover the suitable adsorbents to remove these pollutants from water. In adsorption, a substance can accumulate at a surface or interface of adsorbent. The adsorption process takes place at an interface among solid adsorbent and polluted water in the water treatment process. The contaminant that is adsorbed and the adsorbing phase are called adsorbate and adsorbent, respectively (Ali et al. 2012). These suitable adsorbents could 23  be natural mineral, easily provided natural adsorbents, or modified adsorbents. Activated carbon is used frequently to remove the PAHs from aqueous solution because of its high adsorption capacity, and high surface area (600-2000 m2/g) (Ali et al. 2012; Gök et al. 2008).  However, activated carbon has some limitations in its application. It has a high cost, it is difficult to regenerate adsorbed high- boiling -point organics (Chang et al. 2004) and it  is flammable and not environmentally friendly since the largest feed stock for production of commercial activated carbon are pine wood and coal (Ali et al. 2012).  The focus is on finding cheap and locally available adsorbents that are efficient to remove PAHs. For example, Björklund and Li (2015) used three waste products including two pine barks and a sawdust as a potential adsorbents to remove PAHs (e.g., anthracene, fluorene, pyrene) with concentration of (10-300 µg/L from stormwater), and the results indicated more than 80% of PAHs were adsorbed (Björklund and Li 2015). Aspen wood fibers were able to remove anthracene, fluorene, naphthalene, and pyrene with concentration of 2-50 µg/L from water by more than 95% after 12.5 days (Boving and Zhang 2004). Agricultural residue (soybean stalk based carbons) was able to remove acenaphthene, naphthalene, and phenanthrene by 95.4, 100, 95.64%, respectively from water (Kong et al. 2011). However, these agricultural residue and wood waste products are seasonal, or have other markets and alternative uses (e.g., household fuel, animal feeding and bedding, enhancing soil organic contents, and recycling nutrient) (Smil 1999), so there would be competition for their usage.   Minerals and modified minerals are a perfect applicant to remove PAHs. Clay was able to remove organic pollutants because of having negative charge on the fine grain silicate minerals structure. The adsorption of positively charged cations neutralizes the clay’s negative charge. The clays possess high adsorption capacity because of huge surface area ranging up to an 800 24  m2/g (Ali et al. 2012). For example, bentonite was used to remove the 12 PAHs of EPA prioritized pollutants list with and without UV rays (Karaca et al. 2016).  Table 2.4 presents summary of removal of PAHs from aqueous solution by using mineral and modified minerals. Clinoptilolite was modified by HDTMA (0.094mmol/kg clinoptilolite) to remove naphthalene from n-paraffin, and the adsorption results indicated that naphthalene was removed by more than 50% from n-paraffin (Faghihian and Mousazadeh 2007a). Gök et al., (2008) modified natural sepiolite clay with dodecyltrimethylammonium (DTMA) bromide to adsorb naphthalene from water at different pH values in the range of 1-8. At around neutral pH, naphthalene had the highest adsorption on modified sepiolite, and at pH 6 the maximum adsorption capacity of naphthalene was 2.86 mg/g (Gök et al. 2008). Removal efficiency of naphthalene was investigated on hydrophobic DAY-zeolite from Germany with particle size of 0.595-0.841 mm in aqueous solution. The adsorption capacities of naphthalene were 4.22, 13.22, 22, 27.30, and 31.23 g/kg with initial concentration of 5, 15, 23, 28, 33 mg/L of naphthalene (Chang et al. 2004). The optimum pH values to remove the naphthalene were 4 and 6 for NB and HB, respectively, and the maximum adsorption capacities were 2.797 and 6.795 mg/g for NB and HB, respectively (Kaya et al. 2013). Lightweight expanded clay aggregate (LECA) was used to remove phenanthrene, fluoranthene and pyrene from 100 mL water in a batch test. The removal efficiency of fluoranthene, phenanthrene and pyrene was 70.8, 70.7 and 72.1%, respectively with 0.2 g of LECA with initial PAHs concentration of 20 µg/L. The PAH removal efficiency was 93.9, 92.6, and 94.1% for fluoranthene, phenanthrene and pyrene, respectively, with using 4 g of sorbent (Nkansah et al. 2012). Sepiolite is a fibrous silicate clay mineral and was used to remove 25  phenanthrene and pyrene in batch tests. The adsorption capacity of sepiolite for phenanthrene and pyrene were 1.1, and1.0 µmol/g, respectively (Cobas et al. 2014) . Clinoptilolite- rich zeolite tuff was modified by stearyldimethylbenzylammoniumchloride (SDBAC) to remove the benz[a]anthracene, fluoranthene, fluorene, phenanthrene, and pyrene from distilled water vapor in column experiments. The highest PAHs adsorption (98 %) was achieved with 100 mmol SDBAC/kg of clinoptilolite with particle size of 0.0-0.4 mm for all the PAHs. Benz[a]anthracene was adsorbed 100 % at a concentration of 20 µg/L with 75mmol SDBAC/kg of clinoptilolite with particle size of 0.4-0.8 mm (Lemić et al. 2007). A periodic mesoporous organosilica (PMO) was synthesized by using surfactant Pluronic P123 and silica to remove the PAHS from aqueous solution. The PAHs removal efficiency was 70, 40, 50, 70 and 70 % for acenaphthene, fluoranthene, fluorene, naphthalene, and pyrene with initial concentration of 10 mg/L (Vidal et al. 2011). An immature coal (leonardite) was employed to remove benzo(k) fluoranthene, benzo(a)pyrene, benzo(g,h,i)perylene, fluorene, and pyrene from water. All four PAHs had the removed efficiency of 82%, except fluorene that was 78.4% (Zeledón-Toruño et al. 2007b).  Inorganic adsorbents such as quartz sand, kaolinite, and natural clay, and organic adsorbent such as activated sludge were employed for adsorbing naphthalene, phenanthrene, and pyrene from a wastewater treatment plant. The removal efficiency of naphthalene, phenanthrene, and pyrene were 84.4, 90.1, and 96.5 % by the oxidation ditch (Liu et al. 2011). Quartz sand, kaolinite, and natural clay were used to adsorb naphthalene, phenanthrene, and pyrene from a domestic wastewater treatment plant in Xi’an, China (Liu et al. 2011).  26  Table 2.4 Summary of PAHs removal from various aqueous media by minerals and modified minerals Adsorbent Surfactants Media PAHs References  Clinoptilolite SDBAC1 Distilled Water FLA2, FLU3, PHN4, PYR5, benz[a]ANT6 (Lemić et al. 2007) Clinoptilolite HDTMA7 n-Paraffin NAP8 (Faghihian and Mousazadeh 2007b) Zeolite   Water NAP (Chang et al. 2004) Sepiolite DTMA-Br9 Water NAP (Gök et al. 2008) Natural clay sepiolite  Water PHN and PYR (Cobas et al. 2014) Natural clay  WWTP10 NAP, PHN, and PYR (Liu et al. 2011) LECA11  Distilled Water FLA, PHN, PYR  (Nkansah et al. 2012) Bentonite HDTMA-Br Water NAP (Kaya et al. 2013)  silica Pluronic P12312 Water ACN13, FLA, FLU, NAP, PYR (Vidal et al. 2011) leonardite  Milli Q Water Benzo[k]FLA14, benzo[a]PYR15, benzo[g,h.i]PRY16, FLU,PYR (Zeledón-Toruño et al. 2007b)     1 SDBAC: stearyldimethylbenzylammoniumchloride  2FLA: fluoranthene   3FLU: fluorene      4PHN: phenanthrene     5PYR: pyrene       6benz[a]ANT: benz[a]anthracene    7HDTMA: (hexadecyltrimethylammonium)   8NAP: naphthalene      9DTMA-Br: dodecyltrimethylammonium bromide  10 WWTP: wastewater treatment plant    11LECA: Lightweight Expanded Clay Aggregate   12 Pluronic P123: Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) 13 CAN: acenaphthene     14benzo[k]FLA: benzo(k) fluoranthene 15 benzo[a]PYR: benzo(a)pyrene     16benzo[g,h.i]PRY: benzo(g,h,i)perylene    .  27  Chapter 3: Materials and Methodologies 3.1 Materials & Instruments Natural clinoptilolite zeolite (from here on, called clinoptilolite) has been obtained from Bear River Zeolite Co., United States. Appendix B.1 presents the main properties of this clinoptilolite (Xu et al. 2010; Xu et al. 2013). The Appendix indicates that the chemical composition of clinoptilolite includes Al (6%), Fe (1.3%), K (3.46%), Ca (1.6%) and other elements. In addition, the rock analysis of clinoptilolite includes SiO2 (67.14%), Al2O3 (12.45%), Na2O (2.6%), Fe2O3 (2.56%) and a small amount of other components.  Surfactants and PAHs were supplied by Sigma Aldrich with purity of >98%. They are as follows: cetylpyridinium chloride (CPC), didodecyldimethylammonium bromide (DDAB), hexadecyltrimethylammonium bromide (HDTMA-Br), tetramethylammonium chloride (TMA-Cl), anthracene (ANT), fluoranthene (FLA), fluorene (FLU), phenanthrene (PHN), pyrene (PYR) and phenanthrene-d10 (phenanthrene-d10 used as an internal standard). Acetone and methylene chloride or dichloromethane (DCM; CH2 Cl2) (HPLC grade) were supplied by Fisher Scientific. Toluene (HPLC grade) was purchased from Caledon Laboratories Ltd.  Water was purified with a Synergy UV Milli-Q system from Millipore. Chemical structures and properties of the studied cationic surfactants are given in Appendix B.2 and B.3, respectively. CPC, DDAB, HDTMA, and TMA have 21, 38, 19 and 4 carbons in their structures, respectively. DDAB and HDTMA have two and one long hydrocarbon chains in their structures, respectively, while CPC has one long hydrocarbon chain and one aromatic ring, and TMA does not have any long hydrocarbon chains. To provide the surfactant solutions for modification with concentration above CMC, the amounts of 1.79, 0.925, 0.729, and 2.18 g of CPC, DDAB, HDTMA, and TAM, respectively, were dissolved separately in 1000 ml of deionized water. 28  These solutions correspond to initial concentrations of 5, 2, 2, and 20 mmole/L for CPC, DDAB, HDTMA, and TMA, respectively. Stock standard solutions of single PAHs with concentration of 2.5 g/L for anthracene and 5 g/L for fluoranthene, fluorene, phenanthrene, and pyrene were prepared in toluene. The mixture solution of all PAHs (e.g., anthracene, fluoranthene, fluorene, phenanthrene, and pyrene) was prepared in toluene with concentration of 250 mg/L for anthracene, and 500 mg/L for fluoranthene, fluorene, phenanthrene, and pyrene. The adsorption solution to spike the water samples was prepared in acetone to provide the concentrations of 50 µg/L for anthracene, and 100 µg/L for fluoranthene, fluorene, phenanthrene, and pyrene in deionized water and landfill leachate. All of the stocks, mixture, and adsorption solutions were contained in amber glass bottles and were stored in a freezer at -18oC until use. All glassware was washed with detergent and then washed with water and after that was baked in a Thermo Scientific BF51728C-1Lindberg/Blue M Moldatherm Box Furnace at 500ºC for two hours. After the temperature of the furnace lowered to room temperature, the glassware was taken out and the lids were put on. The glassware without lids were wrapped with aluminum foil to prevent contamination for the next use.   3.2 Na-Pre-treatment of Clinoptilolite Clinoptilolite was sieved by using VWR® Pre-Certified Test Sieves of 30-40 mesh size made by the American Society for Testing, washed with tap water to reduce dust, and dried in the Mechanically Convected L-C Oven. Several studies have suggested that a pre-treatment of clinoptilolite with NaCl solution could increase their ion exchange capacities to achieve a final homoionic or near homoionic Na+ form of the clinoptilolite by increasing the effective cation exchange capacity (Ghiaci et al. 2004; Jarraya et al. 2010; Kuleyin 2007; Wingenfelder et al. 29  2006). Raw clinoptilolite removed Zn ~12–15% less than that of the pretreated clinoptilolite with NaCl (Xu et al. 2013). Clean and dried clinoptilolite with sizes of 595-420 microns has been treated with 1 mol/L NaCl in 1:10 solid –liquid ratio according  to Kuleyin (2007) and Wingenfelder et al. (2006) to homogenize the sodium ions on its exchange sites (Kuleyin 2007; Wingenfelder et al. 2006) for 24 hours at 220 rpm and at room temperature. Then, the supernatant was separated and solids were washed with deionized water until no chloride was detected by using a calorimetric solution of ferricyanide. The solids, Na-clinoptilolite, were dried in the oven at 105oC. The details of pre-treatment of clinoptilolite with NaCl are presented in Appendix B.4. 3.3 Modification of Clinoptilolite All of the modified clinoptilolites were based on the Na-clinoptilolite with sizes of 420-595 microns. The concentrations of CPC, DDAB, HDTMA-Br and TMA-Cl for modification were a 5, 2, 2, and 20 mmol/L, respectively. The selected concentrations for CPC, DDAB, HDTMA-Br surfactants were above their critical micelle concentration (CMC) because when the surfactant concentration is higher than CMC micelles have an significant role in the uptake of organic contaminants, (Park and Jaffe 1993) developing a bilayer or micelle (Rosales-Landeros et al. 2013). In Appendix B.3, surfactant critical micelle concentrations (CMC) are provided. After pre-treatment, 10 g of Na-pretreated clinoptilolite was added to 150 mL solutions of each cationic surfactants separately; CPC (CMC:0.92 mmol/L) (Li et al. 2014; Zhan et al. 2011), HDTMA (CMC:0.9 mmol/L) (Kuleyin 2007; Tashauoei et al. 2010; Wingenfelder et al. 2006), DDAB (CMC:0.0144 mmol/L) (Jarraya et al. 2010), and TMA-Cl (Feliciano Lozada 2000). The mixtures of clinoptilolite and surfactant solution in a flask were shaken for 24 hours at 220 rpm at room temperature. To collect the modified clinoptilolite solids after the 24 hours shaking, and 30  then settling, the solids were kept in the flask, and the supernatant was separated by pouring it into a bottle; later the non-adsorbed surfactant was measured in the solution. The solids were separated from supernatant and the particles were washed with deionized water until the surfactant concentration was below the detection limit of Phoenix 8000 Tekmar Dohrmann TOC UV Persulfate or the UV/Vis instrument to prevent surfactant leaching to the environment. For quality control and assurance, and check the linearity of the results from the TOC analyzer and UV/Vis, calibration standards of at least five concentration levels were carried out for each surfactant. To measure if any contamination was introduced through sample handling, a blank was processed together with the samples. For the measurement of DDAB, HDTMA, and TMA surfactants, the TOC analyzer was used with the detection limit of 0.5 mg/L. The adsorbed amount of surfactant on clinoptilolite was calculated by subtracting the initial concentration of surfactant minus the non-adsorbed concentration of surfactant in the supernatant. The CPC, DDAB, HDTMA, and TMA modified clinoptilolites were dried at 60-65oC  for 24 hours (Chutia et al. 2009; Kuleyin 2007). From here on, CPC, DDAB, HTMA and TMA modified clinoptilolites are called CPC-MC, DDAB-MC, HDTMA-MC and TMA-MC, and NC for the Na treated clinoptilolite.  Figure 3.1 shows the steps of clinoptilolite modifications with cationic surfactants. Figure 3.2 is a pictogram of the three main steps of clinoptilolite modification. The details of modifications are presented in Appendix B.5, B.6, B.7, and B.8 for CPC-MC, DDAB-MC, HDTMA-MC and TMA-MC, respectively. Appendix B.9 provides the calibration curve for CPC standards and the measured concentration of CPC in supernatant after modification and leached CPC from modified clinoptilolite in the solution after each wash with deionized water at room temperature by using an ultraviolet- visible (UV/Vis) spectrophotometer. The leachability concentration of CPC from CPC-MC was low and it could not measure with the TOC analyzer 31  because the leached concentration was close to the TOC analyzer detection limit. Appendix B.10, B.11, and B.12 provide the calibration curves for surfactant standards and the measured concentration of DDAB, HDTMA, and TMA in the supernatant after modifications and leached surfactants after the 9, 11, and 7 numbers of washes of modified clinoptilolites with deionized water at room temperature using a TOC analyzer. The number of washes for each modified clinoptilolite was different because the leachability of each surfactant was different and the aim was to reach the minimum leachability concentration to protect the aquatic life.  32   Figure 3.1 Summary of modification of natural clinoptilolite   33   Figure 3.2 Pictogram of clinoptilolite modification steps 3.4 Thermal Effect on Stability of the Surfactants on Modified Clinoptilolites The potential leachability of surfactants from modified clinoptilolites at different temperatures was investigated to find the potential stable modified clinoptilolites, which might affect the adsorption capacity and impact the environment. Each of the four dried modified clinoptilolites and deionized water was added into a 250 mL Erlenmeyer flask with solid-liquid ratio of 1:100. The flasks were shaken at 150 rpm for 24 hours (Wibowo et al. 2011). The 34  stability test was performed at four different temperatures; 5, 10, 20, and 35oC. After 24 hours, the supernatants were separated and analyzed for the cationic surfactant concentrations using the TOC analyzer and UV/Vis spectrophotometer.  Appendix B.13 provides the calibration curve for CPC standards and the CPC concentration after exposing modified clinoptilolite at different temperatures of solution using the ultraviolet- visible (UV/Vis) spectrophotometer to measure the CPC concentration. Appendix B.14, and B.15 provide the calibration curves for surfactant standards and the TOC and concentration of DDAB, and HDTMA after exposing modified clinoptilolites at different temperatures of solution using a TOC analyzer. 3.5 Batch Adsorption Test Procedure  Clinoptilolite adsorption was determined by adopting the US EPA (1996) batch adsorption method as described by (Björklund and Li 2015; U.S. EPA 1990; U.S. EPA 1996). The details of the batch adsorption procedure are given in Appendix C.1. Five absorbents (CPC-MC, DDAB-MC, HDTMA-MC, NZ, and TMA-MC) have been tested to remove the mixture of anthracene, fluoranthene, fluorene, phenanthrene, and pyrene from deionized water. The solubility of selected PAHs are low (Appendix A, Table A.1): (43-75 µg/L for anthracene, 260 µg/L for fluoranthene, 1900 µg/L for fluorene, 1150 µg/L for phenanthrene, and 132 µg/L for pyrene) in the aqueous environment (Bai et al. 2014; Patrolecco et al. 2010; Zhang et al. 2004). The selected PAH concentrations for the adsorption tests in this study were based on the typical environmental concentrations as indicated in Appendix A.2, Table A.2: 100 mL mixture solution of the five PAHs at 50 µg/L for anthracene, which is the solubility of anthracene in water, and 100 µg/L concentrations for fluoranthene, fluorene, phenanthrene, and pyrene (the solubility of pyrene in water is 132 µg/L), respectively. One gram of each modified clinoptilolite was mixed 35  with 100 mL of solutions containing five PAHs of desired concentrations and was rotated for 24 hours to make sure of adequate equilibration time at room temperature in the bottles. The bottles were placed in an end-over-end shaker on a Dayton-6Z412A Parallel Shaft (USA) roller mixer at 30 rpm. Then, the samples were centrifuged by using a Beckman GS-6 centrifuge for 10 minutes at 1800 rpm and the supernatants were separated and performed liquid- liquid extraction by using a separatory funnel. After extraction, the extracts were evaporated to 1-3 mL by using a Heidolph Laborota 4000 rotary evaporator. After that, the extracts were concentrated further to dryness under a gentle stream of nitrogen gas. To reconstitute the samples, 900 µL toluene was added to each dried sample and shaken, and then 100 µL internal standard (IS) was added before analysis (Björklund and Li 2015). The samples were analyzed for the final concentration of PAHs using a Hewlett- Packard hp 6890 Series GC/MS (Agilent Technologies, Wilmington, USA). Before analysis of the PAHs, a control sample including only PAHs to measure PAHs recovery, a duplicate, and a blank including only deionized water were prepared and analyzed in the same way as samples in each batch sample. In addition, calibrations of six concentration levels were carried out to check the linearity of results of the GC/MS. The detailed experimental data and PAHs adsorption results on various adsorbents are given in Appendix C.2. 3.6 Factors Affecting the Removal Capacity of Modified Clinoptilolites  Adsorption tests have been conducted on four modified clinoptilolites (CPC-MC, DDAB-MC, HDTMA-MC and TMA-MC) and clinoptilolite without any modification to compare the PAHs adsorption results of modified clinoptilolites with non- modified clinoptilolite in order to determine whether modifications are necessary to improve the PAHs adsorption on clinoptilolite. A duplicate for CPC-MC, DDAB-MC, HDTMA-MC, and NC, a control sample including only 36  PAHs to measure recovery, and blank containing only deionized water were analyzed with samples.   Based on preliminary results from PAHs adsorption on five adsorbents, three effective ones (CPC-MC, DDAB-MC, and HDTAM-MC) have been selected to test the effect of contact time, adsorbent dosage, adsorption capacity and stability, pH and temperature. The parameters of the batch adsorption tests on modified clinoptilolites are summarized in Table 3.1.  Table 3.1 Summary of parameters for PAH removal by using modified clinoptilolites Parameters Descriptions Temperature (oC) 5, 20, 35 pH 3, 5.5, 6.5, 9, 11 Contact  time (h) ¼, ½, 1, 2, 4, 8, 24, 48 Solution volume (mL) 100 Adsorbent dose (g) 0.01, 0.05, 0.1, 0.2, 0.5, 1, 2 PAHs concentration  100 µg/L for FLA1, FLU2, PHN3,  PYR4  And 50 µg/L for ANT5 1FLA: fluoranthene    2FLU: fluorene  3PHN: phenanthrene    4PYR: pyrene      5ANT: anthracene 3.6.1 Adsorption Kinetics The effect of contact time on PAHs adsorption was investigated to evaluate the PAH uptake kinetic. Batch sorption experiments have been conducted by mixing 1g of each three modified clinoptilolite (CPC-MC, DDAB-MC, HDTMA-MC) with 100 mL of PAH solutions containing the desired concentration of the PAHs at room temperature (20 ± 2°C) and at different reaction intervals to test the adsorption kinetic. The mixtures were rotated for the desired duration of ¼, ½, 1, 2, 4, 8, 24, and 48 hours to obtain the extent of adsorption. Two duplicates 37  of CPC-MC, six duplicates of DDAB-MC, and one duplicate of HDTMA-MC for different reaction times, and one control sample and a blank were analyzed among the samples as well. Appendix C.3 presents the detailed experimental data and results of PAHs adsorption versus contact time for three modified clinoptilolites.  3.6.2 Effect of Different Adsorbent Dosage  The effect of the adsorbent amounts was investigated with a 100 mL solution of PAHs and varying amounts of each adsorbent from 0.01, 0.05, 0.1, 0.2, 0.5, 1, and 2 g (solid-liquid ratio of 1:10000, 1:2000, 1:1000, 1:500, 1:200,1:100, 1:50, respectively) at room temperature after a 24 hour rotation. The PAH adsorption results for one gram of modified clinoptilolites were adopted from Section 3.6 as a base line. One duplicate and one control sample for each adsorbent, and a blank were analyzed among the samples as well. Appendix C.4 presents the detailed experimental data and results of PAHs adsorption on various dosages of modified clinoptilolites. 3.6.3 Adsorption Capacity of Adsorbents to Remove the PAHs  PAHs have very low solubility in water for example, anthracene, fluoranthene, fluorene, phenanthrene, and pyrene have the solubility of 0.050, 0.26, 1.9, 1.15 and 0.135 mg/L in water, respectively. The results of effect of adsorbent dosage showed that a very small amount of modified clinoptilolites adsorbed the maximum soluble amount of anthracene and phenanthrene from water. To determine the capacity of these modified clinoptilolites, the repeated adsorption tests with a fresh solution of the PAHs mixture was adopted to simulate PAHs removal from continuous water flow such as PAH-contaminated groundwater, surface water, landfill leachate, etc. Based on the preliminary adsorption results, three different absorbents have been used (CPC-MC, DDAB-MC, and HDTMA-MC) with a mixture of five PAHs. In each bottle, 0.1 g of each absorbent was added to 100 mL solution spiked with the PAHs mixture and rotated for 24 hours. 38  After that, the supernatant was separated by centrifuging and was tested for the PAH concentrations. The solids in each bottle were kept, reused, and 100 mL fresh solution of PAH mixture was added. For this study, the process was repeated 21 times. For quality control and quality assurance, one duplicate, and a control sample of only PAHs were included in each successive adsorption batch test. The PAH residual concentrations were measured for 1 out of 3 samples from 21 successive batches. The total number of samples, which were measured for their concentration of PAHs adsorbed on CPC-MC, DDAB-MC, and HDTMA-MC, were 14, 14, and 13, respectively. The accumulated PAH was measured directly, and indirect estimation of PAH residual concentration after each successive batch was performed using interpolation method, assuming linear accumulative uptake, based on the measured data. Linear interpolation method (Section 3.8 data interpretation, equation (8)) was used to estimate the residual PAH concentrations that were not analyzed. The PAHs loaded modified clinoptilolites were stored in freezer for a later leachability test. Appendix C.5 provides the measured and the estimation of PAHs accumulation after 21 successive adsorption batch tests on three different modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). 3.6.4 Leachability of Adsorbed PAHs from Modified Clinoptilolites  The PAHs loaded modified clinoptilolites were tested for leachability. The 0.1 g of each PAHs loaded modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) and 100 mL deionized water was added to the each bottle, containing modified clinoptilolite and rotated for 24 hours at room temperature. Then, the solution was centrifuged and the supernatant was analyzed for PAHs concentration of desorption. In each batch sample, one duplicate, and control samples were included for quality control.  Appendix C.6 provides the detailed experimental data and measured stability of PAHs on modified clinoptilolites at room temperature.  39  3.6.5 Adsorption Competition of Single Vs Mixture PAHs  To investigate the effect of competing fluoranthene adsorption on modified clinoptilolites, and establish a preferential fluoranthene removal on modified clinoptilolites, the adsorption tests have been performed using a single PAH, and mixture of PAHs. To compare the fluoranthene adsorption in a single versus a mixture solution, 100 mL of PAHs mixture solution was added to 0.05 g of DDAB modified clinoptilolite. For individual PAHs, 100 mL of deionized water was spiked by fluoranthene solution and added to 0.05 g of each modified clinoptilolite (CPC-MC, DDAB-MC, and HDTMA-MC). The adsorption results of mixture PAHs on 0.05 g of CPC-MC, and HDTMA-MC from Section 3.6.2 were used to compare to single PAH adsorption results on CPC-MC, and HDTMA-MC. The concentrations of fluoranthene in single and mixture solutions were a 100 µg/L. In addition, two control samples, one including only single PAH (fluoranthene) and the other one including the PAHs mixture solution, and one duplicate were used for quality control. Appendix C.7 shows the experimental data and adsorption results related to competition effect of fluoranthene versus mixture PAHs.   3.6.6 Effect of pH  The effects of pH values on PAHs adsorption were investigated to find any variation on PAHs uptake by the studied sorbents. The initial pH values of PAHs mixture solutions were adjusted at 3, 6.5, 9, and 11with drops of diluted HNO3 or NaOH solution. One gram modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) were added to amber glass bottles containing 100 mL PAHs mixture solution for each pH of interest. For each pH of interest, two bottles were used containing PAHs solution at pH of interest and one without pH adjustment for the PAHs recovery. Three duplicates, and three control samples, one for each pH of interest, were analyzed with samples for quality control as well. The PAHs adsorption results of Section 40  3.6 on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) were used as pH value of 6.5 for comparison to other pH values. Appendix C.8 shows the detailed empirical data and adsorption results related to pH effect on modified clinoptilolites.   3.6.7 Effect of Temperature Temperature effects on the adsorption tests were carried out in environmental temperature control chamber with 100 ml solution of mixture PAHs solution containing the desired concentration of mixture PAHs with one gram of adsorbent at 5, and 35°C for 24 hours. The PAHs adsorption results of Section 3.6 on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) at room temperature (20 ± 2oC) were used for comparison to other temperatures. The complete empirical data and PAHs adsorption results at different temperatures are given in Appendix C.9.  3.6.8 PAH Removals from Landfill Leachate Using Modified Clinoptilolites Although the concentrations of each PAH in landfill leachate were less than 1 µg/L, landfill leachate can be used to investigate the background effect on PAHs adsorption. Landfill leachate has been filtered, using Whatman® glass microfiber filter/binder free Grade GF/C Grade GF/C circles 70mm. The chemical characteristics of landfill leachate were identified by measuring pH, TOC, nutrients including ammonia, NOX, and phosphate, and PAHs.      One gram of each modified clinoptilolite (CPC-MC, and DDAB-MC ) has been put into each bottle in addition to 100 mL filtered landfill leachate, which was spiked with PAHs mixture in order to have 50 µg/L anthracene and 100 µg/L fluoranthene, fluorene, phenanthrene, and pyrene plus the background PAHs in landfill leachate. The bottles were rotated for 24 hours at room temperature and supernatants were separated by centrifuge and were tested for PAHs concentration. In addition, two filtered leachate samples including only landfill leachate, and two 41  control samples including one deionized water and one landfill leachate that were spiked with PAHs mixture, were included for quality control. In Appendix C.10, the detailed empirical data and results of removal of PAHs from landfill leachate using modified clinoptilolites are given. 3.7 QC/QA  For quality control and quality assurance and check the linearity of results of GC/MS, calibrations of six concentration levels were carried out including the concertation of a 2.5, 5, 10, 50, 100, and 200 µg/L in toluene. To confirm linearity in GC/MS response over the period of the run, calibration standards were run before and after a batch samples. To measure contamination introduced throughout sample handling, a blank was processed together with samples. For quality control and assurance, and to check the linearity of results of the TOC analyzer and UV/Vis, calibration standards of at least five concentration levels were carried out for each surfactant in water. To measure any contamination introduced throughout sample handling, a blank was processed together with the samples. The blank concentration was corrected for the TOC concentration for DDAB, HDTMA and TMA, and CPC absorbance for all samples.  3.8 Data Analysis & Interpretation  For data interpretation, statistics were applied, and mean value and error bar are applied.  Very low levels of PAHs (<0.01-0.5 µg/L) were detected in blanks, and background corrections have not been done on data because of low level of PAHs in the blank samples. The blank average PAH concentrations for anthracene, fluoranthene, fluorene, phenanthrene, and pyrene were 0.01, 0.43, 0.06, 0.04, 0.39, respectively)  The average recoveries of fluorene were about 70%-88%. For anthracene, and phenanthrene the average recoveries was 70%-103%, and for fluoranthene, and pyrene the average recoveries were 80% -107%. Due to multisets of the extraction processes, theses recoveries are comparable to 42  those reported in U.S. EPA (1990) for anthracene, fluoranthene, fluorene, phenanthrene, and pyrene (U.S. EPA 1990). All samples containing DDAB-MC, and selected containing CPC-MA and HDTMA-MC were extracted and analyzed in duplicate and selected samples in triplicate. Detection limit of GC/MS for PAHs were 0.001µg/L. Adsorption Capacity Adsorption capacity is the amount of the PAH compound adsorbed by the modified clinoptilolite, at equilibrium (qe, µg/g) and at that specific time t (qt) (Chang et al. 2004; Crisafully et al. 2008):  qe =  (Co− Ce)∙Vm        (1) qt =  (Co− Ct)∙Vm        (2) Co is the initial concentration [µg/L]; Ct is the liquid-phase concentration at that specific time t [µg/L]; Ce is the remaining concentration in the solution at equilibrium [µg/L]; V is the solution volume [L]; and m is the mass of modified clinoptilolite [g].  Removal Efficiency The remaining concentration of the PAH compound in the solution is used to estimate the percentage retention (R, %) or removal efficiency of PAHs compounds (Björklund and Li 2015):  R (%) = (Co−Ce)Co× 100      (3) Co is the initial concentration of PAHs compound [µg/L]; Ce is the residual or remaining PAHs concentration in the solution at equilibrium [µg/L]. Standard Deviation In statistic, the standard deviation (STD) is a measurement of quantifying the degree of variation or dispersion of values of the data points. The lower the standard deviation, the closeness of data points to the mean (more precision) while the higher standard deviation means spread out of the data points over a wide values range ("Standard Deviation." 2014). 43  𝑆𝑆𝑆𝑆𝑆𝑆 = �∑|𝑋𝑋−𝑋𝑋�|2𝑁𝑁       (4) ∑ is the summation, 𝑋𝑋 is a value in the data set,  𝑋𝑋 � is the mean value of the data set, and N is the number of value in the data set. Adsorption Kinetics Models Ion exchange, chelation, physical and chemical sorption are the sorption procedures (Ho et al. 2000) . The liquid-phase transport procedure controls the overall reaction rate once the chemical reaction is very fast at the solid phase and is not related to solid-phase transport procedure. Sorption mechanisms are based on sorbate-sorbent interaction and settings of the system (Ho et al. 2000). To study the controlling mechanisms of adsorption, three kinetic models are available. The pseudo-first-order, pseudo-second-order, and intra-particle diffusion  The pseudo-first-order adsorption rate equation (Chang et al. 2004; Hall et al. 2009): dqtdt= k1  (qe − qt)       (5) When the adsorption rate is reliant on the second order equation on the sorbate removal, the pseudo-second-order adsorption rate equation is presented as (Chang et al. 2004; Hall et al. 2009; Ho and McKay 1999):  dqtdt= k2  (qe − qt)2       (6) The amount of adsorbed PAHs [µg/g] on the modified clinoptilolite at equilibrium and at the specific time t [h] is qe and qt, respectively (equation 1and2); the rate constants of first- and second-order sorption are k1 [1/h] and k2 [g/(µg∙h)], respectively.  If the plot of t/qe versus t provide a linear relationship, then pseudo-second-order kinetics are valid to contaminant-adsorbent procedure, and the slope and intercept define the qe and k2 (Ho et al. 2000). 44  Weber’s intra-particle diffusion model is use to explain the diffusion mechanism, the empirical kinetic data are fitted to the intraparticle diffusion model (Björklund and Li 2015; Hameed et al. 2008) to obtain understanding into the mechanisms and rate limiting steps involving the kinetics of adsorption (Weber and Morris 1963): qt  = kid  t1/2 + C       (7) C is the intercept and kid is the intraparticle diffusion rate constant [µg/(g∙h1/2)] at the specific time t [h]. The amount of adsorbed PAHs [µg/g] on the modified clinoptilolite at the specific time t [h] is qt . The kid is the intraparticle diffusion rate constant [µg/(g.h½) ]. If the regression of qt versus t1/2 is linear and passes through the origin, then intraparticle diffusion is the only rate-controlling step. The graph intercept indicates the boundary layer effect. When intercept is greater, the contribution of the surface sorption is larger in the rate controlling. Linear Interpolation  The linear interpolation is used to estimate the unknown value of a point by connecting two adjacent known point values with a straight line. If the two known point values are (x1, y1), and (x2, y2), then the interpolate point value for point (x, y) is (Bolea et al. 2011; Gouraud 1971): 𝑦𝑦 = 𝑦𝑦1 + (𝑥𝑥 − 𝑥𝑥1) �𝑦𝑦2−𝑦𝑦1𝑥𝑥2−𝑥𝑥1�        (8)  when the function is not varying rapidly between known point values, this model works the best (Bolea et al. 2011)  45  Chapter 4: Results and Discussions  4.1 Modification and Leachability of Surfactant from Modified Clinoptilolites Clinoptilolite was modified by four different cationic surfactants (CPC, DDAB, HDTMA and TMA) to provide four different modified clinoptilolites to use as adsorbents to remove the organic pollutants from the aqueous solutions; Table 4.1 indicates the clinoptilolite modification conditions. Table 4.2 shows the amount of surfactants that were used to modify clinoptilolite, the remaining concentration of surfactants in the solution after modifications, and surfactant concentrations after several washes of modified clinoptilolites to investigate the surfactants leachability from modified clinoptilolites. Figure 4.1(a) indicates the leachability of modified clinoptilolites for 10, 9, 11, and 7 washes of CPC-MC, DDAB-MC, HDTMA-MC, and TMA-MC, respectively with the deionized water. Figure 4.1 (b) presents the percentage of surfactants that were absorbed before washes and after washes on modified clinoptilolites, and the percentage of leached surfactants from modified clinoptilolites. Cationic surfactants can adsorb on solid surface such as zeolite because of surfactants’ dual chemical features by electrostatic and/or hydrophobic interactions, or cation exchange reaction of zeolite (Leone and Iovino 2016). CPC, DDAB, HDTMA and TMA were adsorbed on clinoptilolite about 99.7, 99.3, 95.6, and 98.6 %, respectively. After the number of washes (10, 9, 11, 7 washes for CPC-MC, DDAB-MC, HDTMA-MC, and TMA-MC, respectively), the surfactants were slightly leached from the CPC, DDAB, HDTMA and TMA modified clinoptilolites about 0.7, 0.4, 8.1, and 2.6 mmol surfactant/Kg clinoptilolite, respectively (0.9, 1.4, 28.2, 1.8 % for CPC-MC, DDAB-MC, HDTMA-MC, TMA-MC, respectively) and released to the solution. Therefore, it can be concluded that the adsorbed surfactants of CPC, DDAB and HDTMA on clinoptilolite are stable 46  due to low leachability of surfactants (<1.8%). These leached surfactants into solution could be associated with the non-adsorbed or excess surfactants.  Ion exchange and hydrophobic interaction are the two main adsorption mechanisms of cationic surfactants onto different clay and zeolite minerals (Li and Bowman 1997; Xu and Boyd 1995). Ersoy and Celik (2003) found that the mechanism of adsorption of surfactant on clinoptilolite occurs only in the electrical double layer (EDL) at the clinoptilolite/water interface. The ion-exchange mechanism forms ~35-50% of the total surfactant adsorption on clinoptilolite. Hydrocarbon chain length of surfactants influence the ion exchange and hydrophobic interaction mechanisms significantly (Ersoy and Celik 2003). The surfactants adsorption onto clinoptilolite takes place in two steps based on the adsorption level. First, the surfactant is adsorbed by cation exchange, and then the surfactant is adsorbed on clinoptilolite by hydrophobic interactions (Sullivan et al. 1998). The modified clinoptilolites, which are prepared with surfactant solution above the CMC and ECEC, are the most stable adsorbent and have the quickest adsorption time (Apreutesei et al. 2008).   The leachability result for HDTMA modified clinoptilolite is in agreement with the following study. For example, natural zeolite tuff was modified by HDTMA-Br to remove the antimonite. After threefold washing of modified zeolite with distilled water, the HDTMA leached from zeolite was almost 15% (Wingenfelder et al. 2006).    47  Table 4.1 Summary of experimental conditions for modification of clinoptilolite with surfactants solution, shaken at 220 rpm, at room temperature (20 ± 2oC) for 24 h, and washed with 150 mL of deionized water Surfactant Concentration (mmol/L) Solid-Liquid ratio   Number of solid washes Total Leachability (mg/L) CPC 5 1:15  10 16.30 DDAB 2 1:15  9 12.5 HDTMA-Br 2 1:15  11 197 TMA-Cl 20 2:15 7 37.8   Table 4.2 Summary of estimation of residual surfactant concentrations after modification and leachability concentration after number of washes at room temperature  Description  CPC  DDAB   HDTMA  TMA  Clinoptilolite amount (g) 10 10 10 20 Initial concentration of surfactant (mg/L) 1790 925.3 728.9 2180 Volume of solution (mL)  150 150 150 150 Expected surfactant adsorb on clinoptilolite (mmol/kg) 75 30.0 30.0 149.2 Non-adsorbed surfactant in the solution (mg/L) 5.3 6.5 32.2 31.3 Adsorbed surfactant on clinoptilolite (mmol/kg) 74.8 29.8 28.7 147.0 Adsorbed surfactant on clinoptilolite after modification % 99.7 99.3 95.6 98.6 Leached surfactant in the solution after number of washing  from modified clinoptilolite (mg/L) 16  13  197  38  Leached surfactant after number of washing from modified  clinoptilolite (mmol/kg) 0.7  0.4  8.1  2.6  Leached surfactant after number of washing from the modified clinoptilolites % 0.9  1.4  28.2  1.8  Adsorbed surfactant on clinoptilolite after number of washing (mmol/kg) 74.1  29.4  20.6  144.5  Adsorbed surfactant on clinoptilolite after number of  washing % 98.8  97.9  67.3  96.8   48  (b)SurfactantCPC DDAB HDTMA TMASurfactant %020406080100Adsorbed surfactant before wash Remained surfactant after wash Leached surfactant Number of washes2 4 6 8 10Surfactant residual in the solution (mg/L)051015202530CPC DDABHDTMA TMA(a) Figure 4.1 Surfactant Leachability, (a) The leachability concentration of surfactants (CPC, DDAB, HDTMA, and TMA) from modified clinoptilolites after 10, 9, 11, and 7 washes of CPC-MC, DDAB-MC, HDTMA-MC, and TMA-MC, respectively with deionized water at room temperature. All samples were run in duplicate. Error bar represent the standard division (n=2), (b) surfactant % absorbed before washes and after washes on modified sorbents, and leached surfactant% from modified sorbents.  49  The adsorbed surfactants (CPC, DDAB, HDTMA and TMA) on clinoptilolite after the number of washes were about 98.8, 97.9, 67.3, and 96.8 %, respectively. It is shown in Figure 4.1 (b) that HDTMA-MC and TMA-MC have a higher leachability concentration compared to CPC-MC and DDAB-MC. The maximum leachability of CPC-MC and DDAB -MC in a wash was about 2.6 mg/L, whereas HDTMA-MC and TMA-MC were 28 and 25 mg/L, respectively.  Pictures of clinoptilolite and modified clinoptilolites with CPC, DDAB and HDTMA are given in Figure 4.2. The Appendix B.10, B.11, B.12, and B.13 provide the leached concentration of CPC, DDAB, HDTMA, and TMA after each wash of modified clinoptilolites. The leached CPC from CPC-MC after 10th washes was 0.43 mg/L that is lower than the EC50 of CPC for Bombina orientalis embryos that was 0.531 mg/L (Table 2.1) in Park et al. (2016) study (Park et al. 2016). The leached DDAB from DDAB-MC after 9th washes was 1mg/L that is much lower than the EC50 of DDAB for unicellar green alga Dunaliella sp. that was18 mg/L in Kaj et al. (2014) research (Kaj et al. 2014). The leached HDTMA from HDTM-MC after 11th washes was 3 mg/L that is higher than the EC50 of HDTMA for Marine Macroalga, Ulva lactuca that was 2.4 mg/L in Masakorala et al. (2011) investigation  (Masakorala et al. 2011). The aim was to provide adsorbents that have less leachability to protect the aquatic life. Therefore, it can be assumed that CPC-MC and DDAB-MC are effective adsorbents to remove contaminant from aqueous solution.  It should be noticed that in this study the initial concentration of surfactants was low (CPC, DDAB, HDTMA-Br, and TMA were 5, 2, 2 and 20 mmol/L, respectively) to reduce the potential risk to aquatic life because of potential surfactants leachability. The initial concentrations were low in comparison to other published studies. For instance, 100 mmol/L HDTMA solution (Tashauoei et al. 2010),  30 mmol/L HDTMA (Kuleyin 2007) , a 30 wt.% aqueous HDTMA-Cl 50  solution (Bowman 2003), 50 wt.% HDTMA-Cl, CPB solution (Seifi et al. 2011). In addition, it was reported that HDTMA loading was 208 (Li and Bowman 1997), and 180 (Bowman et al. 2002) mmol HDTMA/kg zeolite that were very high (7 and 6 times, respectively) compared to this study that was 28.7 mmol HDTMA/kg clinoptilolite before washes with deionized water. In addition, Krishna et al. (2001) reported that because of low solubility of the HDTMA in water, at high concentration of surfactant, the HDTMA solution was cloudy, and HDTMA crystallized on the mineral surface and resulted in washing problems (Krishna et al. 2001).     Although there are not any water quality criteria for the most surfactants, including CPC, DDAB, HDTMA, and TMA that were used in this study because of a gap of information related to their toxicity, few surfactants are included in BC working water guidelines. For example, the criterion is a 65 µg/L for linear alkylbenzene sulphonates (LAS) in fresh water aquatic life for long-term concentrations (Gov. BC. Ca. 2015).  TMA has a short hydrocarbon chain (<6 carbons) (Kissa 2001) and HDTMA has only one long hydrocarbon chain (12 carbons) (Kissa 2001); whereas DDAB has two long hydrocarbon chains and CPC has one long carbon chain and one aromatic ring. The two long hydrocarbon chains in a surfactant can increase the positive charge on the nitrogen in the quaternary ammonium cation and could make a stronger electrostatic interaction (Brycki and Szulc 2014) with clinoptilolite based on Coulomb's law. Based on Coulomb's law that is given in Appendix D.1 as discussed by Berg, et al. (2007), the energy of electrostatic interaction is increased by increasing the electrostatic interaction. Therefore, the stronger bond could reduce leachability of surfactant into the environment. From the results, it can be concluded that CPC and DDAB can make a stronger bond to the clinoptilolite.  51   Figure 4.2 Clinoptilolite and modified clinoptilolites’ pictures; (a) clinoptilolite, (b) CPC-MC, (c) DDAB-MC, (d) HDTMA-MC   52  4.2 Temperature Effect on Modified Clinoptilolite Stability  The stability of surfactant on modified clinoptilolite at different temperatures is an important parameter to study in order to estimate whether the surfactant leachability is increased or decreased in the solution at geographic locations with different climate. Thermal stabilities of CPC-MC, DDAB-MC, and HDTMA are shown in Figure 4.3 and the leached surfactants % is summarized in Table 4.3. Data are provided in Appendix in B.13, B.14, and B.15 for CPC-MC, DDAB-MC, and HDTMA-MC, respectively. The concentration of leached HDTMA from HDTAM-MC in the solution was more than the leached concentration of CPC and DDAB from CPC-MC and DDAB-MC at the same temperature, indicating that HDTMA-MC was less stable compared to CPC-MC and DDAB-MC at the same temperature. HDTMA modified clinoptilolite had a higher leachability (28%) and less thermal stability (1.6% at 35ºC) compared to CPC (0.01% at 35ºC) and DDAB (0.18% at 35ºC) modified clinoptilolites. Increasing temperature from 5 to 35oC reduced the chemical stability of DDAB from 0.12 to 0.18 % and 0.48 to 1.6 % for HDTMA modified clinoptilolites. Desorption of HDTMA from the clinoptilolite particles increased with increasing temperature. This thermal instability was insignificant for the DDAB and CPC modified clinoptilolites; in fact, it seems the two long hydrocarbon chains in surfactants make them stronger (CPC and DDAB> HDTMA).   53  Temperature (oC)5 10 20 35Surfactant residual in the solution (mg/L)0246810 CPC DDAB HDTMA  Figure 4.3 Effect of temperatures on stability of surfactants on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). All samples were run in duplicate. Error bar represent the standard division (n=2).   Table 4.3 Summary of surfactant leachability (%) of modified clinoptilolites after number of washes, and at different temperatures   Leachability/adsorbents  CPC-MC DDAB-MC HDTMA-MC Leachability % after number of washes after modification  0.9 1.4 28.2 Leachability % at 5ºC  0.013 0.12 0.48 Leachability % at 10ºC  0.015 0.13 0.82 Leachability % at 20ºC  0.005 0.14 0.98 Leachability % at 35ºC  0.011 0.18 1.6  The CPC that leached into the solution from modified clinoptilolite at 5, 10, 20, and 35oC (0.23, 0.27, 0.08, 0.21 mg/L, respectively, see Figure 4.3 and Appendix B.13, B.14, and B.15) 54  were below the toxicity of the EC50 of CPC for Bombina orientalis embryos that was 0.531 mg/L. The DDAB that leached into the solution from modified clinoptilolite at 5, 10, 20, and 35 oC (1.1, 1.2, 1.3, 1.7 mg/L, respectively) were very much lower than the EC50 of DDAB for unicellar green alga Dunaliella sp. that was18 mg/L in Kaj et al. (2014) study (Kaj et al. 2014). However, the leached HDTMA from modified clinoptilolite at 10, 20, and 35 oC (4, 4.9, 8 mg/L, respectively) were above the EC50 of HDTMA for Marine Macroalga, Ulva lactuca that was 2.4 mg/L in Masakorala et al. (2011) study  (Masakorala et al. 2011), except at 5oC that was 2.4 mg/L. Therefore, using CPC-MC and DDAB-MC as an adsorbent to remove contaminants at different climate is satisfactory in terms of protecting aquatic life whereas HDTMA-MC should be used in cold climate at 5oC.  Based on the equation (4) from Appendix D.2 the temperature has an inverse relation with adsorption. Therefore, when the temperature increased, desorption increased. Increasing the temperature caused an increase of the thermal motion, which could increase the area per molecule which can result in reducing the adsorption (Rosen et al. 2012). Increasing the temperature from 5 to 35oC increased the area per surfactant molecule that consequently decreased the adsorption or increased desorption for HDTMA. Determination of the thermodynamic parameters such as changes in Gibbs-free energy (∆𝐺𝐺ᵒ), enthalpy (∆𝐻𝐻°) and entropy (∆𝑆𝑆°) are shown in the Appendix D.2.    ln(𝑘𝑘𝑑𝑑 ) = ∆𝑆𝑆°𝑅𝑅 − ∆𝐻𝐻°𝑅𝑅𝑅𝑅     (4) 4.3 PAH Removals by Using Different Adsorbents The PAH adsorption results for modified clinoptilolites and clinoptilolite are presented in Figure 4.4. Appendix A.3 provides the water quality criteria for PAHs in different organizations to protect the aquatic life. The comparison of water quality criteria for PAHs and the residual 55  concentration of PAHs for this research are given in Table 4.4. The PAH adsorption results in Figure 4.4 (a) indicated that clinoptilolite and TMA- MC had little PAH adsorptions from aqueous solution. The residual concentrations of anthracene in the solution were 1.0, 0.5, 2.5, 16.8, and 35.2 µg/L by using CPC-MC, DDAB-MC, HDTAMA-MC, TMA-MC and clinoptilolite, respectively. The adsorption results indicate that the water quality criteria is met for anthracene by using CPC-MC, DDAB-MC and HDTMA-MC. The residual concentrations of fluoranthene in the solution were 1.3, 0.6, 2.9, 67.5, and 96.4 µg/L by using CPC-MC, DDAB-MC, HDTAMA-MC, TMA-MC and clinoptilolite, respectively. The adsorption results indicate that the water quality criterion is met for fluoranthene by using CPC-MC, DDAB-MC and HDTMA-MC. The residual concentration of anthracene and fluoranthene exceeded the water quality criteria by using TMA-MC and clinoptilolite. The remaining fluorene concentrations in the solution were 6.1, 4, 16.2, 71.1, 83.5 µg/L when using CPC-MC, DDAB-MC, HDTAMA-MC, TMA-MC, and clinoptilolite adsorbents, respectively. These results also indicate that fluorene met the water quality criteria of BC by using CPC-MC and DDAB-MC adsorbents. The residual concentrations of phenanthrene in the solution were 2.8, 1.2, 6.5, 80.4, and 93.8 µg/L by using CPC-MC, DDAB-MC, HDTAMA-MC, TMA-MC, and clinoptilolite adsorbents. The residual concentrations of phenanthrene which were 0.3 µg/L were above the water quality criterion when using any of the adsorbents,. To meet the water quality criteria for phenanthrene, the GC/MS setup should be changed based on ng/L since the value of 0.3 µg/L is very close to the detection limit of the GC/MS instrument. However, the water quality criterion for phenanthrene was met by using a higher amount of adsorbent, as discussed in Section 4.5. The residual concentrations of pyrene in the solution were 0.9, 0.3, 2.6, 78.9, and 94.8 µg/L by using 56  CPC-MC, DDAB-MC, HDTAMA-MC, TMA-MC, and clinoptilolite adsorbents, respectively. There is no recommended concentration of pyrene for the water quality criterion in fresh water.  Removal of anthracene, fluoranthene, fluorene, phenanthrene, and pyrene by using clinoptilolite were close to 30, 3, 16, 6, and 5%, respectively (Figure 4.4 (b)). Removal of anthracene, fluoranthene, fluorene, phenanthrene, and pyrene by using TMA-MC were approximately 66, 32, 28, 19 and 21%, respectively. However, the removal of PAHs by CPC-MC, DDAB-MC, and HDTMA-MC were high. CPC-MC, DDAB-MC, and HDTMA-MC removed anthracene about 98, 99, and 95%, respectively. Removal of fluoranthene was about 99, 99, and 97% by CPC-MC, DDAB-MC, and HDTMA-MC, respectively. Adsorption of fluorene by CPC-MC, DDAB-MC and HDTMA-MC were 94, 96, and 84%, respectively. Phenanthrene was removed about 97, 99, and 94 % by CPC-MC, DDAB-MC, and HDTMA-MC, respectively. Pyrene removal by CPC-MC, DDAB-MC, and HDTMA-MC was 99, 99, and 97%, respectively.    57  (a)AnthraceneFluorantheneFluorenePhenanthrenePyreneResidual PAHs in the solution (g/L)020406080100(b)PAH compoundsAnthraceneFluorantheneFluorenePhenanthrenePyreneRemoval of PAHs %020406080100Recovery concentration  CPC-MC DDAB-MC HDTMA-MC NZ TMA-MC  Figure 4.4 PAHs adsorption by using various adsorbents at room temperature for 24 hours contact time at pH value of 6.5: (a) residual PAH concentrations in the solution (µg/L), error bar represent the standard deviation of n=3 (b) removal percentage of PAHs from water by using different adsorbents, error bar represent the standard deviation of n=3. The initial PAH concentrations were 50 µg/L for anthracene and 100 µg/L for fluoranthene, fluorene, phenanthrene, and pyrene. 58  Table 4.4 The comparison of BC water quality criterial and the residual concentration of PAHs in the solution by using different adsorbents at room temperature for 24 hours contact time      Adsorbent Description Anthracene Fluoranthene Fluorene BC. Water Quality Criteria (µg/L) 4 4 12 CPC-MC Average Remaining Concentration (µg/L) after Adsorption 1 1.3 6 DDAB-MC 0.5 0.6 4 HDTMA-MC 2.5 2.9 16 TMA-MC 16.8 67.5 71 Clinoptilolite 35 96 83.5  PAH adsorption mechanisms are a primarily hydrophobic process, which are driven by PAH hydrophobicity, Kow, (Nkansah et al. 2012). Based on 16 PAHs’ hydrophobicity (Appendix A.1), the adsorption data in this study for PAH removals on modified clinoptilolites is ordered as follows, from highest adsorption to lowest adsorption:  Pyrene > fluoranthene >anthracene >phenanthrene>fluorene.  The molecular structures of anthracene and fluorene are linear, fluoranthene, and phenanthrene are angular and pyrene is cluster (Sho et al. 2004). This study demonstrates the molecular arrangement of PAHs slightly affects the PAH adsorption, so that PAHs with clustered or linear molecular structures have higher adsorption compared to angular molecular structure with the same molecular weights. For example, although pyrene and fluoranthene have the same molecular weights, pyrene (clustered structure) had slightly higher adsorption (≥0.4 % on CPC-MC, ≥ 0.3 % on DDAB-MC, and ≥ 0.3 % on HDTMA) than fluoranthene (angular structure). In another example, anthracene (linear structure) had slightly higher adsorption (≥0.8 % on CPC-59  MC, ≥0.1 % DDAB-MC, and ≥1.6 % HDTMA) than phenanthrene (angular structure), even though anthracene and phenanthrene have the same molecular weights.  For PAH sorption mechanisms based on the PAHs’ hydrophobicity, several studies have reported with similar results: Nkansah, et al. (2012) examined on lightweight expanded clay aggregate (LECA) with removal order of pyrene > fluoranthene > phenanthrene.  Additionally, Lemić, et al. (2007) investigated on modified zeolite with Stearyldimethylbenzylammoniumchloride (SDBAC) with removal order of benz[a]anthracene >pyrene > fluoranthene > phenanthrene>fluorene, and Cobas et al. (2014) evaluated the removal order of pyrene > phenanthrene on the natural sepiolite clay as sorbents (Cobas et al. 2014).  In this study, on CPC-MC and DDAB-MC, the adsorption of anthracene, fluoranthene, fluorene, phenanthrene, pyrene were higher (3, 2, 10, 4, and 2 % more, respectively) than HDTMA-MC, and very greater (32, 66, 65, 77, and 78 % more, respectively) than TMA-MC. The PAHs affinity on DDAB-MC could be related to chemical structure of this surfactant that contains two long hydrocarbon chains, which makes the modified clinoptilolites more hydrophobic, unlike HDTMA that has one and TMA does not have any. Therefore, hydrophobicity of adsorbents is an important factor beside the sorbate as well.  4.4 Adsorption Kinetics of PAHs  The removal rate of contaminant from aqueous environment is an important factor to estimate properly the design of treatment system. The investigation of adsorption kinetics in wastewater treatment provides information related to adsorption reactions mechanism (Ho and McKay 1999), and explains the solute removal rate that estimate the residence time needed to complete the adsorption reaction (Ho et al. 2000). Adsorption kinetics is an important parameter 60  to study because the adsorption rate, which is one of principles of the adsorbent efficiency and the adsorption mechanism, can be evaluated from kinetic studies (Aljeboree et al. 2017).   Figure 4.5 shows the adsorption of PAHs in relation to contact time, in which amount of PAHs removal increases within contact time. For all PAHs, the 90 % uptake on the DDAB-MC occurred within 30 minutes. More than 80% of all PAHs in aqueous solution were eliminated within the first 15 minutes by the CPC-MC, while the same percentage of PAH removal needed 30 minutes by HDTMA-MC. The maximum (>96%) adsorption of anthracene, fluoranthene, phenanthrene, and pyrene on CPC-MC and DDAB-MC were completed after two hours of contact, whereas the adsorption of anthracene, fluoranthene, phenanthrene, and pyrene on HDTMA-MC took eight hours to reach >92%. Fluorene removals were 91% by the CPC-MC within one hour and 93 % by DDAB-MC within half hour and 81% by the HDTMA-MC after two hours contact time.  The water quality criterion for anthracene (4 µg/L) was met after a contact time of two hours (1.42 µg/L) on CPC-MC; 30 minutes (2.2 µg/L) on DDAB-MC; and four hours (3.9 µg/L) on HDTMA-MC. The water quality criterion for fluoranthene (4 µg/L) was met after a contact time of two hours (1.8 µg/L) on CPC-MC; one hour (1.5 µg/L) on DDAB-MC; and eight hours (3.3 µg/L) on HDTMA-MC. The water quality criterion for fluorene (12µg/L) was met after a contact time of one hour (8.1 µg/L) on CPC-MC and 30 minutes (6.9 µg/L) on DDAB-MC. However, the fluorene concentration in the solution was above the water quality criterion for fluorene (12 µg/L) even after a 48-hour contact time on HDTMA-MC. 61  c) HDTMA-MCLog time (h)0.1 1 10 100708090100b) DDAB-MCLog time (h)0.1 1 10 100Removal % of PAHs from aqueous water 8486889092949698100a) CPC-MC80859095100Anthracene Fluoranthene Fluorene Phenanthrene Pyrene  Figure 4.5 PAH removal % versus log of contact time on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC with initial concentration of 50 µg/L for anthracene, and 100 µg/L for fluoranthene, fluorene, phenanthrene, and pyrene at room temperature at pH 6.5.   62  Figure 4.6 indicates that the adsorption of fluoranthene (9.9, 9.9, 9.7 µg/g) and pyrene (9.9, 10, 9.7 µg/g) were higher than fluorene (9.4, 9.6, 8.4 µg/g) and phenanthrene (9.7, 9.9, 9.1 µg/g) on CPC, DDAB and HDTMA modified clinoptilolites, respectively after 24 hours contact time, where the maximum potential adsorption could be 10 µg/g. The adsorption of anthracene on CPC-MC (4.9 µg/g) and DDAB-MC (4.94 µg/g) were higher than HDTMA-MC (4.76 µg/g) after 24 hours contact time, where the maximum potential adsorption could be 5 µg/g. The adsorption of PAHs on the CPC-MC and DDAB-MC adsorbents were greater than HDTMA-MC. Therefore, it is expected that a larger amount of anthracene, fluoranthene, phenanthrene, and pyrene were partitioned onto modified clinoptilolites. These higher adsorption results of pyrene and fluoranthene are in agreement with the following studies: pyrene adsorption was higher than phenanthrene on the natural clay sepiolite (Cobas et al. 2014). Also, fluoranthene and pyrene had higher adsorption that phenanthrene and fluorene on organo-zeolite (Lemić et al. 2007), and pyrene adsorption was greater than fluorene on pine bark and Ecoprool sawdust (Björklund and Li 2015).  In addition, adsorptions of PAHs on the CPC-MC and DDAB-MC adsorbents were greater than HDTMA-MC.  Anthracene (Kow of 4.54), fluoranthene (Kow of 5.22), phenanthrene (Kow of 4.57) and pyrene (Kow of 5.18) possessed a higher value of partition coefficients, Kow, (higher Kow, more hydrophobicity) compared to fluorene (Kow of 4.181). More hydrophobic PAH such as pyrene, fluoranthene, and anthracene adsorbed faster and more on modified clinoptilolites. The adsorption results suggest that the hydrophobic sites available on the modified clinoptilolites were occupied quickly by the more hydrophobic PAHs such as fluoranthene, and pyrene.    63    Figure 4.6 Equilibrium concentrations of mixed PAH in the solution at different times (log t) on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) with initial concentration of 50 µg/L for anthracene, and 100 µg/L for fluoranthene, fluorene, phenanthrene, and pyrene. The error bars denote the standard deviation of duplicate on CPC-MC and HDTMA-MC and triplicate on DDAB-MC. CPC-MZLog time (h)0.1 1 10 10005101520HDTMA-MZ0.1 1 10 100010203040PAHs Equilibrium Concentration in the Solution (g/L)DDAB-MZLog time (h)0.1 1 10 10005101520 Anthracene  Fluoranthene  Fluorene  Phenanthrene  Pyrene  64  Three different time-dependent adsorption kinetic models have been applied to empirical data of this study for interpretation. Table 4.5 represents the values of the R2, the kinetic constant, and the calculated and experimental qe. From examining the three models of adsorption kinetic mechanisms described in Section 3.8, it is clear that the mechanisms for PAH removal by modified clinoptilolites fit the pseudo-second-order model with an excellent correlation coefficient (>0.999) for all PAHs. In addition, the relationship of t/q and time was linear for all PAHs (Figure 4.7) in the pseudo-second-order model; this R2 result shows much stronger correlation to pseudo-second-order model than the pseudo-first-order model. For these PAH adsorptions, qe experimental values are nearly identical to qe calculated values in the pseudo-second-order model, and R2 has the highest values in this kinetic model. These adsorption kinetic mechanisms are in agreement with the results of (Björklund and Li 2015) for adsorption of anthracene, fluorene, and pyrene on heat-treated pine bark, Zugol pine bark, and Ecoprool sawdust, and (Vidal et al. 2011) for fluoranthene, pyrene, and fluorine on a periodic mesoporous organosilica (PMO).      65  Table 4.5 Coefficient of determination (R2) for pseudo-first, second-order, and intra-particle linear model plots, and second-order model parameters for adsorption onto CPC-MC, DDAB-MC and HDTMA-MC  Pseudo- First-order  Pseudo -Second-order  Intraparticle Diffusion    R2 k1a qe b  R2 k2 c qe   R2 kintd qe,expe CPC-MC Anthracene 0.02 0.021 4.4  1 216 4.91  0.47 0.07 4.91 Fluoranthene 0.01 0.01 6.3  1 115 9.89  0.4 0.13 9.89 Fluorene 3E-05 0.000 4.5  1 9.28 9.36  0.26 0.10 9.2 Phenanthrene 5E-05 0.001 5.2  1 1241 9.72  0.42 0.14 9.72 Pyrene 0.008 0.009 6.5  1 155.4 9.93  0.4 0.13 9.93 DDAB-MC Anthracene 0.12 0.046 39  1 220.4 4.96  0.26 0.04 4.95 Fluoranthene 0.03 0.022 8.5  1 59.13 9.94  0.26 0.11 9.92 Fluorene 0.18 0.037 5.3  1 15.81 9.62  0.19 0.07 9.6 Phenanthrene 0.09 0.037 8.2  1 98.74 9.88  0.26 0.09 9.87 Pyrene 0.03 0.026 11  1 157.4 9.97  0.25 0.11 9.96 HDTMA-MC Anthracene 0.001 0.002 2.9  0.999 48.7 4.84  0.6 0.12 4.84 Fluoranthene 0.006 0.006 2.5  1 53.8 9.8  0.45 0.21 9.80 Fluorene 0.003 0.002 1.7  0.999 18.4 8.64  0.45 0.18 8.64 Phenanthrene 0.02 0.006 1.2  0.999 10.5 9.5  0.52 0.26 9.5 Pyrene 0.009 0.007 2.3  1 69.4 9.8  0.44 0.21 9.8  a k1 rate constant [g/(µg.h)]   b adsorption capacity (µg/g) from the model c k2 rate constant [g/(µg.h)]   d kint rate constant [µg/(g.h 0.5)] e experimental adsorption capacity (µg/g)   66                     Figure 4.7 Pseudo–second–order sorption kinetics model of PAHs, (a) anthracene, (b) fluoranthene, (c) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). The t/qe values versus contact time (t). The contact time (t) is in hours (h), and the PAH adsorption capacity (qe) of modified clinoptilolites is in µg/g.  (a) Anthracene0246810CPC-MC DDAB-MC HDTMA-MC (b) Fluoranthenet/qe (h g/g)0123456(c) Fluorene(d) PhenanthreneTime (h)0 10 20 30 40 500123456(e) PyreneTime (h)0 10 20 30 40 50 67  The experimental adsorption results were fitted to Weber’s intraparticle diffusion model (Figure 4.8, and Table 4.5) in order to examine the diffusion mechanism. The regression of qt versus t1/2 was not linear and did not pass through the origin. Therefore, it can be assumed that intraparticle diffusion was not the rate-limiting step. In addition, Ho and McKay (2000) proposed that if the equilibrium is reached within three hours, the process is kinetic controlled and if equilibrium period is above 24 hours, the process is diffusion controlled. Within three to twenty four hours, both kinetic and diffusion or either one process might be the rate controlling (Ho et al. 2000). In addition, the pseudo-second-order model assumes that the rate controlling step could be associated with chemisorption including valency interactions via electron sharing or exchanging between adsorbent and sorbate (Ho and McKay 1999). From this assumption, it can be assumed that PAHs can share electrons with nitrogen, which has a net positive charge in cationic surfactant. Aromatic structures in PAHs can act as electron donors (Zhang et al. 2014). The aromatic ring in CPC-MC can act as an electron acceptor. This interaction results in a π-π electron-donor- acceptor (EDA) interaction that is a strong sorption interaction (Olivella et al. 2013; Sun et al. 2010) between PAHs and CPC-MC. Therefore, PAHs with more aromatic rings and higher hydrophobicity have more adsorption affinity, leading to the higher adsorption coefficient (Zhang et al. 2014).       68  (a) Anthracene3.54.04.55.05.5CPC-MC DDAB-MC HDTMA-MC (b) Fluorantheneq e (g/g)67891011(c) Fluorene(d) Phenanthrenet1/2 (h)0 2 4 667891011(e) Pyrenet1/2 (h)0 2 4 6 Figure 4.8 Weber intraparticle diffusion model, adsorption capacity at equilibrium of PAHs mixture (a) anthracene, (b) fluoranthene, (c) fluorene, (d) phenanthrene, and (e) at different times on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). 69  4.5 Effect of Dosage Adsorbent Optimization for Treatment Process  The adsorbent dosage is a significant factor to find optimum dosage that affects the extent of pollutant uptake from the water (Tumin et al. 2008). By using higher dosage of adsorbent in the solution, the exchangeable sites availability for metal ions is increased (Babel and Kurniawan 2004). Different quantities of modified clinoptilolites have been used to gain various values of PAHs equilibrium concentrations in water to evaluate the dosage effect.  Figure 4.9 shows the effect of modified clinoptilolite dosages on PAH removal from the aqueous solution to meet the local water quality criteria. Appendix A.3 provides the water quality criteria for PAHs in different organizations to protect the aquatic life. Dosage optimization was targeted at the water quality criteria of BC, the modified clinoptilolite dosages was increased from 0.01 to 2 g to the solution, which resulted in increasing the removal percentage of PAHs from the aqueous solution by the modified clinoptilolites. With increasing the amount of modified clinoptilolites, the total surface area of the modified clinoptilolite was increased for PAHs adsorption.  The increase of the modified clinoptilolite dosage led to an increase in the adsorption of five PAHs. Two grams of DDAB-MC adsorbed more than 99% of five PAHs (anthracene (0.2 µg/L), fluoranthene (0.52 µg/L), fluorene (0.92 µg/L), phenanthrene (0.26 µg/L), pyrene (0.19 µg/L)), as well as CPC-MC (anthracene, fluoranthene, phenanthrene, pyrene; 0.42, 0.63, 0.55, 0.29 µg/L, respectively). However, fluorene had 96% PAH removal (3.69 µg/L). More than 92% of PAHs from 100 mL of the mixture solution were removed when the DDAB modified clinoptilolite dosage was 0.2 g. However, the CPC-MC and HDTMA-MC dosage should be at least 0.5 g to remove 82% of PAHs from 100 mL of the mixture solution. Even in a low dosage of absorbents, such as 0.05 g, removal of fluoranthene and pyrene was above 86% (13.24, 13.41 70  µg/L, respectively), 95% (4.58, 4.55 µg/L, respectively), and 75% (23.12, 24.23 µg/L, respectively) on CPC-MC, DDAB-MC, and HDTMA-MC, respectively.  The PAHs removal results of optimization dosage were compared to local water quality criteria for protecting aquatic life in order to investigate the effectiveness of modified clinoptilolite adsorbents.  With a dosage of 2 g of CPC-MC, DDAB-MC, or HDTMA-MC, the concentration of anthracene, fluoranthene, and fluorene was below the local aquatic life freshwater quality guideline for PAHs (4, 4, 12 µg/L, respectively) (British Columbia 1993). The solid liquid ratio required to meet the aquatic life criteria in BC for removal of anthracene and fluoranthene was 0.2:100 for CPC-MC, 0.1:100 for DDAB-MC, 0.5:100 for HDTMA-MC. For fluorene, the ratio was 1:100 for CPC-MC, 0.2:100 for DDAB-MC, and 2:100 for HDTMA-MC. Therefore, using DDAB-MZ as an adsorbent to remove the PAHs would be more cost effective because of using less dosage with higher efficiency.    71   Figure 4.9 Effect of modified clinoptilolite dosage (CPC-MC, DDAB-MC, and HDTMA-MC) on PAH removal at room temperature and pH value of 6.5 for 24 hours contact time.  The remaining PAH concentrations were compared to the BC, Canada, water quality criteria. The error bars denote the standard deviation of triplicate for CPC-MC and HDTMA-MC, and quadruplicates for DDAB-MC.(c) FluoreneCPC-MC DDAB-MC HDTMA-MC Water Quality Criteria 0.05 0.1 0.2 0.5 1 2(b) FluoranthenePAHs equlibrium concentration in the solution (g/L)020406080(d) Phenanthrene0.01020406080(a) Anthracene051015202530(e) Pyrene0.01 0.05 0.1 0.2 10.5 2Dosage (g) Dosage (g)  72  4.6 Adsorption Capacity of Adsorbent for PAH Adsorption  The successive batch tests were performed to assess the performance of modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA), these results can be applied in a permeable reactive barriers (PRBs) (Cobas et al. 2014).  Figure 4.10, 4.11 and 4.12 indicate the adsorption capacity of PAHs on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA) after 21 successive adsorption batch tests. The successive adsorption capacities of each of five PAHs were similar across each modified clinoptilolite. However, each PAH adsorption capacity varied from the other PAHs regardless of modified clinoptilolites. There was an almost linear relationship between successive addition of fluoranthene and pyrene and the uptake on three adsorbents (CPC-MC, DDAB-MC, and HDTMA-MC). The adsorption capacity of fluoranthene and pyrene were decreasing linearly with exposure to successive adsorption batch tests. The uptake of phenanthrene was not linear on any of three adsorbent. The phenanthrene adsorptions were decreased with exposure to 10 successive batch tests and after that, the adsorptions were increased for both CPC-MC and DDAB-MC. However, the adsorption of phenanthrene on HDTMA fluctuated after six 6 successive batch tests. The uptake of anthracene was almost unchanged with 21 successive batches on CPC-MC, while the anthracene adsorptions fluctuated on both DDAB-MC and HDTMA-MC. Fluorene adsorption was decreased linearly with 10 successive batch tests, and then was increased linearly on CPC-MC. The uptake of fluorene on DDAB-MC and HDTMA-MC fluctuated greatly and was hard to predict. However, after 10 times of repeated adsorption batch assays, the fluorene adsorption was increasing slightly on DDAB-MC. The increase in fluorene adsorption after 10 successive batch tests could likely be related to a potential flocculation process on modified clinoptilolite, further investigation will be needed.  73   Figure 4.10 The PAHs adsorption capacity (µg/g) on CPC-MC at room temperature and pH 6.5. The successive batch tests were run 21 times. The total volume of contaminated solution was 2100 mL for CPC-MC. The total amounts of 2100 µg/L of each PAHs (fluoranthene, fluorene, phenanthrene, and pyrene), and 1050 µg/L of anthracene were used.  (a) Anthracene01020304050(b) FluoranthenePAHs adsorption capacity at equilibrium, q e (g/g)0204060801000 5 10 15 20020406080100(e) Pyrene0 5 10 15 20(d) PhenanthreneFluoreneNumber of repeated test Number of repeated test(c) Fluorene 74   Figure 4.11 The PAHs adsorption capacity (µg/g) on DDAB-MC at room temperature and pH 6.5. The successive batch tests were run 21 times. All samples were run in duplicate. The total volume of contaminated solution was 2100 mL for DDAB-MC. The total amounts of 2100 µg/L of each PAHs (fluoranthene, fluorene, phenanthrene, and pyrene), and 1050 µg/L of anthracene were used.      (a) Anthracene20253035404550(b) FluoranthenePAHs adsorption capacity at equilibrium, qe (g/g)20406080100(d) PhenanthreneNumber of repeated test0 5 10 15 2020406080100(c) Fluorene(e) PyreneNumber of repeated test0 5 10 15 20 75   Figure 4.12 The PAHs adsorption capacity (µg/g) on HDTMA-MC at room temperature and pH 6.5. The successive batch tests were run 21 times. The total volume of contaminated solution was 2100 mL for HDTMA-MC. The total amounts of 2100 µg/L of each PAHs (fluoranthene, fluorene, phenanthrene, and pyrene), and 1050 µg/L of anthracene were used.    (e) PyreneNumber of repeated test0 5 10 15 20(d) PhenanthreneNumber of repeated test0 5 10 15 2020406080100(c) Fluorene(b) FluoranthenePAHs adsorption capacity at equilibrium,qe (g/g)20406080100(a) Anthracene20253035404550 76  The PAHs adsorption over the course of 21 successive batch assays is shown in Figure 4.13. By using 100 mL of PAHs solution with concertation of 50 µg/L for anthracene (the maximum solubility of anthracene is 50 µg/L in water) and 100 µg/L for fluoranthene, fluorene, phenanthrene and pyrene with equilibrium time of 24 hours. A linear relationship between an addition of PAHs and adsorption of PAHs were seen. The adsorption results indicated that modified clinoptilolites are excellent candidates to remove PAHs from groundwater in the manner of PRB. These results are in agreement with Cobas et al. (2014), in which they used clay sepiolite to adsorb the phenanthrene and pyrene in five successive batch assays in order to simulate sepiolite as a PRB in groundwater  (Cobas et al. 2014).  The highest amount of PAH accumulations on CPC-MA, DDAB-MC and HDTMA-MC after using 2100 mL of  PAHs contaminated solution including 1050 µg/L of anthracene and 2100 µg/L of fluoranthene, fluorene, phenanthrene, and pyrene were in order of fluoranthene>pyrene>fluorene>phenanthrene>anthracene. On DDAB-MC, fluoranthene (1583 µg/g), pyrene (1560 µg/g), fluorene (1060 µg/g), and phenanthrene (1057 µg/g) were accumulated in amounts more than 1mg/g of clinoptilolite, except for anthracene (737 µg/g). While the accumulation of only fluoranthene (1355 µg/g) and pyrene (1343 µg/g) were in amounts more than 1 mg/g of clinoptilolite on CPC-MC. On HDTMA-MC, accumulation of fluoranthene (1303 µg/g), pyrene (1269 µg/g), and fluorene (1147 µg/g) were more than 1mg/g of clinoptilolite.  77    Figure 4.13 The PAHs uptake after exposure of CPC-MC, DDAB-MC, and HDTMA-MC to 21 successive batch assays at room temperature and pH 6.5. The total volume of PAHs contaminated solution was 2100 mL.  (a) Anthracene200400600800(b) FluoranthenePAHs accumulation (g/g) on modified clinoptilolites20040060080010001200140016001800CPC-MC DDAB-MC HDTMA-MC (c) Fluorene20040060080010001200(d) PhenanthreneNumber of repeated test0 5 10 15 202004006008001000 (e) PyreneNumber of repeated test0 5 10 15 202004006008001000120014001600 78  It seems that the PAHs with the same molecular weights, with different molecular structures, accumulate different amount onto same modified clinoptilolite. The angular molecular structure had a higher accumulation than linear or cluster molecular structures. For example, fluoranthene (202 g/mol, angular) had higher accumulation (1355, 1583, 1303 µg/g on CPC-MC, DDAB-MC, HDTMA-MC, respectively) compared to pyrene (202 g/mol, cluster) (1343, 1560, 1269 µg/g on CPC-MC, DDAB-MC, HDTMA-MC, respectively). Phenanthrene (178 g/mol, angular) had a higher accumulation (844, 1057, 989 µg/g on CPC-MC, DDAB-MC, HDTMA-MC, respectively) compared to anthracene (178 g/mol, linear) (708, 737, 750 µg/g on CPC-MC, DDAB-MC, HDTMA-MC, respectively).  4.7 Stability of Adsorbed PAHs on Modified Clinoptilolites  To protect aquatic life, the adsorbed PAHs on an adsorbent should be stable and the adsorbed PAHs should not leach into the aquatic environment. To my knowledge, this is the first study of investigation of PAH leachability in the solution after adsorption test.  Table 4.6 shows the total amount of accumulated PAHs on each modified clinoptilolite after 21 successive batch tests, the amount of leached PAHs from modified clinoptilolites after the stability tests were performed one time on each modified clinoptilolite (CPC-MC, DDAB-MC and HDTMA-MC), and the BC water quality criteria. Figure 4.14, Figure 4.15, and Figure 4.16 show the accumulated PAH and the leached PAH portion on CPC-MC, DDAB-MC, and HDTMA-MC, respectively.  After running the stability test, the maximum leachability of fluoranthene, fluorene, and pyrene were less than 5% after accumulation of 1mg of those PAHs per 1g of clinoptilolite for the three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). Phenanthrene had highest leachability at 4.6% from CPC-MC, DDAB-MC, and HDTMA-MC (Figure 4.14, Figure 79  4.15, and Figure 4.16). Anthracene and fluorene had less than 2% leachability from CPC-MC and HDTMA-MC, while just anthracene had less than 2% PAH leachability from DDAB-MC. Despite the low percentage of PAH leachability, the leached concentrations are above the BC water quality criteria for anthracene, fluoranthene, phenanthrene, and fluorene, except for fluorene on CPC-MC. Further study to stabilize the adsorbed PAHs is recommended.   Table 4.6 Estimation of PAHs accumulation and leachability from three modified clinoptilolites Description Total PAHs accumulation on modified clinoptilolites after 21 successive batches (µg/g) Leached PAHs from modified clinoptilolites after leachability test µg/g (µg/L) Leachability %from modified clinoptilolites Water quality criteria in BC (µg/L) CPC-MC     Anthracene 708 12.3  (12.4) 1.7 4 Fluoranthene 1355 45.1  (45.4) 3.6 4 fluorene 973 9.8    (9.8) 1 12 Phenanthrene 843.7 38.8  (39.1) 4.6 0.3 Pyrene 1343 44.8  (45.1) 3.3  DDAB-MC     Anthracene 737 12.3  (12.4) 1.7 4 Fluoranthene 1583 35.5  (35.6) 2.2 4 fluorene 1060 26.4  (26.5) 2.5 12 Phenanthrene 1057 48.3  (48.4) 4.6 0.3 Pyrene 1560 35.0   (35) 2.2  HDTMA-MC     Anthracene 750 10.6  (10.7) 1.4 4 Fluoranthene 1303 42.2  (42.3) 3.2 4 fluorene 1147 20.1  (20.1) 1.75 12 Phenanthrene 989 45.1  (45.2) 4.6 0.3 Pyrene 1269 41.9  (42) 3.3   The strength of PAHs leachability from modified clinoptilolites were in the following order according to clinoptilolite; on CPC-MC , fluorene< anthracene < pyrene < phenanthrene; on DDAB-MC, anthracene <pyrene =fluoranthene<fluorene< phenanthrene<fluoranthene; and on HDTMA-MC, anthracene < fluorene< fluoranthene<pyrene< phenanthrene. It appears that 80  PAH with linear structure (anthracene, and fluorene) had less leachability from CPC-MC, DDAB-MC and HDTMA-MC, in contrast to angular and cluster geometry (fluoranthene and pyrene). This low PAHs leachability from modified clinoptilolites makes the adsorbents an excellent candidates to remove the PAH contaminants from aqueous solution and safely dispose of them at disposal sites. This low desorption results are in agreement with the observation of Hiller et al. (2008); for example after conducting one adsorption test, desorption experiment was performed, and phenanthrene was desorbed from soil and sediment by 5% that suggest of irreversible sorption-desorption phenomenon of PAHs (Hiller et al. 2008).   81    Figure 4.14 Comparison of total accumulated PAHs on CPC-MC after 21 successive batch tests with leached PAHs from CPC-MC after performing leachability test.  82    Figure 4.15 Comparison of total accumulated PAHs on DDAB-MC after 21 successive batch tests with leached PAHs from DDAB-MC after performing leachability test.   83   Figure 4.16 Comparison of total accumulated PAHs on HDTMA-MC after 21 successive batch tests with leached PAHs from HDTMA-MC after performing leachability test. 84  4.8 Competition Effect of Single versus Mixture PAH Adsorptions   In real-life situation, there are multiple contaminants and many studies using a single contaminant (Chang et al. 2004; El Khames Saad et al. 2014; Garcı́a et al. 2004; Gök et al. 2008; Kaya et al. 2013) . To investigate the competition effect, the adsorption of single PAH, fluoranthene, versus mixed PAHs were studied. Figure 4.17 (a) compares the removal percentage of fluoranthene in single PAH solution and mixed PAHs solution and Figure 4.17 (b) shows the comparison of adsorption capacity of fluoranthene in single PAH solution and the mixed PAHs in the solution. Figure 4.17 (a) shows that adsorptions of fluoranthene individually were 27 % and 40% higher than in the mixture on CPC-MC and DDAB-MC, respectively. Figure 4.17 (b) indicates that fluoranthene adsorption capacities from single PAH solution were 7 and 4 µg/g higher than mixed PAHs on CPC-MC and DDAB-MC, respectively. Fluoranthene adsorption on DDAB-MC, both individually and in a mixture (195 µg/g, individual PAH; 191 µg/g, mixture PAHs), was greater than CPC-MC (178 µg/g, individual PAH; 171 µg/g, mixture PAHs), which was followed by HDTMA (152 µg/g, individual PAH; 152 µg/g, mixture PAHs). This could be related to there being more sties available for individual fluoranthene in single PAH solution to adsorb on modified clinoptilolites because active sites were shared between five PAHs in mixed solution. The 0.05 g of modified clinoptilolites can provide the same availability of active sites for individual PAH and mixture PAHs. However, fluoranthene adsorptions both individually and in the mixture were almost similar on HDTMA-MC. This adsorption result indicates that, besides the contaminant properties, the characteristic of adsorbent also affects the PAH adsorption. CPC and DDAB contain two long hydrocarbon chains that make them more hydrophobic than HDTMA, which has one long hydrocarbon chain. Lemić et al. (2007) showed that the PAHs adsorption was a competitive procedure and primarily hydrophobic. The PAHs 85  with lower partition coefficients had lower adsorption, and the PAHs adsorption was in the following order: benz[a]anthracene>pyrene>fluoranthene>phenanthrene>fluorene. In the mixture solution, after PAHs have occupied the available sites on the adsorbent, the more hydrophobic PAHs chemicals start to replace the less hydrophobic PAHs (Lemić et al. 2007).  In this study with five PAHs, fluoranthene is less hydrophobic than anthracene and pyrene.    86                     Figure 4.17 The competition effect of fluoranthene in single versus mixture PAHs solution at room temperature and pH value of 6.5 after 24 hours contact time. (a) Removal % of fluoranthene from single PAH and mixture PAHs solution on modified clinoptilolites. (b) Adsorption capacity of fluoranthene in single PAH and mixture PAHs solution on modified clinoptilolites. All DDAB-MC samples were run in duplicate.   AdsorbentCPC-MC DDAB-MC HDTMA-MCAdsorption capacity of fluoranthene (g/g)140150160170180190200CPC-MC DDAB-MC HDTMA-MCRemoval % of fluorathene from aqueous solution7580859095100Single PAH Mixture PAHs(a)(b) 87  4.9 Effect of pH on PAH Removals An important parameter in water chemistry is pH, which can affect the speciation of solutes and the adsorbents’ surface charge (Huang et al. 2016). pH is one of the significant factors that control the heavy metal uptake from aqueous solution (Tumin et al. 2008). In addition, it is important to investigate the effect of pH on PAHs adsorption for treatment of contaminated water from different sources, since the contaminated water might have different pH value. For example landfill leachate has pH of 6.93 to 8.37 (Aziz et al. 2010), untreated wastewater has pH 7.9-8.48 (Stark et al. 2015), ocean water possess pH of 8.15-8.26 (Krause et al. 2012), and coal mine drainage treatment include the pH of 4.2-7.3 (Mien 2012).  To estimate the optimum pH for the PAHs adsorption on modified clinoptilolites, the adsorption tests have been carried out at different pH values. Figure 4.18 and Figure 4.19 represents the removal percentage of PAHs and PAH adsorption capacity, respectively at different pH values on modified clinoptilolites. At different pH values, the adsorption of PAHs on DDAB modified clinoptilolite was not affected significantly. Differences in removal of anthracene, fluoranthene, phenanthrene, and pyrene on the DDAB-MC at different pH values were less than 1% (0.1 µg/g). For the CPC-MC, the changes in removal of anthracene, fluoranthene, phenanthrene, and pyrene at different pH values was less than 3% (0.1 µg/g) and for HDTMA-MC was less than 5% (0.4 µg/g). As indicated by the results, the adsorptions of these four PAHs were not affected by pH, which indicates that the chemical properties of modified clinoptilolites and PAHs were not affected by various pH values. The highest removal for anthracene (4.99 µg/g), fluoranthene (9.99 µg/g), phenanthrene (9.8 µg/g), and pyrene (9.99 µg/g) was obtained at pH 5.5 and 9 for CPC-MC and DDAB-MC adsorbents. The highest adsorption for anthracene (4.99 µg/g), fluoranthene (9.9 µg/g), phenanthrene (9.8 µg/g), and 88  pyrene (9.9 µg/g) was obtained at pH 9 for HDTMA-MC adsorbent. However, fluorene adsorption on modified clinoptilolites was affected at different pH values. Differences in removal of fluorene at various pH values were 7, 4, and 13% on CPC-MC, DDAB-MC, and HDTMA-MC, respectively. Variation in adsorption of fluorene at different pH values were 0.4 µg/g on CPC-MC, 0.4 µg/g on DDAB-MC, and 1.2 µg/g on HDTMA-MC. However, this finding was in disagreement to the result of Olu-Owolabi et al. (2015) who has found that the fluorene adsorption was decreased continuously by increasing the pH from 3 to 9 (Olu-Owolabi et al. 2015).  Table 4.7 presents the comparison of the water quality criteria of BC government and the remained concentration of PAHs in the solution at different pH values. The remaining concentrations of anthracene, fluoranthene, and fluorene in the solution were below the water quality criteria of BC with changing pH values from 3 to 11 on CPC-MC, DDAB-MC, and HDTMA, except for fluorene at pH value of 6.5 on HDTMA-MC. Therefore, the water quality criteria of BC were met at all pH values on CPC-MC, DDAB-MC, and HDTMA, except for fluorene on HDTMA-MC at neutral pH values of 6.5.   89                         (c) Fluorene(d) PhenanthrenepH2 4 6 8 10 128486889092949698100(b) FluoranthenePAHs removal % from aqueous solution8486889092949698100(e) PyrenepH2 4 6 8 10 12(a) Anthracene8486889092949698100CPC-MC DDAB-MC HDTMA-MC  Figure 4.18 Effect of pH values on the PAHs removal (a) anthracene, (b) fluoranthene, (c) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) at room temperature. All DDAB-MC samples were run in duplicate. Error bar denote the standard deviation of duplicate for DDAB-MC. 90     (e) PyrenepH2 4 6 8 10 12(d) PhenanthrenepH2 4 6 8 10 12PAHs equilibrium adsorption capacity, qe (g/g)8.68.89.09.29.49.69.810.0(a) Anthracene4.24.44.64.85.05.2CPC-MZ DDAB-MZ HDTMA-MZ (b) Fluoranthene8.68.89.09.29.49.69.810.0(c) Flourene Figure 4.19 Effect of pH values on the PAHs adsorption capacity at equilibrium; (a) anthracene, (b) fluoranthene, (c) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) at room temperature. All DDAB-MC samples were run in duplicate.  91  Table 4.7 The comparison of water quality criteria of BC for PAHs with the PAH residual concentrations in the solution by using modified clinoptilolites at different pH values at room temperature for 24 hours contact time   Adsorbent pH  Anthracene Fluoranthene Fluorene Phenanthrene   Water Quality Criteria (µg/L)  4  4  12  0.3 CPC-MC 3     Average Remaining Concentration (µg/L) after Adsorption 0.5 0.3 4.5 2.2 5.5 0.3 0.31 0.18 0.85 6.5 1.1 1.0 7.4 2.5 9 0.5 0.3 3 1.8 11 0.6 0.3 5 2.2 DDAB-MC 3 0.2 0.1 1.6 0.8 5.5 0.14 0.07 0.23 0.4 6.5 0.7 0.6 4.2 1.1 9 0.2 0.1 0.4 0.3 11 0.5 0.1 3 1.0 HDTMA-MC 3 1.5 1.3 7.1 4.8 5.5 0.49 0.97 1.37 1.39 6.5 2.3 2.5 14 5.5 9 0.7 1.0 1.7 2.1 11 0.88 0.9 4.1 2.5  Zeledón-Toruño et al. (2007) discovered that pH had less effect on the heavier PAHs with more C=C bonds (e.g., pyrene, benzo (a) pyrene, benzo (k) fluoranthene, and benzo (g,h,i)perylene) because PAHs are inert chemically and stable chemically because of bond linkages. The PAH removal differences in his work were less than 9% on immature coal (leonardite) in pH range of 2, 4, and 6. In addition, by changing pH, the heavier PAHs did not have a functional group or element (e.g., oxygen or nitrogen) in their structure to be protonated or ionized. Because of hydrophobic interaction between PAHs and leonardite, the pH values had less effect on heavier PAHs (Zeledón-Toruño et al. 2007a). In this study, because of hydrophobic interaction between PAHs and surfactants on the surface of modified clinoptilolites, pH did not impact the adsorption of the heavier PAHs. However, fluorene adsorption slightly changed with changing pH value due to having a C-H group that could be protonated. The fluorene had the 92  highest removal rate at pH 5.5 on CPC-MC, pH 5.5, and 9 on DDAB-MC, and 5.5 on HDTMA-MC, suggestion that a week acidic or basic environment were ideal for the fluorene adsorption process. This finding is in accordance with the result of Zeledón-Toruño, et al. (2007), who realized that when pH was changed from 2-6, adsorption of pyrene did not change significantly on immature coal (leonardite), except fluorene, and the result of EI Khames Saad et al. (2014) indicates that the adsorption of anthracene on activated carbon and posidonia oceanica did not change by varying pH from 2 to 12 (El Khames Saad et al. 2014). Since the adsorption of PAHs did not change significantly by different ranges of pH, the adsorption mechanism could be the physical adsorption such as Van der Waals interaction (Zeledón-Toruño et al. 2007a).  4.10 Effect of Temperature on PAH Removals  Different temperatures can influence on sorption-desorption of PAHs from adsorbents at different geographic climatic locations.  This study investigated the changes in PAHs adsorption at different temperatures to simulate geographic climate locations in order to better understand the efficiency of adsorption and to predict the environmental risks of leached PAH adsorption in different seasons of the year (summer and winter), or different range of natural water temperature (0-35oC) (Hiller et al. 2008). Figure 4.20 represents the PAHs removal percentage in aqueous solution on three modified clinoptilolites at temperature of 4 to 35oC. The extent of PAHs adsorption reduced as the temperature increased from 4 to 35°C. The increase in temperature from 4 to 35°C resulted in a reduction of PAHs adsorption for anthracene, fluoranthene, fluorene, phenanthrene and pyrene by 2, 1, 7, 3 and 0.9 % on CPC-MC, 0.8, 0.5, 5, 1, and 0.4 % on DDAB-MC, and 3, 2, 13, 5, 2 % on HDTMA-MC, respectively.    93                     Figure 4.20 The effect of temperature on the PAHs adsorption, (a) anthracene, (b) fluoranthene, (C) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTNA-MC) from 4 to 35oC. All samples were run in duplicate. Error bar denote the standard deviation of duplicate for modified clinoptilolites. (e) PyreneTemperature (oC)0 5 10 15 20 25 30 35 40(c) FluoreneCPC-MC DDAB-MC HDTAM-MC (d) PhenanthreneTemperature (oC)0 5 10 15 20 25 30 35 4080859095100(a) Anthracene80859095100(b) FluoranthenePAH removal % from aqueous solution 80859095100 94  Figure 4.21 represents the PAHs adsorption capacity of PAHs in aqueous solution on three modified clinoptilolites at temperature of 4 to 35oC. The adsorption capacity of anthracene, fluoranthene, and pyrene were reduced by 0.1 µg/g on CPC-MC and DDAB-MC, while the adsorption capacity of phenanthrene was reduced 0.3 µg/g and 0.2 µg/g on CPC-MC and DDAB-MC, respectively, whereas the fluorene adsorption capacity was reduced 0.7 µg/g and 0.5 µg/g on CPC-MC and DDAB-MC. On HDTMA-MC, the adsorption capacity of anthracene, fluoranthene, and pyrene were decreased by 0.2 µg/g, and adsorption capacity of phenanthrene was reduced by 0.4 µg/g, while the adsorption capacity of fluorene decreased by 1.4 µg/g.. At 298 K, vapor pressure of anthracene, fluorene, phenanthrene, and pyrene are 7.65 x 10-4, 6.58 x 10-2, 1.98 x 10-2, and 5.40 x 10-4 Pa, respectively (Goldfarb 2013). The vapor pressure of fluorene > phenanthrene > anthracene > pyrene; therefore, changes in temperature have a greater effect on the fluorene and phenanthrene adsorption compared to anthracene, fluoranthene and pyrene (see Figure 4.20 and Figure 4.21). These results are in accordance with the result of Zhang et al. (2014), who revealed that adsorption of phenanthrene significantly decreased on lignin, a naturally synthesized biopolymer, when the temperature increased (Zhang et al. 2014). In addition, the adsorptions of naphthalene, phenanthrene and pyrene were reduced when the temperature increased from 4 to 27oC on soil and sediment by 27.3%, 17%, and 27.4 %, respectively (Hiller et al. 2008).     95   (a) Anthracene4.04.24.44.64.85.0(b) Fluoranthene8.08.59.09.510.0(c) FluorenePAHs equilibrium adsorption capacity, qe (g/g)(d) PhenanthreneTemperature (oC)  0 5 10 15 20 25 30 35 408.08.59.09.510.0 CPC-MZ DDAB-MZ HDTMA-MZ (e) PyreneTemperature (oC)0 5 10 15 20 25 30 35 40 Figure 4.21 The effect of temperature on the PAHs equilibrium adsorption capacity (qe, µg/g),  (a) anthracene, (b) fluoranthene, (C) fluorene, (d) phenanthrene, and (e) pyrene, on three modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC) at 4, 20 and 35oC. All samples were in duplicate.   96  Table 4.8 represents the PAHs adsorption concentration on modified clinoptilolites at different temperatures and the BC water quality criteria. The temperature effect on PAH adsorption was relatively small on DDAB-MC compared to CPC-MC and HDTMA-MC. The anthracene and fluoranthene adsorptions on CPC-MC, DDAB-MC, and HDTMA-MC met the BC water quality criteria at different temperatures. The fluorene adsorption on CPC-MC and DDAB-MC met the BC water quality criteria. However, HDTMA-MC at 20, and 35 oC did not meet the BC water quality criteria. The modified clinoptilolite with HDTMA had the highest percentage of PAH desorption, which could be related to the structure of the surfactant which contains one long hydrocarbon chain. DDAB-MC has two long hydrocarbon chains on its structure that provide more hydrophobic surface and stronger bond of surfactant and clinoptilolite for PAH adsorption compare to HDTMA-MC. The formula (4) in Appendix D.2 indicates that temperature and adsorption have an inverse relationship. When the temperature increases, the adsorption decreases. At 4oC,  there could be two reasons that adsorption is higher compared to higher temperatures: (1) reduce the solubility of PAHs in the water, (2) Gibbs-free energy (∆𝐺𝐺ᵒ).  According to Piatt et al. (1996) the solubility of PAHs was reduced by two to three times when the temperature decreased from 26 to 4oC (Piatt et al. 1996). The results of current experiment demonstrate that the temperature effect shows that the removal reductions are in accordance with the equation (4).     97  Table 4.8 The comparison of water quality criteria of BC for PAHs with the PAH residual concentrations in the solution by using modified clinoptilolites at different temperatures at pH 6.5 for 24 hours contact time   Adsorbent Temp. (oC)  Anthracene Fluoranthene Fluorene   BC. Water Quality Criteria (µg/L)  4  4  12 CPC-MC 4   Average Remaining  Concentration (µg/L) after Adsorption 0.4 0.3 2.9 20 1.1 1.3 6.4 35 1.4 1.4 10.2 DDAB-MC 4 0.3 0.3 2.3 20 0.5 0.6 4 35 0.7 0.8 6.9 HDTMA-MC 4 1.4 1.4 6.3 20 2.4 2.6 16 35 3 3.1 20 Temp: Temperature 4.11 Removal of PAHs from Landfill Leachate Using Modified Clinoptilolites   Simple solute (e.g., deionized water) was compared to complex background such as landfill leachate. It is important to investigate whether there is any background effect on PAH adsorption by using modified clinoptilolites in real media such a landfill leachate. Before performing PAH adsorption test, the landfill leachate was characterized to measure the PAHs, nutrients, metals, and TOC concentrations as a background effect. The chemical characteristics of landfill leachate are presented in Table 4.9.  Landfill leachate has been analyzed and the concentration of total PAH compounds was 1.2 µg/L including 0.1, 0.1, 0.5, 0.4, and 0.07 µg/L for anthracene, fluoranthene, fluorene, phenanthrene, and pyrene, respectively. Fluorene and phenanthrene have the highest concentration in the local landfill leachate. These results are in agreement with Han et al. (2013) investigation of the PAHs occurrence in groundwater around Zhoukou landfill, China. They found that fluoranthene, fluorene and phenanthrene were the three dominant PAHs between the eleven detected PAHs in most groundwater samples. The fluoranthene, fluorene, and phenanthrene concentrations were 0.36, 0.68, and 0.83 µg/L in the groundwater samples around the Zhoukou landfill (Han et al. 2013).  98  Table 4.9 Main chemical characteristics of landfill leachate Parameters Landfill Leachate pH 7.04 TOC1 (mg/L) 167.7 Phosphate (mg/L) 0.01 NOx (mg/L) 0.23 Ammonia (mg/L) 103.8 Total PAHs2 (µg/L)   1.2 Total Metals3 (mg/L) 212.55 1TOC: total organic carbon  2 Total PAHs: five PAHs were included (anthracene, fluoranthene, fluorene, phenanthrene, pyrene) 3Total Metals: metals including Ca, Fe, Mg, K, and Si  After the landfill leachate was spiked with the PAHs, the modified clinoptilolites were used to remove the PAHs. The results of PAH removal percentage and adsorption capacity from landfill leachate and deionized water by using modified clinoptilolites are presented in Figure 4.22, and Figure 4.23. Figure 4.22 (a) and Figure 4.23 (a) indicates that removal percentage of anthracene, fluoranthene, phenanthrene, and pyrene on CPC-MC from deionized water and landfill leachate were similar, while fluorene removal from landfill leachate was almost 2% (0.2 µg/g) higher than deionized water. The same results were obtained for PAH removal from deionized water and landfill leachate from DDAB-MC (Figure 4.22 (b) and Figure 4.23 (b)). The adsorption capacity of anthracene in landfill leachate was 4.9 µg/g and 5 µg/g on CPC-MC and DDAB-MC, respectively from the maximum adsorption capacity of 5 µg/g. The adsorption capacity of fluoranthene, fluorene, phenanthrene, and pyrene in landfill leachate were 9.9, 9.6, 9.8, and 9.9 µg/g on CPC-MC and 10, 9.8, 9.9, and 10 µg/g on DDAB-MC, respectively from the maximum adsorption capacity of 10 µg/g.  99                      AnthraceneFluorantheneFluorenePhenanthrenePyrene949698100(b)PAH compounds AnthraceneFluorantheneFluorenePhenanthrenePyrenePAHs removal % from aqueous solution by using modified clinoptilolites  949698100DDAB-MC; Deionized Water DDAB-MC; Landfill Leachate (b)(a)(a)CPC-MC; Deionized Water CPC-MC; Landfill Leachate  Figure 4.22 Comparison of removal% of PAHs from deionized water and landfill leachate solution on CPC and DDAB modified clinoptilolites (CPC-MC and DDAB-MC) at room temperature. Samples were run in duplicate at room temperature. 100  (a)AnthraceneFluorantheneFluorenePhenanthrenePyrene0246810CPC-MC: Deionized Water CPC-MC: Landfill Leachate (b)PAHsAnthraceneFluorantheneFluorenePhenanthrenePyreneAdsorption capacity of PAHs in aqueous solution; qe (g/g)0246810DDAB: Deionized Water DDAB: Landfill Leachate (a) (b)  Figure 4.23 Comparison of adsorption capacity of PAHs from deionized water and landfill leachate solution on CPC and DDAB modified clinoptilolites (CPC-MC and DDAB-MC) at room temperature. Samples were run in duplicate and error bar denote the standard deviation of duplicate for modified clinoptilolites. 101  In Table 4.10, the residual PAH concentration in deionized water and landfill leachate after adsorption on modified clinoptilolites are compared with the water quality criteria of BC (Figure 4.24). The equilibrium concentration of anthracene, fluoranthene, and fluorene in landfill leachate were lower than the water quality criteria of BC and met the BC water quality criteria. To test whether landfill leachate meets the water quality criteria of BC for phenanthrene, as it noted before, the set up of GC/MS should be changed based on ng/L, because 0.3 µg/L is very close to the detection limit of instrument. The removals of anthracene, fluoranthene, fluorene, phenanthrene, and pyrene from landfill leachate were 97.8, 98.6, 95.7, 97.2, 98.5% by CPC-MC, and 99, 99.6, 98, 99, 99.6% by DDAB-MC, respectively. The removal results confirm that the matrix of landfill leachate did not affect the removal of PAHs from landfill leachate by CPC-MC and DDAB-MC. However, the removal of fluorene from landfill leachate increased by 2% (0.2 µg/g) by CPC-MC and DDAB-MC. The increase of fluorene adsorption could be due to colloids or other organic materials attaching to fluorene and modified clinoptilolite in the landfill matrix. This results in an increase in hydrophobic materials, which increases fluorene adsorption on modified clinoptilolite. Kalmykova et al. (2014) used activated carbon and peat filter to remove the US- EPA’s 16 priority pollutant PAHs from landfill leachate, and the PAH removal efficiency were 50 and 63% from landfill leachate for activated carbon and peat, respectively (Kalmykova et al. 2014).  Figure 4.25 represents the schematic of general adsorption of anthracene on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC). The other PAHs are assumed to adsorb the same way as anthracene.    102  Table 4.10 Comparison of water quality criteria of BC with PAH removal percentage (R%) in aqueous solution by using modified clinoptilolites    Anthracene Fluoranthene Fluorene Phenanthrene Pyrene Water Quality Criteria of BC (µg/L) 4 4 12 0.3  adsorbents Media % (µg/L)1 CPC-MC D.W2 98   (1.03) 98.5  (1.5) 94.1  (5.9) 96.9  (3.1) 98.9  (1.05) LL3 97.8  (1.08) 98.6  (1.43) 95.7  (4.3) 97.2  (2.86) 98.5  (1.45) DDAB-MC D.W 99.2  (0.4) 99.4  (0.56) 96.2  (3.8) 98.8  (1.21) 99.7  (0.33) LL 99    (0.52) 99.6  (0.38) 98    (2.06) 99     (1) 99.6  (0.42) 1 % (µg/L): PAH residual in the solution after adsorption   2D.W: Deionized water   3LL: Landfill leachate                PAHsAnthracene Fluoranthene FluorenePAH concentration (g/L)02468101214CPC-MC: Deionized Water CPC-MC: Landfill Leachate DDAB-MC: Deionized Water DDAB-MC: Landfill Leachate BC Water Quality Criteria            Figure 4.24 Comparison of BC water quality criteria with the residual PAH concentrations in deionized water and landfill leachate solution after adsorption on one gram of CPC-MC, and DDAB-MC at room temperature. 103    Figure 4.25 The schematic of adsorption of anthracene on modified clinoptilolites (CPC-MC, DDAB-MC, and HDTMA-MC).    104  Chapter 5: Conclusion & Recommendations 5.1 Conclusion  The leachability and thermal stability results of this study indicate that the presence of two long hydrocarbon chains in surfactants (DDAB and CPC) results in low surfactant leachability from clinoptilolite, and results in higher thermal stability on clinoptilolite at different studied temperatures compared to one long hydrocarbon chain surfactant (HDTMA).  The non-modified clinoptilolite (NC) and tetramethylammonium chloride modified clinoptilolite (TMA-MC) revealed insignificant removal (<30% and < 66%, respectively) of the PAHs at 1:100 solid: liquid ratio from deionized water. CPC-MC and DDAB-MC are excellent adsorbents to remove PAHs (>94%) from water, compared to HDTMA-MC (removal >84%), TAM-MC, and clinoptilolite (natural zeolite). PAH adsorptions on selected modified clinoptilolites are in decreasing order of adsorption capacity as follows: DDAB-MC> CPC-MC> HDTMA-MC>TMA-MC.  The amount of PAHs adsorption on modified clinoptilolites depends on the type of surfactant that has been used for modification, PAH hydrophobicity, Kow, PAH molecular weight, and PAH molecular structure. PAHs with higher molecular weight or higher hydrophobicity have higher adsorption on adsorbent. In addition, PAHs with similar molecular weight, but with linear or cluster molecular structure have slightly higher adsorption compared to those with angular molecular structure. On three modified clinoptilolites in this study, the PAH adsorptions are in decreasing order of adsorption amounts as follows: pyrene >fluoranthene >anthracene >phenanthrene >fluorene. These PAH adsorption results are in agreement with the hydrophobicity of PAHs. Although the adsorptions of pyrene and fluoranthene, which have   the same molecular weight, are not significantly different on modified clinoptilolites, the adsorption 105  results indicated that molecular structure has an effect on PAH adsorption, kinetics, and capacity of PAHs adsorption. The results of the adsorption of anthracene, fluoranthene, fluorene, phenanthrene, and pyrene on three modified clinoptilolites appeared to be the best fit for the kinetic model of pseudo-second order. All five PAHs were adsorbed at more than 90, 85, and 80% on DDAB, CPC, and HDTMA modified clinoptilolites respectively, within 30 minutes. These fast PAH adsorptions on modified clinoptilolites indicate feasibility of using these adsorbents for water treatment in moderate moving environments such as groundwater, landfill leachate and ponds.  In addition, these adsorbents had high PAH adsorption capacities, almost 1 mg of PAH/g of adsorbent for fluoranthene, fluorene, phenanthrene, and pyrene. The PAHs accumulation on modified clinoptilolites after 21 successive batch adsorption tests were in decreasing order of fluoranthene>pyrene<fluoranthene>phenanthrene>anthracene. These PAH accumulations indicate that in contrast to adsorption, the PAHs with the same molecular weight with angular molecular structure had slightly higher accumulations compared to those cluster molecular structure. The fluorene with the lowest molecular weight showed different accumulation ability which was higher than phenanthrene and anthracene and which could be associated with flocculated process.  By increasing the amount of modified clinoptilolites from 0.01 to 2 g, the PAH removal results reached the highest percentage up to almost 100% and met the local water quality standards for anthracene, fluoranthene, and fluorene.  Different pH and temperatures have insignificant effects on the removal of anthracene, fluoranthene, phenanthrene, and pyrene. Fluorene, which has higher vapor pressure and slightly acidic properties, shows modest change in adsorption. Increasing temperature from 5 to 35ºC 106  slightly decreased the PAH adsorptions on modified clinoptilolites. The PAH adsorptions with higher molecular weight were less affected by temperatures and pH values such as pyrene and fluoranthene.  The capabilities of CPC and DDAB modified clinoptilolites to remove PAHs from landfill leachate were similar to deionized solution, except for fluorene. Fluorene was adsorbed nearly 2% more on CPC-MC and DDAB-MC respectively, from landfill leachate compared to deionized water solution and met the water quality criteria of BC for anthracene, fluoranthene, and fluorene. This adsorption increase may be related to the attachment of fluorene to other organic materials in landfill leachate such as colloids, which makes the adsorbed fluorene on the colloid more hydrophobic, resulting in more removal.   5.2 Recommendations  It is recommended to investigate the effect of different pH values on stability of surfactants on modified clinoptilolites. There is not a global consensus regarding levels of PAHs; the recommended level in BC of several PAHs is below 1µg/L. Therefore, it is recommended to set up the detection limit of GC/MS in ng/L to be able to evaluate the PAH concentrations. In addition, because of the effect of other organic materials such as natural organic matter (NOM), multiple contaminated effects are recommended to be investigated.  Research may consider the use of modified clinoptilolites at scale to explore the potential applications. The PAHs-loaded clinoptilolite after adsorption can be combusted in an incinerator, and the cost would be similar to combustion of contaminated soil and sediment for the soil treatment in a contaminated site. However, the potential regeneration and reuse of the PAH-loaded clinoptilolites should be explored to achieve low-solid waste production during the treatment process.  It is recommended to study the regeneration of clinoptilolite by using an 107  organic solvent such as dichloromethane (DCM), acetone, or hexane on the PAH- loaded clinoptilolites. Further study of regeneration’s efficiency and longevity is also recommended.              108  References  "Standard Deviation." (2014). 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These chemical are mostly colorless, white, or pale with high melting and boiling points and very low solubility in water. They are very lipophilic and soluble in organic solvents. By increasing PAH molecular weight, the PAH solubility and vapor pressure decreases. In contrast, the resistance to oxidation and reduction increases (Abdel-Shafy and Mansour 2016). The solubility and vapor pressure of PAHs with two to seven aromatic rings decreases, while melting point and boiling point increases with increasing the molecular weight (Albers 2002).       126  Table A.1 US- EPA’s 16 priority pollutant PAHs and their physical and chemical properties (CCME 2010b; Wick et al. 2011) PAHs name Formula No.  of R.* Molecular Structure Molecular  Weight (gmol-1) Solubility  in water  (mgL-1) Vapor Pressure  (Pa) Log  Kow pKa Naphthalene C10H8 2  128.17 31.7 11.606 3.37  Acenaphthene C12H10 3  154.21 3.8  0.500 3.92  Acenaphthylene C12H8 3  152.2 16.1 3.866 4  Fluorene C13H10 3  166.22 1.9 0.432 4.18 22.6 Anthracene C14H10 3  178.23 0.043-0.075 3.4 × 10−3 4.54  Phenanthrene C14H10 3  178 1.15 9.1 × 10−2 4.57  Fluoranthene C16H10 4  202.20 0.26 1.1 × 10−2 5.22  Pyrene C16H10 4  202 0.132 5.7 × 10−4 5.18  Benz[a]anthracene* C18H12 4  228.29 0.011 2. 1 × 10−5 5.91  Chrysene*  C18H12 4  228.29 0.0015 1.0 × 10−6 5.91  Benzo[a]pyrene* C20H12 5  252.32 0.0038 6.5 × 10−7 5.91  Benzo[b]fluoranthene* C24H14 5  252.32 0.0015 1.1 × 10−5 5.80  Benzo[k]fluoranthene* C24H14 5  252.32 0.0008 1.3 × 10−8 6.00  Dibenz[a,h]anthracene* C22H14 6  278.35 0.0005 2.8 × 10−9 6.75  Benzo[g,h,i]perylene* C22H12 6  276.34 0.00026 1.3 × 10−8 6.50  Indeno[1,2,3-cd] pyrene* C22H12 6  276.34 0.062 1.9 × 10−8 6.50  *No. of R.: Number of rings        127  A.2 Occurrence of PAHs in the Environment  Table A.2 provides the concentration of five PAHs (anthracene, fluoranthene, fluorene, phenanthrene, and pyrene) from the 16 EPA prioritized pollutants list that are predominantly found in rivers, air, sediment, stormwater runoff and groundwater. Among those PAHs, phenanthrene and fluoranthene have the highest concentrations in rivers, air and sediment. However, fluoranthene and pyrene have the maximum concentration in stormwater.  Table A.2 Summary of occurrence of PAHs in the environment Reference/PAHs  Anthracene Fluoranthene Fluorene Phenanthrene Pyrene   Water (ng/L)    (Luo et al. 2004) Pearl River Delta, China 3.14 4.06 2.26 10.74 1.82 (Zhang et al. 2004) Tonghui River, Beijing, China 14.98  34.75 58.19 122.9 28.30 (Bai et al. 2014) The Liaohe River Basin, China 6.8 30.5 42.6 89.9 21.6 ((Patrolecco et al. 2010) the River Tiber (Italy)  14.3      Air (ng/m3)    (Albinet et al. 2007) Marseilles, France 0.767  3.488 1.098 8.470  5.832  (Wang et al. 2011) Beijing Tianjin region, China 19.91 48.16 116.06 153.49 24.99 Sediment (ng/g) (Zhang et al. 2004) Tonghui River, Beijing, China 16.23 93.82 21.88 87.21 80.28 (Navarro-Ortega et al. 2010) Ebro River Basin, Spain 14.71 147.46 28.01 45.48 117.87 Stormwater runoff (ng/L) (Hwang and Foster 2006) Tidal Anacostia River 5.43-119 86.5-1380 8.8-152 26.1-338 65.6-774 (Menzie et al. 2002) 102 1,288 55 821 670 (Selbig 2009)  parking lots Parking lot—Sealed 250 13810 <520 5410 9200 Groundwater (µg/L) (Han et al. 2013) Zhoukou, China 0.168 0.261 0.682 0.519 0.158 *The arterial street is a length of U.S. Highway 151 in Madison, Wis.;   <, less than     128  A.3 Water Quality Criteria  Regulation of PAHs: The EU and the governments of British Columbia (BC) and Canada have guidelines for water quality criteria for PAHs to protect drinking water, fresh and marine water aquatic life, and food processing manufacturing shown in (Appendix A.3). In British Columbia, Canada, the fresh water quality criteria to protect aquatic life for anthracene, fluoranthene, fluorene, and phenanthrene are 4, 4, 12, 0.3 µg/L, respectively (British Columbia 1993) . The Canadian Council of Ministers of the Environment has adopted even lower amounts of anthracene, fluoranthene, fluorene, phenanthrene, and pyrene (e.g. 0.012, 0.04, 3, 0.4, 0.025 µg/L, respectively) to protect aquatic life (CCME 2010b). The European Parliament and of the Council has adopted the environmental quality standard for surface water quality to protect aquatic life to maximum allowable concentration of 0.1 and 0.12 µg/L for anthracene and fluoranthene, respectively (The European Parliament and of the Council 2013) . These existing water criteria and standards for PAHs can drive one to uptake the PAHs from water to required level to protect aquatic life.      129  Table A.3 Guidelines and regulations for PAHs in the environment (British Columbia 1993; The European Parliament and of the Council 2013; CCME 2010b) PAH Fresh Water ( µg/L) Marine Water ( µg/L) Sediments (Fresh Water) ( µg/kg) Sediments (Marine) (µg/kg) BC Ministry of Environment Anthracene 4  NR*  600 NR  Fluoranthene 4  NR  2000  NR  Fluorene 12  12  200  200  Phenanthrene 0.3  NR  40 NR  Pyrene NR NR NR NR CCME (2003) Anthracene 0.012  46.9 46.9 Fluoranthene 0.04  111 113 Fluorene 3.0  21.2 21.2 Phenanthrene 0.4  41.9 86.7 Pyrene 0.025  53.0 153 European Union (maximum allowable concentration) Anthracene 0.1    Fluoranthene 0.12    Fluorene     Phenanthrene     Pyrene     *NR: not recommended    130  Appendix B  Modification of Clinoptilolite B.1 Main Properties of Bear River Zeolite   The mineral components of Bear River zeolite are 85% clinoptilolite, and balance opaline silica. The chemical composition of Bear River zeolite are cations including K (3.47%), Ca (1.60%) and Na (0.44%), and other elements such as Al (6.1%) , Fe (1.3%), Ba (1200 ppm), Sr (560 ppm), Zr (480 ppm), Ce (130 ppm), Rb (120 ppm), La (55 ppm), Y (55 ppm), Nd (45 ppm), Zn (35 ppm), Cu (25 ppm), and Pb (20 ppm) (Xu et al. 2010).  The rock analytical data were SiO2 (67.14%), Al2O3 (12.45%), Fe2O3 (2.56%), MgO (0.84%), CaO (2.49%), Na2O (2.6%), and K2O (2.35%) that were provided by the supplier (Xu et al. 2010). The cation exchange capacity of Bear River zeolite was 2.16 mol/kg (Xu et al. 2010).    131  B.2 Chemical Structure of Cationic Surfactants  ) Cetylpyreneidinium chloride (CPC)  ) Didodecyldimethylammonium bromide (DDAB)  ) Hexadecyltrimethylammonium bromide (HDTMA-Br) )    ) Tetramethylammonium chloride (TMA-Cl)     Online sources Figure B.2 Chemical structure of cationic surfactants   132  B.3 Properties of Cationic Surfactants  Table B.3 Summary of cationic surfactant properties Surfactant Formula Molar Mass  (g/mol) CMCa  (mmol/L) CPB C21H38NBrl 384.437 0.82b  CPC C21H38NCl 339.99  0.92c  DDAB C38H80NBr 462.63 0.0144d  HDTMA-Br C19H42NBr 364.45  0.9e  TMA-Cl C4H12NCl 109.6 NAf a Critical Micelle Concentration    b (Li et al. 2014)   c (Choi et al. 2009)      d (Mehta et al. 2006)    e (Li and Bowman 1997; Wibowo et al. 2011)  f Not Available  B.4 Preparation of Pretreated Clinoptilolite The natural clinoptilolite was sieved to retain particles between 30-40 mesh. Then, these clinoptilolite particles were washed with tap water and then distilled water to remove dust and then placed into an oven at 105oC for 24 hours to be dried (Chutia et al. 2009).  For homogenizing ions in the adsorption sites, the clinoptilolite was pretreated with NaCl solution (Xu et al. 2013). To perform this, 15 g of washed and dried clinoptilolite was placed in a 250 mL Erlenmeyer flask and added 150 mL NaCl of 1 mol/L to saturate the exchange sites with sodium ions for 24 hours (Kuleyin 2007; Wingenfelder et al. 2006). After saturation, the supernatants were discarded and pretreated clinoptilolites were washed with deionized water to remove the chloride ions using reagent colour solution as an indicator and then dried in the oven at 105℃ for 24 hours (Tashauoei et al. 2010).   133  B.5 Modification of Clinoptilolite with CPC Modification of Clinoptilolite with CPC: 10 g pretreated clinoptilolite was placed in a 250 mL Erlenmeyer flask and then 150 mL of five mmol/L CPC solution was added (Li et al. 2014; Zhan et al. 2011) and shaken at 220 rpm for 24 hours at room temperature. The CMC of CPB is 0.82 mmol/L in aqueous solution (Li et al. 2014). The supernatant was separated and the solids were washed with deionized water 10 times until the detected CPC was below 0.5 mg/L in the solution. The solids were dried at 60-65oC for 24 hours. The non-absorbed CPC concentration in the supernatant was measured by employing a UV/Vis spectrophotometer at λ max = 259 nm (Li et al. 2014; Zhan et al. 2011).    B.6 Modification of Clinoptilolite with DDAB Modification of Clinoptilolite with DDAB: 10 g Na form of clinoptilolite was placed in a 250 mL Erlenmeyer flask and then 150 mL of DDAB solution (2 mmol/L) was added and shaken at 220 rpm for 24 hours at room temperature. The supernatant was separated and the solids were washed with deionized water nine times until the detected DDAB was below 0.5 mg/L in the solution. The solids were dried at 60℃ for 24 hours. The residual DDAB concentration in the supernatant was measured by using a TOC Analyzer. The initial concentration of DDAB solution was chosen similar to HDTMA-Br to find any similar behaviour because these two chemicals have similar chemical structure, except DDAB has two long carbon chains and HDTMA-Br has one. B.7 Modification of Clinoptilolite with HDTMA-Br Modification of Clinoptilolite with HDTMA-Br: 10 g pretreated clinoptilolite and 150 mL of two mmol/L HDTMA-Br were placed in a 250 mL flask; clinoptilolite particles sizes were between mesh numbers of 30-40. The CMC for HDTMA-Br is 0.9 mmol/L at 25oC (Li et al. 134  1998; Li and Bowman 1997). In one study, the HDTMA loading was 208 (Li and Bowman 1997), and in another study it was180 (Bowman et al. 2002) mmol HDTMA/kg zeolite. The mixture was stirred for 24 hours at room temperature (20 ± 2 oC) at 220 rpm (Kuleyin 2007; Tashauoei et al. 2010; Wingenfelder et al. 2006). Then, supernatant was separated and the solid particles were washed 11 times with 150 mL deionized water until HDTMA concentration in the solution was close to the detection limit of the TOC instrument. Then solids were dried in an oven at 60℃ for 24 hours (Chutia et al. 2009; Kuleyin 2007) for future use. Then, the non-absorbed and leachate HDTMA concentration in the supernatant was measured using a TOC Analyzer (Wingenfelder et al. 2006). B.8 Modification of Clinoptilolite with TMA-Cl Modification of Clinoptilolite with TMA – Chloride: 2.18 g of TMA-Cl was placed in a 1000 mL flask and deionized water was added to reach the volume of 1000 mL. 20 g pretreated clinoptilolite was placed into a 250 mL Erlenmeyer flask and 150 mL prepared TMA-Cl solution was added. The mixture was shaken at 220 rpm for 24 hours and then the supernatant was separated and the solid was washed seven times with 100 mL deionized water. The supernatant was separated and the residual TMA concentration in the supernatant was measured by using a TOC Analyzer. The solid was placed into an oven at 65oC for 24 hours for drying.    135  B.9 Residual Concentration of CPC in Supernatant after Modification and Washes  The calibration standards of eight concentration levels of CPC were carried out including the concentration of  0.5, 1, 2, 4, 5, 20, 50.12, and 71.6 mg/L in water. To measure contamination introduced throughout sample handling, a blank was processed together with the samples and the concentration of the blank was corrected for samples.   Figure B.9 The calibration curve of eight calibration standard levels for CPC        y = 0.0127x R² = 0.9992 00.10.20.30.40.50.60.70.80.910 10 20 30 40 50 60 70 80Absorbance CPC concentration (mg/L) CPC 136  Table B.9 Residual concentration of CPC in supernatant after modification and 10 time washes with deionized water at room temperature Description  UV/Vis Absorbance sample 1  UV/Vis Absorbance sample 2  UV/Vis Average absorbance   Corrected UV/Vis Absorbance for Blank CPC Concentration (mg/L)  STD1  blank 0.003 0.003 0.003    waste solution (supernatant) 0.07 0.071 0.0705 0.0675 5.31 0.0005 Number of washes of modified clinoptilolite after modification 1st  0.037 0.035 0.036 0.033 2.60 0.001 2nd  0.019 0.018 0.0185 0.0155 1.22 0.0005 3th 0.024 0.022 0.023 0.02 1.57 0.001 4th  0.027 0.022 0.0245 0.0215 1.69 0.0025 5th 0.029 0.025 0.027 0.024 1.89 0.002 6th  0.03 0.029 0.0295 0.0265 2.09 0.0005 7th 0.024 0.025 0.0245 0.0215 1.69 0.0005 8th  0.021 0.021 0.021 0.018 1.42 0 9th 0.027 0.022 0.0245 0.0215 1.69 0.0025 10th 0.009 0.008 0.0085 0.0055 0.43 0.0005 Leached2     16.3  1STD: Standard deviation, n=2 2Leached: Total leached CPC concentration from CPC-MC after number of washes   137  B.10 Residual Concentration of DDAB in Supernatant after Modification and Washes  The calibration standards of five concentration levels of DDAB were carried out including the concentration of  0.34, 0.69, 1.36, 2.15 and 3.4 mg/L in water. To measure contamination introduced throughout sample handling, two blanks were processed together with the samples and the concentrations of the blanks were corrected for five calibration standard levels and samples.   Figure B.10 The calibration curve of five calibration standard levels for DDAB       y = 168198x - 62788 R² = 0.9937 01000002000003000004000005000006000000 0.5 1 1.5 2 2.5 3 3.5 4Response Area TOC (mg/L) DDAB 138  Table B.10 Residual concentration of DDAB in supernatant after modification and nine time washes with deionized water at room temperature Description  TOC1 Response Area   Blank Correction  TOC (mg/L)   Average TOC (mg/L) DDAB  (mg/L)  STD2  blank 210728      195105      Waste3 957530 754613.5 4.9 4.4 6.5 0.46 804181 601264.5 4    Number of washes of modified clinoptilolite after modification 1st   451778 248861 1.9 1.7 2.6 0.12 409920 207003 1.6    2nd   427421 224504 1.7 1.7 2.5 0.0 427421 224504 1.7    3th  225134 22217 0.5 0.5 0.8 0.01 226863 23946 0.5    4th   273186 70269 0.8 0.7 1.0 0.10 240291 37374 0.6    5th  285619 82702 0.9 0.7 1.1 0.14 239753 36836 0.6    6th   266125 63208 0.7 0.7 1.0 0.09 234278 31361 0.6     7th 386271 183354 1.5 1.1 1.6 0.38 260243 57326 0.7     8th  246053 43136 0.6 0.7 1.0 0.04 259176 56259 0.7     9th 246825 43908 0.6 0.6 1.0 0.01 250823 47906 0.7    Leached4     12.55   1TOC: Total organic carbon 2 STD: Standard deviation, n=2 3Waste: waste solution (supernatant) after modification  4Leached: Total DDAB leached concentration from DDAB-MC after number of washes    139  B.11 Residual Concentration of HDTAM in Supernatant after Modification and Washes  The calibration standards of seven concentration levels of HDTMA were carried out including the concentration of 0.3, 0.6, 1.3, 1.9, 3.1, 6.3, 12.6 mg/L in water. To measure contamination introduced throughout sample handling, two blanks were processed together with the samples and the concentrations of the blanks were corrected for seven calibration levels and samples.  Figure B.11 The calibration curve of seven calibration standard levels for HDTMA         y = 82220x + 72969 R² = 0.9523 0.00200000.00400000.00600000.00800000.001000000.001200000.000 2 4 6 8 10 12 14Response Area TOC (mg/L) HDTMA 140  Table B.11 Residual concentration of HDTMA in supernatant after modification and 11 time washes with deionized water at room temperature Description  TOC1  Response Area   Blank Correction  TOC (mg/L)    Average  TOC (mg/L) HDTMA (mg/L)  STD2  Blank  212101      189107      Waste3  1898102 1697498 19.8 20.2 32.25 0.43 1969194 1768590 20.6    Number of washes of modified clinoptilolite after modification 1st  714301 513697 5.4 5.1 8.1 0.28 668669 468065 4.8    2nd  1692216 1491612 17.3 17.7 28.3 0.47 1768881 1568277 18.2    3th  566337 365733 3.6 3.4 5.4 0.19 535691 335087 3.2    4th  1689544 1488940 17.2 17.6 28.1 0.36 1748543 1547939 17.9    5th  1643611 1443007 16.7 17.0 27.2 0.36 1703132 1502528 17.4    6th  1251172 1050568 11.9 11.9 19.0 0.00 1251172 1050568 11.9     7th 1363445 1162841 13.3 13.4 21.4 0.13 1385503 1184899 13.5     8th 1166974 966370 10.9 10.9 17.5 0.08 1180634 980030 11.0     9th 1105173 904569 10.1 10.1 16.2 0.04 1110992 910388 10.2    10th   1433412 1232808 14.1 14.1 22.5 0.00 1433412 1232808 14.1    11th  424574 223970 1.8 1.9 3.0 0.06 434156 233552 2.0    Leached4      197  1TOC: Total organic carbon 2 STD: Standard deviation, n=2 3Waste: waste solution (supernatant) after modification  4Leached: Total HDTMA leached concentration from HDTMA-MC after number of washes   141  B.12 Residual Concentration of TMA in Supernatant after Modification and Washes  The calibration standards of five concentration levels of TMA were carried out including the concentration of 0.48, 0.96, 2.4, 4.8, 9.6 mg/L in water. To measure contamination introduced throughout sample handling, two blanks were processed together with the samples and the concentrations of the blanks were corrected for five calibration levels and samples.  Figure B.12 The calibration curve of five calibration standard levels for TMA        y = 1E+06x + 417754 R² = 0.9911 020000004000000600000080000001000000012000000140000000 2 4 6 8 10 12Response Area TOC (mg/L) TMA-Cl 142  Table B.12 Residual concentration of TMA in supernatant after modification and seven time washes with deionized water at room temperature Description  TOC1 Response Area   Blank Correction  TOC (mg/L)  Average  TOC (mg/L) TMA  (mg/L)  STD2  Blank 2002817       1994203      Waste3 15990537 14067445 13.6 13.7 31.3 0.06  16113621 14190529 13.8    Number of washes of modified clinoptilolite after modification 1st 2830042 906950 0.5 0.5 1.1 0.00  2824950 901858 0.5    2nd 13537315 11614223 11.2 11.1 25.4 0.07  13400893 11477801 11.1    3th 4610182 2687090 2.3 2.2 5.1 0.04  4524295 2601203 2.2    4th 3408808 1485716 1.1 1.1 2.4 0.00  3414111 1491019 1.1    5th 3072756 1149664 0.7 0.7 1.7 0.00  3065267 1142175 0.7    6th 2805067 881975 0.5 0.5 1.1 0.02  2836416 913324 0.5    7th 2784176 861084 0.4 0.4 1.0 0.01  2769432 846340 0.4    Leached4      37.8  1TOC: Total organic carbon 2 STD: Standard deviation, n=2 3Waste: waste solution (supernatant) after modification  4Leached: Total TMA leached concentration from TMA-MC after number of washes   143  B.13 Thermal Stability of CPC on CPC-MC at Different Temperatures  The calibration standards of eight concentration levels of CPC were carried out including the concentration of 0.1, 0.5, 1, 2, 4, 5, 10, and 20 mg/L in water. To measure contamination introduced throughout sample handling, a blank was processed together with the samples and the concentration of the blank was corrected for all samples.  Figure B.13 The calibration curve of eight calibration standard levels for CPC       Table B.13 Thermal stability of CPC on CPC-MC at different temperature CPC-MC      Temp.1 (oC)  Absorbance   Average Absorbance Blank correction  CPC  (mg/L)  STD2  5 0.004 0.00375 0.00275 0.23 0.0003 0.0035     10 0.004 0.00425 0.00325 0.27 0.0003 0.0045     20 0.004 0.004 0.001 0.08 0.00 0.004     35 0.005 0.0055 0.0025 0.21 0.0005 0.006     1Temp: temperature 2 STD: Standard deviation, n=2   y = 0.012x R² = 0.9994 00.050.10.150.20.250.30 5 10 15 20 25Absorbance CPC concentration (mg/L) CPC 144  B.14 Thermal Stability of DDAB on DDAB-MC at Different Temperatures  The calibration standards of six concentration levels of TMA were carried out including the concentration of 0.68, 1.35, 2.02, 3.37, 6.75, and 13.5 mg/L in water. To measure contamination introduced throughout sample handling, a blank was processed together with the samples and the concentration of the blank was corrected for six calibration levels and samples.  Figure B.14 The calibration curve of six calibration standard levels for DDAB       Table B.14 Thermal stability of DDAB on DDAB-MC at different temperature     DDAB-MC Temp.1 (oC) TOC2 Response Area Blank  correction TOC  (mg/L) Average  TOC (mg/L) DDAB (mg/L) STD3 5 1106966 196208 0.7 0.7 1.10 0.1 1204950 294191 0.8    10 1179241 225658 0.7 0.8 1.21 0.1 1333864 380281 0.9    20 1425191 372217 0.9 0.9 1.31 0.0 1386225 333250 0.9    35 1630429 527594 1.1 1.1 1.67 0.0 1655970 553134 1.1    1Temp: temperature 2TOC: Total organic carbon 3 STD: Standard deviation, n=2   y = 763910x - 322111 R² = 0.9922 0.02000000.04000000.06000000.08000000.010000000.012000000.00 5 10 15Response Area TOC (mg/L) DDAB 145  B.15 Thermal Stability of HDTMA on HDTMA-MC at Different Temperatures  The calibration standards of six concentration levels of TMA were carried out including the concentration of 0.63, 1.26, 1.9, 3.2, 6.3, and 12.6 mg/L in water. To measure contamination introduced throughout sample handling, a blank was processed together with the samples and the concentration of the blank was corrected for six calibration levels and samples.  Figure B.15 The calibration curve of six calibration standard levels for HDTMA      Table B.15 Thermal stability of HDTMA on HDTMA-MC at different temperature      HDTMA-MC Temp.1 (oC) TOC2 Response Area  Blank  correction TOC (mg/L) Average TOC (mg/L) HDTMA (mg/L) STD3  5 1293662 382904 1.9 1.5 2.4 0.45 1220425 309666 1.2    10 1634074 376572 3.3 2.6 4.1 0.77 1478901 525321 1.8    20 1330155 578362 3.8 3.1 4.9 0.92 1477640 424665 2.3    35 1955388 852553 6.6 5.0 8.0 1.5 1644271 541436 3.5    1Temp: temperature 2TOC: Total organic carbon 3 STD: Standard deviation, n=2 y = 100045x + 194115 R² = 0.9369 020000040000060000080000010000001200000140000016000000 5 10 15Response Area TOC (mg/L) HDTMA 146  Appendix C  Batch Adsorption Test C.1 Batch Adsorption Test Procedure A 100 mL graduated cylinder was used to measure 100 mL of PAHs solution sample. 250 mL amber bottles with a screw lid lined with Teflon were used to place a desired amount of each modified clinoptilolite and 100 mL measured mixture PAHs solution with different concentration (50 µg/L for anthracene, and 100 µg/L for fluoranthene, fluorene, phenanthrene, and pyrene). The amber bottles were tighten with a screw lid lined with Teflon and put into shaker for a desired time (e.g., 24 hours); after desired time, the solution from sample bottle were transferred into a 250 mL separatory funnel. A 25 mL of methylene chloride were used to extract PAHs. The separatory funnels were sealed and shaken vigorously for 2 minutes with regular venting to discharge surplus pressure. The methylene chloride layer was allowed to separate from the water phase for 10 minutes. The solvent extract was collected in a 125 mL evaporative flask. Then, the extraction was repeated two more times by using 25 mL fresh solvent and combined the three solvent extract.  The evaporative flask including collected organic solvent was placed into a Rotary Vacuum Evaporator to evaporate methylene chloride (DCM) at 50oC. After the collected extract was reduced to 1-3 mL, the reduced extract was transferred to 10 mL vial and the evaporative flask was washed with few milliliter methylene chlorides and added to concentrated extract. Further concentration to dryness was performed under a gentle stream of clean nitrogen. Then 900 µl toluene and 100 µl internal standard solution (pheneantheren-d10) was added and the final solution was analyzed by GC/Mass. For quality control and quality assurance, a blank, control, and duplicate samples were included and were exactly subjected the same analytical process as the actual sample (Björklund and Li 2015; U.S. EPA 1990; U.S. EPA 1996). All 147  glassware was washed with detergent, then washed with tap water, and baked at 500oC for two hours.   C.2 Removal of PAHs by Using Different Adsorbents The results of PAHs removal by using different adsorbents are shown in different Tables. Table C.2.1 Experimental data of anthracene for different adsorbents at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hours with initial concentration of 50 µg/L  Adsorbents   Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal R% STD2  CPC-MC 1.0009 1 1.0 4.9 98.0 0.07 1.0009 0.91        1.0008 1.09        DDAB-MC 1.0004 0.39 0.5 4.9 98.9 0.12 1.0004 0.43        1.0003 0.66        1.0001 0.65        HDTMA-MC 1.0018 2.73 2.5 4.7 95.1 0.19 1.0005 2.38        1.0009 2.29        TMA-MC 1.0005 16.83 16.8 3.3 66.3  Clinoptilolite 1.0004 34.94 35.2 1.5 29.6 0.26 1.0009 35.45     1Conc.: Concentration    2STD: Standard deviation, n=2, 3, or 4    148  Table C.2.2 Experimental data of fluoranthene for different adsorbents at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  CPC-MC 1.0009 1.51 1.3 9.9 98.7 0.20 1.0009 1.23        1.0008 1.02        DDAB-MC 1.0004 0.31 0.6 9.9 99.4 0.20 1.0004 0.86        1.0003 0.63        1.0001 0.64        HDTMA-MC 1.0018 3.45 2.9 9.7 97.1 0.40 1.0005 2.91        1.0009 2.47        TMA-MC 1.0005 67.51 67.5 3.2 32.5  Clinoptilolite 1.0004 93.47 96.4 0.4 3.6 2.98 1.0009 99.42     1Conc.: Concentration    2STD: Standard deviation, n=2, 3, or 4 Table C.2.3 Experimental data of fluorene for different adsorbents at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  CPC-MC 1.0009 4.96 6.1 9.4 93.9 0.90 1.0009 6.11        1.0008 7.17        DDAB-MC 1.0004 4.32 4.0 9.6 96.0 0.36 1.0004 3.4        1.0003 4.23        1.0001 4.07        HDTMA-MC 1.0018 18.65 16.2 8.4 83.8 1.92 1.0005 15.84        1.0009 13.97        TMA-MC 1.0005 71.1 71.1 2.9 28.9  Clinoptilolite 1.0004 80.57 83.5 1.7 16.6 2.88 1.0009 86.33        1Conc.: Concentration    2STD: Standard deviation, n=2, 3, or 4  149  Table C.2.4 Experimental data of phenanthrene for different adsorbents at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  CPC-MC 1.0009 2.99 2.8 9.7 97.2 0.18 1.0009 2.8        1.0008 2.54        DDAB-MC 1.0004 1.17 1.2 9.9 98.8 0.09 1.0004 1.32        1.0003 1.09        1.0001 1.09        HDTMA-MC 1.0018 7.52 6.5 9.3 93.5 0.83 1.0005 6.6        1.0009 5.49        TMA-MC 1.0005 80.39 80.4 2.0 19.6  Clinoptilolite 1.0004 90.08 93.8 0.6 6.2 3.73 1.0009 97.54      1Conc.: Concentration    2STD: Standard deviation, n=2, 3, or 4 Table C.2.5 Experimental data of pyrene for different adsorbents at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  CPC-MC 1.0009 1.16 0.9 9.9 99.1 0.20 1.0009 0.8        1.0008 0.68        DDAB-MC 1.0004 0.31 0.3 10.0 99.7 0.04 1.0004 0.38        1.0003 0.27        1.0001 0.28        HDTMA-MC 1.0018 3.01 2.6 9.7 97.4 0.33 1.0005 2.6        1.0009 2.2        TMA-MC 1.0005 78.85 78.9 2.1 21.2  Clinoptilolite 1.0004 92.45 94.8 0.5 5.2 2.35 1.0009 97.14        1Conc.: Concentration    2STD: Standard deviation, n=2, 3, or 4  150  C.3 PAH Adsorption Kinetics Table C.3.1 Experimental data of anthracene for CPC-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times  Adsorbents    Time (h) Adsorbent (g) Initial  Solution  Conc.1 Co (µg/L) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2      CPC-MC        0.25 1.0009 50 6.66 6.66 4.3 86.7 0.06  0.5 1.0009 50 4.67 4.67 4.5 90.7 0.11  1 1.0008 50 2.46 4.78 4.5 90.4 0.22 2.32 1 1.0003 50 7.1         2 1.0009 50 1.42 1.42 4.85 97.2 0.41  4 1.0003 50 1.28 1.28 4.87 97.4 0.82  8 1.0008 50 0.96 1.005 4.90 98.0 1.63 0.05 8 1.0007 50 1.05         24 1.0009 50 1.08 1.05 4.89 97.9 4.91 0.05 24 1.0009 50 0.97         24 1.0008 50 1.09         48 1.0009 50 0.89 0.89 4.91 98.2 9.78  1Conc.: Concentration     2STD: Standard deviation, n=2, or 3    151  Table C.3.2 Experimental data of fluoranthene for CPC-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times  Adsorbents    Time (h) Adsorbent (g) Initial  Solution  Conc.1 Co (µg/L) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2  CPC-MC       0.25 1.0009 100 13.4 13.4 8.7 86.6 0.03  0.5 1.0009 100 9.0 9.0 9.1 91.0 0.06  1 1.0008 100 3.4 5.2 9.5 94.8 0.11 1.87 1 1.0003 100 7.1         2 1.0009 100 1.8 1.8 9.8 98.2 0.20  4 1.0003 100 1.5 1.5 9.8 98.5 0.41  8 1.0008 100 1.2 1.2 9.9 98.8 0.81  8 1.0007 100 1.2         24 1.0009 100 1.7 1.3 9.9 98.7 2.43 0.27 24 1.0009 100 1.3         24 1.0008 100 1.0         48 1.0009 100 1.0 1.0 9.9 99.0 4.85  1Conc.: Concentration     2STD: Standard deviation, n=2, or 3   152  Table C.3.3 Experimental data of fluorene for CPC-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%  t/qe STD2  CPC-MC       0.25 1.0009 18.83 18.8 8.1 81.2 0.03  0.5 1.0009 15.1 15.1 8.5 84.9 0.06  1 1.0008 9.09 8.1 9.2 91.9 0.11 1.00 1 1.0003 7.1         2 1.0009 6.5 6.5 9.3 93.5 0.21  4 1.0003 7.76 7.8 9.2 92.2 0.43  8 1.0008 6.96 7.4 9.3 92.6 0.86 0.44 8 1.0007 7.83         24 1.0009 5.35 6.3 9.4 93.7 2.56 0.75 24 1.0009 6.52         24 1.0008 7.17         48 1.0009 7.65 7.7 9.2 92.4 5.20  1Conc.: Concentration     2STD: Standard deviation, n=2, or 3  Table C.3.4 Experimental data of phenanthrene for CPC-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%  t/qe STD2     CPC-MC      0.25 1.0009 16.3 16.3 8.4 83.7 0.03  0.5 1.0009 12.2 12.2 8.8 87.8 0.06  1 1.0008 6.5 6.8 9.3 93.2 0.11 0.29 1 1.0003 7.1         2 1.0009 4.1 4.1 9.6 96.0 0.21  4 1.0003 3.7 3.7 9.6 96.3 0.42  8 1.0008 2.8 2.9 9.7 97.1 0.82 0.13 8 1.0007 3.1         24 1.0009 3.2 2.9 9.7 97.2 2.47 0.28 48 1.0009 2.73  9.7 97.3   1Conc.: Concentration     2STD: Standard deviation, n=2, or 3    153  Table C.3.5 Experimental data of pyrene for CPC-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%   t/qe STD2       CPC-MC        0.25 1.0009 13.0 13.0 8.7 87.0 0.03  0.5 1.0009 8.5 8.5 9.1 91.6 0.05  1 1.0008 3.0 5.0 9.5 95.0 0.11 2.07 1 1.0003 7.1         2 1.0009 1.5 1.5 9.8 98.6 0.20  4 1.0003 1.2 1.2 9.9 98.8 0.40  8 1.0008 0.8 0.8 9.9 99.2 0.81  8 1.0007 0.8         24 1.0009 1.3 0.9 9.9 99.1 2.42 0.24 24 1.0009 0.9         24 1.0008 0.7         48 1.0009 0.6 0.6 9.9 99.4 4.84  1Conc.: Concentration     2STD: Standard deviation, n=2, or 3    154  Table C.3.6 Experimental data of anthracene for DDAB-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 50 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2   DDAB-MC               0.25 1.0007 4.72 5.405 4.458 89.2 3.36 0.69 0.25 1.0001 6.09          0.5 1.0007 2.23 2.205 4.777 95.6 6.28 0.02 0.5 1.0002 2.18          1 1.0006 1.09 1.07 4.891 97.9 12.27 0.10 1 1.0008 1.17          1 1.0002 0.94          2 1.0002 0.73 0.60 4.939 98.8 24.30 0.13 2 1.0001 0.47          4 1.0004 0.49 0.49 4.949 99.0 48.49   8 1.0005 0.45 0.45 4.954 99.1 96.90 0.01 8 1.0002 0.44          24 1.0004 0.32 0.61 4.938 98.8 291.63 0.17 24 1.0004 0.79          24 1.0003 0.66          24 1.0001 0.66          48 1.0005 0.43 0.42 4.955 99.2 581.23 0.01 48  1.0007 0.41          1Conc.: Concentration     2STD: Standard deviation, n=2, 3 or 4    155  Table C.3.7 Experimental data of fluoranthene for DDAB-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2  DDAB-MC             0.25 1.0007 12.0 13.9 8.6 86.1 1.74 1.86 0.25 1.0001 15.7          0.5 1.0007 5.9 6.3 9.4 93.7 3.20 0.44 0.5 1.0002 6.8          1 1.0006 1.7 1.5 9.8 98.5 6.10 0.34 1 1.0008 1.9          1 1.0002 1.1          2 1.0002 1.0 0.8 9.9 99.2 12.10 0.19 2 1.0001 0.6          4 1.0004 0.7 0.7 9.9 99.3 24.18   8 1.0005 0.7 0.7 9.9 99.3 48.37 0.01 8 1.0002 0.7          24 1.0004 0.3 0.6 9.9 99.4 144.91 0.17 24 1.0004 0.8          24 1.0003 0.6          24 1.0001 0.6          48 1.0005 0.8 0.8 9.9 99.3 290.35 0.05 48 1.0007 0.7       1.74 1.86 1Conc.: Concentration     2STD: Standard deviation, n=2, 3 or 4    156  Table C.3. 8 Experimental data of fluorene for DDAB-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc.1 Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%  t/qe STD2  DDAB-MC             0.25 1.0007 12.75 13.52 8.6 86.5 0.029 0.77 0.25 1.0001 14.29          0.5 1.0007 7.48 6.91 9.3 93.1 0.054 0.58 0.5 1.0002 6.33          1 1.0006 5.6 4.38 9.6 95.6 0.105 0.97 1 1.0008 4.31          1 1.0002 3.23          2 1.0002 5.04 3.76 9.6 96.2 0.208 1.29 2 1.0001 2.47          4 1.0004 4.11 4.11 9.6 95.9 0.417   8 1.0005 4.05 4.18 9.6 95.8 0.835 0.13 8 1.0002 4.3          24 1.0004 4.46 3.97 9.6 96.0 2.500 0.51 24 1.0004 3.13          24 1.0003 4.23          24 1.0001 4.07          48 1.0005 4.39 4.44 9.6 95.6 5.026 0.05 48 1.0007 4.48   8.6 86.5    1Conc.: Concentration     2STD: Standard deviation, n=2, 3 or 4    157  Table C.3. 9 Experimental data of phenanthrene for DDAB-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe  STD2   DDAB-MC             0.25 1.0007 11.3 12.8 8.7 87.2 1.72 1.49 0.25 1.0001 14.3          0.5 1.0007 5.1 5.0 9.5 95.0 3.16 0.06 0.5 1.0002 5.0          1 1.0006 2.7 2.5 9.7 97.5 6.15 0.33 1 1.0008 2.7          1 1.0002 2.0          2 1.0002 1.7 1.5 9.8 98.5 12.19 0.17 2 1.0001 1.3          4 1.0004 1.4 1.4 9.9 98.6 24.35   8 1.0005 1.2 1.2 9.9 98.8 48.60 0.03 8 1.0002 1.2          24 1.0004 1.2 1.2 9.9 98.8 145.72 0.06 24 1.0004 1.2          24 1.0003 1.1          24 1.0001 1.1          48 1.0005 1.3 1.2 9.9 98.8 291.70 0.06 48 1.0007 1.2       1.72 1.49 1Conc.: Concentration     2STD: Standard deviation, n=2, 3 or 4    158  Table C.3.10 Experimental data of pyrene for DDAB-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2   DDAB-MC             0.25 1.0007 11.7 13.5 8.6 86.5 1.73 1.82 0.25 1.0001 15.3          0.5 1.0007 5.6 6.1 9.4 93.9 3.20 0.47 0.5 1.0002 6.6          1 1.0006 1.4 1.3 9.9 98.7 6.08 0.23 1 1.0008 1.6          1 1.0002 1.0          2 1.0002 0.6 0.5 10.0 99.5 12.06 0.17 2 1.0001 0.3          4 1.0004 0.4 0.4 10.0 99.7 24.09   8 1.0005 0.4 0.4 10.0 99.7 48.2 0.02 8 1.0002 0.3          24 1.0004 0.3 0.3 10.0 99.7 144.5 0.03 24 1.0004 0.4          24 1.0003 0.3          24 1.0001 0.3          48 1.0005 0.4 0.4 10.0 99.6 289.29 0.06 48 1.0007 0.3       1.73 1.82 1Conc.: Concentration     2STD: Standard deviation, n=2, 3 or 4    159  Table C.3.11 Experimental data of anthracene for HDTMA-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 50 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2   HDTMA-MC        0.25 1.0007 12.17 12.17 3.78 75.7 4.0   0.5 1.0004 8.55 8.55 4.14 82.9 7.2   1 1.0004 6.6 6.6 4.34 86.8 13.8   2 1.0005 4.76 4.76 4.52 90.5 26.5   4 1.0003 3.9 3.9 4.61 92.2 52.1   8 1.0001 2.99 2.85 4.71 94.3 101.8 0.1 8 1.0004 2.71          24 1.00014 2.53 2.40 4.76 95.2 302.6 0.1 24 1.00018 2.38          24 1.0009 2.29          48 1.0006 1.62 1.62 4.84 96.8 595.6   1Conc.: Concentration     2STD: Standard deviation, n=2, or 3    160  Table C.3.12 Experimental data of fluoranthene for HDTMA-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2   HDTMA-MC        0.25 1.0007 22.4 22.4 7.8 77.6 1.93   0.5 1.0004 15.1 15.1 8.5 84.9 3.54   1 1.0004 8.3 8.3 9.2 91.7 6.54   2 1.0005 5.0 5.0 9.5 95.0 12.64   4 1.0003 4.1 4.1 9.6 95.9 25.04   8 1.0001 3.2 3.3 9.7 96.7 49.64   8 1.0004 3.3          24 1.00014 3.2 2.9 9.7 97.1 148.29 0.29 24 1.00018 2.9          24 1.0009 2.5          48 1.0006 2.3 2.3 9.8 97.7 294.93   1Conc.: Concentration     2STD: Standard deviation, n=2, or 3    161  Table C.3.13 Experimental data of fluorene for HDTMA-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2   HDTMA-MC        0.25 1.0007 35.49 35.5 6.4 64.5 0.04  0.5 1.0004 18.46 18.5 8.2 81.5 0.06  1 1.0004 22.1 22.1 7.8 77.9 0.13  2 1.0005 18.43 18.4 8.2 81.6 0.25  4 1.0003 18.63 18.6 8.1 81.4 0.49  8 1.0001 17.21 16.8 8.3 83.2 0.96 0.4 8 1.0004 16.35          24 1.00014 17.24 15.7 8.4 84.3 2.85 1.3 24 1.00018 15.84          24 1.0009 13.97          48 1.0006 13.57 13.6 8.6 86.4 5.56  1Conc.: Concentration     2STD: Standard deviation, n=2, or 3    162  Table C.3.14 Experimental data of phenanthrene for HDTMA-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2   HDTMA-MC        0.25 1.0007 30.2 30.2 7.0 69.8 2.15   0.5 1.0004 19.7 19.7 8.0 80.3 3.74   1 1.0004 15.5 15.5 8.4 84.5 7.10   2 1.0005 11.3 11.3 8.9 88.7 13.54   4 1.0003 9.8 9.8 9.0 90.2 26.62   8 1.0001 7.8 7.6 9.2 92.4 51.95   8 1.0004 7.4          24 1.00014 6.9 9.2 9.1 90.8 158.60 3.40 24 1.00018 6.6          24 1.0009 14.0          48 1.0006 5.0 5.0 9.5 95.0 303.40   1Conc.: Concentration       2STD: Standard deviation, n=2, or 3    163  Table C.3.15 Experimental data of pyrene for HDTMA-MC adsorbent at 1g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and different sorption times with initial concentration of 100 µg/L Adsorbents    Time (h) Adsorbent (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%   t/qe STD2   HDTMA-MC        0.25 1.0007 22.19 22.19 7.8 77.8 1.93   0.5 1.0004 15.45 15.45 8.5 84.6 3.55   1 1.0004 8.35 8.35 9.2 91.7 6.55   2 1.0005 4.9 4.9 9.5 95.1 12.62   4 1.0003 3.96 3.96 9.6 96.0 25.00   8 1.0001 2.94 2.98 9.7 97.0 49.49   8 1.0004 3.02          24 1.00014 2.78 2.53 9.7 97.5 147.79 0.24 24 1.00018 2.6          24 1.0009 2.2          48 1.0006 1.95 1.95 9.8 98.1 293.90   1Conc.: Concentration     2STD: Standard deviation, n=2, or 3    164  C.4 Adsorbent Dosage Effect Table C.4.1 Experimental data of anthracene for CPC-MC adsorbent at different amount to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5and sorption time of 24 hour with initial concentration of 50 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2       CPC-MC       2.0007 0.42  2.5 99.2  1.0009 1 1.0 4.9 98.0 0.07 1.0009 0.91     1.008 1.09     0.5008 1.67  9.7 96.7  0.2006 3.93  23.0 92.1  0.1002 7.31 7.42 42.4 85.2 0.08 0.1006 7.49     0.1007 7.46     0.0503 13.21  73.1 73.6  0.01 22.15  278.5 55.7  1Conc.: Concentration     2STD: Standard deviation, n=3  Table C.4.2 Experimental data of fluoranthene for CPC-MC adsorbent at different amount to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2   CPC-MC           2.0007 0.63  5.0 99.4  1.0009 1.51 1.3 9.9 98.7 0.20 1.0009 1.23     1.008 1.02     0.5008 1.59  19.7 98.4  0.2006 3.43  48.1 96.6  0.1002 6.39 6.35 93.2 93.7 0.03 0.1006 6.33     0.1007 6.32     0.0503 13.24  172.5 86.8  0.01 46.91  530.9 53.1  1Conc.: Concentration     2STD: Standard deviation, n=3 165  Table C.4.3 Experimental data of fluorene for CPC-MC adsorbent at different amount to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2   CPC-MC           2.0007 3.69  4.8 96.3  1.0009 4.96 6.1 9.4 93.9 0.90 1.0009 6.11     1.008 7.17     0.5008 13.02  17.4 87.0  0.2006 25.44  37.2 74.6  0.1002 39.11 37.35 62.3 62.6 2.59 0.1006 39.26     0.1007 33.69     0.0503 52.94  93.6 47.1  0.01 63.84  361.6 36.2  1Conc.: Concentration     2STD: Standard deviation, n= 3  Table C.4.4 Experimental data of phenanthrene for CPC-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2   CPC-MC            2.0007 0.55  5.0 99.5  1.0009 2.99 2.8 9.7 97.2 0.18 1.0009 2.8     1.008 2.54     0.5008 4.9  19.0 95.1  0.2006 11.15  44.3 88.9  0.1002 19.47 19.88 79.7 80.1 0.30 0.1006 20.01     0.1007 20.16     0.0503 32.28  134.6 67.7  0.01 65.04  349.6 35.0  1Conc.: Concentration     2STD: Standard deviation, n= 3  166  Table C.4.5 Experimental data of pyrene for CPC-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2   CPC-MC           2.0007 0.29  5.0 99.7  1.0009 1.16 0.9 9.9 99.1 0.20 1.0009 0.8     1.008 0.68     0.5008 1.21  19.7 98.8  0.2006 3.1  48.3 96.9  0.1002 6.27 6.28 93.3 93.7 0.23 0.1006 6.01     0.1007 6.57     0.0503 13.41  172.1 86.6  0.01 44.87  551.3 55.1  1Conc.: Concentration     2STD: Standard deviation, n= 3 Table C.4.6 Experimental data of anthracene for DDAB-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 50 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  DDAB-MC             2.0001 0.2  2.5 99.6  1.0004 0.39 0.5325 4.9 98.9 0.12 1.0004 0.43     1.0001 0.66     1.0003 0.65     0.5002 0.57  9.9 98.9  0.2001 1.41  24.3 97.2  0.1002 3.11 3.5025 46.4 93.0 0.28 0.1003 3.4     0.1001 3.84     0.10 3.66     0.05 6.57  86.9 86.9  0.0101 14.28  353.7 71.4  1Conc.: Concentration     2STD: Standard deviation, n= 4  167  Table C.4.7 Experimental data of fluoranthene for DDAB-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  DDAB-MC            2.0001 0.52  5.0 99.5  1.0004 0.31 0.61 9.9 99.4 0.20 1.0004 0.86     1.0001 0.63     1.0003 0.64     0.5002 0.73  19.8 99.3  0.2001 1.18  49.4 98.8  0.1002 2.28 2.2325 97.6 97.8 0.04 0.1003 2.25     0.1001 2.18     0.10 2.22     0.05 4.58  190.8 95.4  0.0101 30.55  687.6 69.5  1Conc.: Concentration     2STD: Standard deviation, n= 4    168  Table C.4.8 Experimental data of fluorene for DDAB-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  DDAB-MC             2.0001 0.92  5.0 99.1  1.0004 4.32 4.005 9.6 96.0 0.36 1.0004 3.4     1.0001 4.23     1.0003 4.07     0.5002 3.9  19.2 96.1  0.2001 7.68  46.1 92.3  0.1002 16.76 21.08 78.8 78.9 3.09 0.1003 19.55     0.1001 23.97     0.10 24.04     0.05 27.64  144.7 72.4  0.0101 37.32  620.6 62.7  1Conc.: Concentration     2STD: Standard deviation, n= 4    169  Table C.4.9 Experimental data of phenanthrene for DDAB-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  DDAB-MC             2.0001 0.26  5.0 99.7  1.0004 1.17 1.1675 9.9 98.8 0.09 1.0004 1.32     1.0001 1.09     1.0003 1.09     0.5002 1.73  19.6 98.3  0.2001 4.15  47.9 95.9  0.1002 8.42 9.2525 90.6 90.7 0.58 0.1003 9.06     0.1001 9.95     0.10 9.58     0.05 16.57  166.9 83.4  0.0101 41.6  578.2 58.4  1Conc.: Concentration     2STD: Standard deviation, n= 4   170  Table C.4. 10 Experimental data of pyrene for DDAB-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R% STD2  DDAB-MC             2.0001 0.19  5.0 99.8  1.0004 0.31 0.31 10.0 99.7 0.04 1.0004 0.38     1.0001 0.27     1.0003 0.28     0.5002 0.4  19.9 99.6  0.2001 0.89  49.5 99.1  0.1002 2.03 2.2475 97.6 97.8 0.24 0.1003 1.99     0.1001 2.52     0.10 2.45     0.05 4.55  190.9 95.5  0.0101 29.16  701.4 70.8  1Conc.: Concentration     2STD: Standard deviation, n= 4   171  Table C.4.11 Experimental data of anthracene for HDTMA-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5 and sorption time of 24 hour with initial concentration of 50 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal% R%  STD2   HDTMA-MC        2.0003 0.77  2.5 98.5  1.0009 2.73 2.47 4.8 95.1 0.19 1.0009 2.38     1.0008 2.29     0.5003 3.35  9.3 93.3  0.2005 6.75  21.6 86.5  0.1007 10.23 11.40 38.5 77.2 0.84 0.1002 11.77     0.1002 12.19     0.0501 18.01  63.9 64.0  0.0101 24.8  249.5 50.4  1Conc.: Concentration     2STD: Standard deviation, n= 3  Table C.4.12 Experimental data of fluoranthene for HDTMA-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5 and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2      HDTMA-MC         2.0003 1.31  4.9 98.7  1.0009 3.45 2.94 9.7 97.1 0.40 1.0009 2.91     1.0008 2.47     0.5003 3.28  19.3 96.7  0.2005 6.46  46.7 93.5  0.1007 11.32 12.43 2.3 87.6 1.17 0.1002 11.92     0.1002 14.05     0.0501 23.12  153.5 76.9  0.0101 63.09  365.4 36.9  1Conc.: Concentration     2STD: Standard deviation, n= 3  172  Table C.4.13 Experimental data of fluorene for HDTMA-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH value of 6.5 and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2      HDTMA-MC        2.0003 3.9  4.8 96.1  1.0009 18.65 16.15 8.4 83.8 1.92 1.0009 15.84     1.0008 13.97     0.5003 17.62  16.5 82.4  0.2005 30.01  34.9 70.0  0.1007 36.62 41.38 58.4 58.6 3.42 0.1002 44.49     0.1002 43.02     0.0501 62.27  75.3 37.7  0.0101 65.91  337.5 34.1  1Conc.: Concentration     2STD: Standard deviation, n= 3  Table C.4.14 Experimental data of phenanthrene for HDTMA-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH 6.5 and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2   HDTMA-MC           2.0003 2.35  4.9 97.7  1.0009 7.52 6.54 9.3 93.5 0.83 1.0009 6.6     1.0008 5.49     0.5003 8.65  18.3 91.4  0.2005 16.28  41.8 83.7  0.1007 23.93 27.42 72.3 72.6 2.52 0.1002 28.57     0.1002 29.77     0.0501 45.43  108.9 54.6  0.0101 74.37  253.8 25.6  1Conc.: Concentration     2STD: Standard deviation, n= 3  173  Table C.4.15 Experimental data of pyrene for HDTMA-MC adsorbent at different amounts to 100 mL of mixed PAHs solution sorption ratio at room temperature, pH 6.5 and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents    Dosage (g) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) Removal  R%  STD2     HDTAM-MC        2.0003 0.92  5.0 99.1  1.0009 3.01 2.60 9.7 97.4 0.20 1.0009 2.6     1.0008 2.2     0.5003 2.98  19.4 97.0  0.2005 6.4  46.7 93.6  0.1007 11.77 13.13 0.7 86.9 1.51 0.1002 12.3     0.1002 15.33     0.0501 24.23  151.2 75.8  0.0101 63.49  361.5 36.5  1Conc.: Concentration     2STD: Standard deviation, n= 3     174  C.5 PAH Adsorption Capacity of Adsorbents  Table C.5.1 Experimental data for repeated mixture sorption test of anthracene with CPC-MC for PAHs solution for 24 hours with 0.1007 g to 100 mL ratio at room temperature with initial concentration of 50 µg/L  No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) 1st  7.46 42.2 85.1 42.2 2nd  14.14 35.6 71.7 77.9 3rd  12.6 37.1 74.8 115.0 4th  15.65 34.1 68.7 149.1 5th  13.45 36.3 73.1 185.4 6th  12.64 37.1 74.7 222.5 7th  11.83 37.9 76.3 260.4 8th  15.88 33.9 68.2 294.3 9th  15.17 34.6 69.7 328.9 10th  17.48 32.3 65.0 361.2 11th  33.24  394.4 12th  32.87  427.3 13th  16.05 33.7 67.9 461.0 14th  32.13  493.1 15th  31.76  524.9 16th  18.3 31.5 63.4 556.4 17th  31.16  587.6 18th  30.8  618.4 19th  30.44  648.8 20th 20.87 28.9 58.3 677.7 21th  19.44 30.3 61.1 708.1 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    175  Table C.5.2 Experimental data for repeated mixture sorption test of fluoranthene with CPC-MC for PAHs solution for 24 hours with 0.1007 g to 100 mL ratio at room temperature with initial concentration of 100 µg/L   No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) 1st  6.32 93.0 93.7 93.0 2nd  13.86 85.5 86.1 178.6 3rd  13.48 85.9 86.5 264.5 4th  18.59 80.8 81.4 345.3 5th  22.08 77.4 77.9 422.7 6th  29.7 69.8 70.3 492.5 7th  27.23 72.3 72.8 564.8 8th  40.94 58.6 59.1 623.4 9th  34.37 65.2 65.6 688.6 10th  41.01 58.6 59.0 747.2 11th  61  808.2 12th  59.82  868.0 13th  38.47 61.1 61.5 929.1 14th  57.46  986.6 15th  56.28  1042.9 16th  43.05 56.6 57.0 1098.4 17th  53.92  1152.3 18th  52.74  1205.0 19th  51.56  1256.6 20th  53.28 46.4 46.7 1303.3 21th  47.55 52.1 52.5 1355.4 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    176  Table C.5.3 Experimental data for repeated mixture sorption test of fluorene on CPC-MC for PAHs solution for 24 hours with 0.1007 g to 100 mL ratio at room temperature with initial concentration of 100 µg/L    No. of Sorption   Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) 1st  33.69 65.8 66.3 65.8 2nd  45.17 54.4 54.8 120.3 3rd  53.87 45.8 46.1 166.1 4th  74.64 25.2 25.4 191.3 5th  70.37 29.4 29.6 220.7 6th  75.19 24.6 24.8 245.4 7th  65.42 34.3 34.6 279.7 8th  82.18 17.7 17.8 297.4 9th  73.48 26.3 26.5 323.7 10th  69.87 29.9 30.1 353.6 11th  35.4  389.0 12th  39.54  428.6 13th  47.36 52.3 52.6 480.9 14th  47.82  528.7 15th  51.96  580.7 16th  53.15 46.5 46.9 627.2 17th  60.24  687.4 18th  64.38  751.8 19th  68.52  820.3 20th  21.66 77.8 78.3 898.1 21th  24.31 75.2 75.7 973.3 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    177  Table C.5. 4 Experimental data for repeated mixture sorption test of phenanthrene with CPC-MC for PAHs solution for 24 hours with 0.1007 g to 100 mL Ratio at room temperature with initial concentration of 100 µg/L No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) 1st  20.16 79.3 79.8 79.3 2nd  31.59 67.9 68.4 147.2 3rd  37.51 62.1 62.5 209.3 4th  50.18 49.5 49.8 258.7 5th  53.07 46.6 46.9 305.4 6th  61.45 38.3 38.6 343.6 7th  64.08 35.7 35.9 379.3 8th  76.08 23.8 23.9 403.1 9th  72.3 27.5 27.7 430.6 10th  78.68 21.2 21.3 451.7 11th   27.4  479.1 12th   29.02  508.2 13th  64.51 35.2 35.5 543.4 14th   32.28  575.6 15th   33.91  609.6 16th  69.72 30.1 30.3 639.7 17th   37.17  676.8 18th   38.8  715.6 19th   40.4  756.1 20th  57.87 41.8 42.1 797.9 21th  53.85 45.8 46.2 843.7 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    178  Table C.5.5 Experimental data for repeated mixture sorption test of pyrene with CPC-MC for PAHs solution for 24 hours with 0.1007 g to 100 mL ratio at room temperature with initial concentration of 100 µg/L    No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) 1st  6.57 92.8 93.4 92.8 2nd  14.49 84.9 85.5 177.7 3rd  13.97 85.4 86.0 263.1 4th  19.14 80.3 80.9 343.4 5th  21.91 77.5 78.1 421.0 6th  29.47 70.0 70.5 491.0 7th  27.95 71.5 72.1 562.6 8th  41.35 58.2 58.7 620.8 9th  35.22 64.3 64.8 685.1 10th  42.63 57.0 57.4 742.1 11th  59.88  802.0 12th  58.81  860.8 13th  39.79 59.8 60.2 920.6 14th  56.67  977.3 15th  55.6  1032.9 16th  44.66 55.0 55.3 1087.9 17th  53.46  1141.3 18th  52.39  1193.7 19th  51.32  1245.0 20th  53.85 45.8 46.2 1290.8 21th  47.25 52.4 52.8 1343.2 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    179  Table C.5.6 Experimental data for 21 successive mixture sorption test of anthracene with DDAB-MC for PAHs solution with initial concentration of a 50 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature  No. of  Sorption  Equilibrated Conc.* Ce (µg/L) Average Conc. Ce µg/L) Average Adsorptivity  qe (µg/g) Removal % R% Accumulation (µg/g) STD**  1st 3.84 3.75 46.2 92.5 46.2 0.09 3.66      2nd 13.56 13.76 36.2 72.5 82.3 0.20 13.96      3rd 10.56 10.98 38.9 78.0 121.3 0.42 11.4      4th 15.09 15.38 34.6 69.3 155.8 0.29 15.66      5th 14.18 14.67 35.3 70.7 191.1 0.49 15.16      6th 13.31 15.02 34.9 70.0 226.0 1.71 16.73      7th 12.25 12.89 37.0 74.2 263.0 0.64 13.52      8th 15.31 14.90 35.0 70.2 298.1 0.41 14.49      9th 14.65 15.17 34.8 69.7 332.8 0.52 15.69      10th 14.26 14.24 35.7 71.5 368.5 0.02 14.21      11th   33.03  403.5  12th   34.61  438.2  13th 15.9 16.17 33.8 67.7 472.0 0.27 16.44      14th   33.77  505.7  15th   33.35  539.1  16th 16.51 16.75 33.2 66.5 572.3 0.24 16.99      17th   32.78  605.1  18th   32.92  638.0  19th   33.06  671.0  20th 17.89 19.25 30.7 61.5 701.7 1.36 20.6      180  No. of  Sorption  Equilibrated Conc.* Ce (µg/L) Average Conc. Ce µg/L) Average Adsorptivity  qe (µg/g) Removal % R% Accumulation (µg/g) STD**  21th 15.58 14.51 35.4 71.0 737.1 1.08 13.43      *Conc.: concentration    **STD: standard deviation, n=2 Bold black number: using interpolation method to calculate adsorption capacity   Table C. 5. 7 Experimental data for 21 successive mixture sorption test of fluoranthene with DDAB-MC for PAHs solution with initial concentration of a 100 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature  No. of Sorption   Equilibrated Conc.* Ce (µg/L) Average Conc. Ce (µg/L) Average Adsorptivity qe (µg/g)  Removal % R%  Accumulation (µg/g)  STD**   1st  2.18 2.2 97.6 97.8 97.6 0.0 2.22      2nd  15.55 15.76 84.1 84.2 181.7 0.2 15.96      3rd  8.19 9.23 90.6 90.8 272.3 1.0 10.26      4th  11.71 13.11 86.7 86.9 359.0 1.4 14.5      5th  15.74 16.76 83.1 83.2 442.1 1.0 17.78      6th  17.39 19.45 80.4 80.6 522.5 2.1 21.51      7th  16.64 19.15 80.7 80.9 603.1 2.5 21.66      8th  32.9 27.52 72.3 72.5 675.5 5.4 22.14      9th  25.57 28.25 71.6 71.8 747.1 2.7 30.93      10th  21.22 24.61 75.2 75.4 822.3 3.4 27.99      11th   75.02  897.35  12th   74.07  971.43  13th  24.74 27.02 72.8 73.0 1044.23 2.3 29.3      14th   72.08  1116.31  181  No. of Sorption   Equilibrated Conc.* Ce (µg/L) Average Conc. Ce (µg/L) Average Adsorptivity qe (µg/g)  Removal % R%  Accumulation (µg/g)  STD**   15th   71.02  1187.32  16th  29.57 31.67 68.2 68.3 1255.52 2.1 33.77      17th   68.78  1324.30  18th   67.6  1391.90  19th   66.38  1458.27  20th  34.22 36.40 63.5 63.6 1521.77 2.2 38.57      21th  34.29 38.20 61.7 61.8 1583.47 3.9 42.1      *Conc.: concentration    **STD: standard deviation, n=2 Bold black number: using interpolation method to calculate adsorption capacity  Table C.5. 8 Experimental data for 21 successive sorption test of fluorene with DDAB-MC for PAHs solution with initial concentration of a 100 µg/L in 24 hours with 0.1002 g to 100 mL Ratio at room temperature    No. of Sorption  Equilibrated Conc.* Ce (µg/L) Average Conc. Ce (µg/L) Average Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) STD**  1st  23.97 24.005 75.8 76.0 75.8 0.035 24.04      2nd  41.42 42.24 57.6 57.8 133.5 0.82 43.06      3rd  49.42 47.91 52.0 52.1 185.5 1.51 46.4      4th  68.53 68.61 31.3 31.4 216.8 0.08 68.69      5th  68.49 68.085 31.9 31.9 248.7 0.40 67.68      6th  70.77 71.945 28.0 28.1 276.7 1.17 73.12      7th  54.36 52.68 47.2 47.3 323.9 1.68 51      8th  70.41 71.975 28.0 28.0 351.8 1.56 73.54      9th  77.11 75.31 24.6 24.7 376.5 1.8 73.51      182  No. of Sorption  Equilibrated Conc.* Ce (µg/L) Average Conc. Ce (µg/L) Average Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) STD**  10th  50.79 50.79 49.1 49.2 425.6  11th   56.28  481.88  12th   58.66  540.55  13th  53.21 46.275 53.6 53.7 594.15 6.93 39.34      14th   60.42  654.57  15th   59.8  714.37  16th  58.39 51.47 48.4 48.5 762.77 6.92 44.55      17th   51.15  813.92  18th   55.22  869.44  19th   59.89  929.33  20th  37.16 44.095 55.8 55.9 985.13 6.93 51.03      21th  34.14 24.52 75.3 75.5 1060.43 9.62 14.9      *Conc.: concentration    **STD: standard deviation, n=2 Bold black number: using interpolation method to calculate adsorption capacity   Table C. 5. 9 Experimental data for 21 successive mixture sorption test of phenanthrene with DDAB-MC for PAHs solution with initial concentration of a 100 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature   No. of Sorption  Equilibrated Conc.* Ce (µg/L) Average Conc. Ce (µg/L) Average Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) STD**  1st  9.95 9.765 90.1 90.2 90.1 0.19 9.58      2nd  25.52 24.93 74.9 75.1 165.0 0.60 24.33      3rd  26.3 26.33 73.5 73.7 238.5 0.03 26.35      4th  34.85 34.98 64.9 65.0 303.4 0.13 35.11      5th  40.78 41.06 58.8 58.9 362.2 0.27 183  No. of Sorption  Equilibrated Conc.* Ce (µg/L) Average Conc. Ce (µg/L) Average Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) STD**  41.33      6th  45.49 46.99 52.9 53.0 415.1 1.50 48.48      7th  47.78 48.38 51.5 51.6 466.7 0.59 48.97      8th  59.87 57.75 42.2 42.3 508.8 2.12 55.63      9th  61.69 62.66 37.3 37.3 546.1 0.97 63.62      10th  54.9 46.42 53.5 53.6 599.6 8.48 37.94      11th   49.97  649.54  12th   46.95  696.49  13th  56.93 56.97 42.9 43.0 739.39 0.04 57      14th   40.91  780.30  15th   37.89  818.19  16th  67.85 64.58 35.3 35.4 852.72 3.27 61.31      17th   36.32  889.04  18th   39.13  928.17  19th   41.43  969.60  20th  58.37 62.89 37.0 37.1 1006.60 4.52 67.41      21th  52.87 49.48 50.4 50.5 1057.00 3.40 46.08      *Conc.: concentration    **STD: standard deviation, n=2 Bold black number: using interpolation method to calculate adsorption capacity    184  Table C.5. 10 Experimental data for 21 successive mixture sorption test of pyrene with DDAB-MC for PAHs solution with initial concentration of a 100 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature     No. of Sorption   Equilibrated Conc.* Ce (µg/L) Average Conc. Ce (µg/L) Average Adsorptivity qe (µg/g)  Removal% R%  Accumulation (µg/g)  STD**   1st  2.52 2.485 97.3 97.5 97.3 0.035 2.45      2nd  17.08 17.48 82.4 82.5 179.7 0.395 17.87      3rd  8.8 9.90 89.9 90.1 269.6 1.1 11      4th  12.79 14.11 85.7 85.9 355.3 1.31 15.42      5th  15.62 16.63 83.2 83.4 438.5 1.01 17.64      6th  17.25 19.30 80.5 80.7 519.1 2.05 21.35      7th  17.2 19.77 80.1 80.2 599.1 2.56 22.33      8th  33.11 28.04 71.8 72.0 671.0 5.07 22.96      9th  26.47 29.13 70.7 70.9 741.7 2.65 31.78      10th  22.74 26.16 73.7 73.8 815.4 3.415 29.57      11th   73.43  888.8  12th   72.58  961.4  13th  25.85 27.81 72.0 72.2 1033.4 1.96 29.77      14th   70.64  1104.0  15th   69.55  1173.6  16th  30.27 32.86 67.0 67.1 1240.6 2.58 35.44      17th   67.13  1307.7  18th   65.8  1373.5  19th   64.39  1437.9  185  No. of Sorption   Equilibrated Conc.* Ce (µg/L) Average Conc. Ce (µg/L) Average Adsorptivity qe (µg/g)  Removal% R%  Accumulation (µg/g)  STD**   20th  35.51 37.42 62.5 62.6 1500.4 1.91 39.33      21th  36.48 39.74 60.1 60.3 1560.5 3.25 42.99      *Conc.: concentration     **STD: standard deviation, n=2 Bold black number: using interpolation method to calculate adsorption capacity   Table C.5. 11 Experimental data for 21 successive mixture sorption test of anthracene with HDTMA-MC for PAHs solution with initial concentration of a 50 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature     No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal % R% Accumulation  (µg/g) 1st  12.19 37.7 75.6 37.7 2nd  19.65 30.3 60.7 68.0 3rd  19.28 30.7 61.4 98.7 4th  17.86 31.9 64.3 130.6 5th  33.94  164.54 6th  13.78 36.0 72.4 200.54 7th  12.06 37.7 75.9 238.24 8th  13.67 36.1 72.7 274.34 9th  35.93  310.27 10th  13.97 35.8 72.1 346.07 11th  16.25 33.5 67.5 379.57 12th  34.4  413.97 13th  14.46 35.3 71.1 449.27 14th  37.96  487.23 15th  37.1  524.33 16th  11.77 38.0 76.5 562.33 17th  39.69  602.02 18th  40.01  642.03 19th  38.93  680.96 20th  13.31 36.4 73.4 717.36 21th  17.22 32.6 65.6 749.96 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    186   Table C.5. 12 Experimental data for 21 successive mixture sorption test of fluoranthene with HDTMA-MC for PAHs solution with initial concentration of a 100 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature    No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal % R% Accumulation  (µg/g) 1st  14.05 85.8 86.0 85.8 2nd  24.73 75.1 75.3 160.9 3rd  25.34 74.5 74.7 235.4 4th  23.91 75.6 76.1 311.0 5th  72.5  383.5 6th  30.07 69.4 69.9 452.9 7th  38.3 61.3 61.7 514.2 8th  35.72 63.8 64.3 578 9th  63.54  641.54 10th  36.3 63.3 63.7 704.84 11th  41.12 58.5 58.9 763.34 12th  60.4  823.74 13th  37.28 62.3 62.7 886.04 14th  57.4  943.44 15th  55.9  999.34 16th  44 55.6 56.0 1054.94 17th  52.9  1107.84 18th  51.3  1159.14 19th  49.8  1208.94 20th  49.62 50.0 50.4 1258.94 21th  55.87 43.8 44.1 1302.74 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity     187  Table C.5. 13 Experimental data for 21 successive mixture sorption test of fluorene with HDTMA-MC for PAHs solution with initial concentration of a 100 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature    No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal % R% Accumulation  (µg/g) 1st  43.02 56.9 57.0 56.9 2nd  54.16 45.7 45.8 102.6 3rd  54.73 45.2 45.3 147.8 4th  70.35 29.4 29.7 177.2 5th   30.32  207.52 6th  68.58 31.2 31.4 238.72 7th  69.77 30.0 30.2 268.72 8th  28.95 70.6 71.1 339.32 9th   58.23  397.55 10th  53.78 45.9 46.2 443.45 11th  47.29 52.3 52.7 495.75 12th   55.0  550.75 13th  43.16 56.4 56.8 607.15 14th   63.7  670.85 15th   68.1  738.95 16th  25.82 73.7 74.2 812.65 17th   71.63  884.28 18th   69.17  953.45 19th   66.71  1020.16 20th  32.84 66.7 67.2 1086.86 21th  39.63 60.0 60.4 1146.86 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    188  Table C.5. 14 Experimental data for 21 successive mixture sorption test of phenanthrene with HDTMA-MC for PAHs solution with initial concentration of a 100 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature    No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) 1st  29.77 70.1 70.2 70.1 2nd  43.8 56.1 56.2 126.2 3rd  46.51 53.4 53.5 179.6 4th  48.5 51.1 51.5 230.7 5th  46.06  276.76 6th  58.73 41.0 41.3 317.76 7th  68.62 31.2 31.4 348.96 8th  51.76 47.9 48.2 396.86 9th   43.15  440.01 10th  61.33 38.4 38.7 478.41 11th  60.14 39.6 39.9 518.01 12th   42.7  560.71 13th  53.71 46.0 46.3 606.71 14th   47.63  654.34 15th   49.5  703.84 16th  49.41 50.2 50.6 754.04 17th   50.24  804.28 18th   49.11  853.39 19th   46.98  900.37 20th  51.31 48.4 48.7 948.77 21th  59.95 39.8 40.1 988.57 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    189   Table C.5. 15 Experimental data for 21 successive mixture sorption test of pyrene with HDTMA-MC for PAHs solution with initial concentration of a 100 µg/L for 24 hours with 0.1002 g to 100 mL ratio at room temperature     No. of Sorption    Equilibrated Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% Accumulation  (µg/g) 1st 15.33 84.5 84.7 84.5 2nd 26.55 73.3 73.5 157.8 3rd 27.35 72.5 72.7 230.3 4th 25.86 73.6 74.1 303.9 5th  71.65  375.55 6th 29.84 69.7 70.2 445.25 7th 39.62 60.0 60.4 505.25 8th 37.73 61.8 62.3 567.05 9th  61.76  628.81 10th 37.88 61.7 62.1 690.51 11th 42.75 56.9 57.3 747.41 12th  58.6  806.01 13th 39.04 60.5 61.0 866.51 14th  55.6  922.11 15th  54.1  976.21 16th 45.93 53.7 54.1 1029.91 17th  51  1080.91 18th  49.5  1130.41 19th  48  1178.41 20th 50.97 48.7 49.0 1227.11 21th 57.46 42.2 42.5 1269.31 *Conc.: concentration Bold black number: using interpolation method to calculate adsorption capacity    190  C.6 Stability of Loaded PAHs from Adsorbents Table C.6 Experimental data for PAHs leachability test for modified clinoptilolites after 21 time repeated sorption tests for 24 hours with 0.1007 g of CPC-MC and 0.1002 g of DDAB-MC and HDTMA-MC to 100 mL deionized water ratio at pH 6.5 and room temperature     Adsorbents    D.W.*  Solution  Conc.** Co (µg/L) Equilibrated  Conc. Ce (µg/L) Average  Conc. Ce (µg/L) Average  Adsorptivity,  qe (µg/g) STD***  Anthracene   CPC-MC 0 12.42 12.3 12.3  DDAB-MC 0 9.23 12.4 12.3 3.1 DDAB-MC 0 15.48    HDTMA-MC 0 10.67  10.6  Fluoranthene   CPC-MC 0 45.44  45.1  DDAB-MC 0 25.59 35.6 35.5 10.0 DDAB-MC 0 45.56    HDTMA-MC 0 42.3  42.2  Fluorene   CPC-MC 0 9.85  9.8  DDAB-MC 0 15.38 26.49 26.4 11.1 DDAB-MC 0 37.59    HDTMA-MC 0 20.14  20.1  Phenanthrene   CPC-MC 0 39.08  38.8  DDAB-MC 0 34.36 48.42 48.3 14.1 DDAB-MC 0 62.48    HDTMA-MC 0 45.19  45.1  Pyrene   CPC-MC 0 45.07  44.8  DDAB-MC 0 25.43 35.04 35.0 9.6 DDAB-MC 0 44.65    HDTMA-MC 0 41.98  41.9  *Deionized water      **Conc.: concentration    ***STD: standard deviation, n=2   191  C.7 Competition Effect of Fluoranthene Table C.7 Experimental data of fluoranthene for different adsorbents at 0.05 g to 100 mL of PAHs mixture or single solution sorption ratio at room temperature, pH 6.5 and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbents   PAH  Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC Single  0.0507 9.64 9.64 178.2 90.4  CPC-MC  Mixture  0.0507 13.24 13.24 171.1 86.8  DDAB-MC Single  0.0502 2.32 2.28  194.9  97.7 0.04 2.24 DDAB-MC  Mixture   0.0503 4.58 3.795 191.5  96.2  0.8 3.01 HDTMA-MC  Single  0.0503 152.2 23.46 152.2 76.5  HDTMA-MC  Mixture  0.0503 152.8 23.12 152.8 76.9  1Conc.: concentration    2STD: standard deviation, n=2   192  C.8 Effect of pH on PAH Adsorptions Table C.8.1 Experimental data of anthracene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 50 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC 3 1.0004 0.51 0.51 4.9 99.0  5.5 1.0006 0.31 0.31 5 99.4  6.5 1.0008 1.09 1.05 4.9 97.9 0.05 1.08 0.97 9 1.0001 0.53 0.53 4.9 98.9  11 1.0003 0.59 0.59 4.9 98.8  HDTMA-MC 3 1.0001 1.49 1.49 4.9 97.0  5.5 1.0005 0.51  4.9 99.0  6.6  2.53 2.40 4.8 95.2 0.1 2.38 2.29 9 1.0008 0.67 0.67 4.9 98.7  11 1.0001 0.78 0.78 4.9 98.4  1Conc.: concentration    2STD: standard deviation, n=3  Table C.8.2 Experimental data of fluoranthene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC 3 1.0004 0.3 0.3 10.0 99.7  5.5 1.0006 0.3 0.3 10.0 99.7  6.5 1.0008 1.02 1.34 9.9 98.7 0.3 1.69 1.3 9 1.0001 0.53 0.25 10.0 99.8  11 1.0003 0.29 0.29 10.0 99.7  HDTMA-MC 3 1.0001 1.33 1.33 9.9 98.7  5.5 1.0005 0.98  9.9 99.0  6.5 1.0009 3.18 2.85 9.7 97.1 0.3 2.91 2.47 9 1.0008 1.04 1.04 9.9 99.0  11 1.0001 0.92 0.92 9.9 99.1  1Conc.: concentration    2STD: standard deviation, n=3 193  Table C.8.3 Experimental data of fluorene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC 3 1.0004 4.45 4.45 9.6 95.6  5.5 1.0006 0.19 0.19 10 99.8  6.5 1.0008 7.17 6.35 9.4 93.7 0.8 5.35 6.52 9 1.0001 2.99 2.99 9.7 97.0  11 1.0003 4.95 4.95 9.5 95.1  HDTMA-MC 3 1.0001 7.07 7.07 9.3 92.9  5.5 1.0005 1.45  9.9 98.6  6.5 1.0009 18.65 16.2 8.4 83.8 1.92 15.84 13.97 9 1.0008 1.69 1.69 9.8 98.3  11 1.0001 4.05 4.05 9.6 96.0  1Conc.: concentration    2STD: standard deviation, n=3  Table C.8. 4 Experimental data of phenanthrene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC 3 1.0004 2.16 2.16 9.8 97.8  5.5 1.0006 0.85  9.9 99.2  6.5 1.0008 2.54 2.91 9.7 97.1 0.3 3.22 2.98 9 1.0001 1.82 1.82 9.8 98.2  11 1.0003 2.2 2.2 9.8 97.8  HDTMA-MC 3 1.0001 4.83 4.83 9.5 95.2  5.5 1.0005 1.39  9.9 98.6  6.5 1.0009 6.94 6.34 9.4 93.7 0.6 6.6 5.49 9 1.0008 2.09 2.09 9.8 97.9  11 1.0001 2.47 2.47 9.8 97.5  1Conc.: concentration    2STD: standard deviation, n=3   194  Table C.8. 5 Experimental data of pyrene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC 3 1.0004 0.31 0.31 10.0 99.7  5.5 1.0006 0.33 0.33 10.0 99.7  6.5 1.0008 0.68 0.93 9.9 99.1 0.24 1.25 0.86 9 1.0001 0.32 0.32 10.0 99.7  11 1.0003 0.29 0.29 10.0 99.7  HDTMA-MC 3 1.0001 1.51 1.51 9.8 98.5  5.5 1.0005 0.97 0.97 9.9 99  6.5 1.0009 2.78 2.53 9.7 97.5 0.2 2.6 2.2 9 1.0008 1.05 1.05 9.9 99.0  11 1.0001 1.02 1.02 9.9 99.0  1Conc.: concentration    2STD: standard deviation, n=3    195  Table C.8. 6 Experimental data of anthracene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 50 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2      DDAB-MC 3 1.0003 0.14 0.18 5.0 99.7 0.04 0.21     5.5 1.0005 0.17 0.14 5.0 99.7 0.03 0.11     6.5 1.0002 0.66 0.66 4.9 98.7 0.01 0.65     9 1.0006 0.17 0.15 5.0 99.7 0.02 0.12     11 1.0005 0.67 0.52 4.9 99.0 0.16 0.36     1Conc.: concentration    2STD: standard deviation, n=2  Table C.8.7 Experimental data of fluoranthene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2     DDAB-MC 3 1.0003 0.08 0.10 10.0 99.9 0.015 0.11     5.5 1.0005 0.08 0.07 10.0 99.9 0.010 0.06     6.5 1.0002 0.64 0.64 9.9 99.4 0.005 0.63     9 1.0006 0.05 0.05 10.0 100.0 0.005 0.04     11 1.0005 0.03 0.1 10.0 99.9 0.070 0.17     1Conc.: concentration    2STD: standard deviation, n=2    196   Table C.8.8 Experimental data of fluorene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2    DDAB-MC 3 1.0003 1.08 1.60 9.8 98.4 0.52 2.11     5.5 1.0005 0.21 0.23 10.0 99.8 0.02 0.24     6.5 1.0002 4.23 4.15 9.6 95.9 0.08 4.07     9 1.0006 0.72 0.43 10.0 99.6 0.29 0.14     11 1.0005 2.41 3.00 9.7 97.0 0.58 3.58     1Conc.: concentration    2STD: standard deviation, n=2  Table C.8.9 Experimental data of phenanthrene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2     DDAB-MC 3 1.0003 0.63 0.77 9.9 99.2 0.145 0.90     5.5 1.0005 0.46 0.40 10.0 99.6 0.06 0.33     6.5 1.0002 1.09 1.09 9.9 98.9 0.00 1.09     9 1.0006 0.22 0.3 10.0 99.7 0.08 0.38     11 1.0005 0.86 1.02 9.9 99.0 0.16 1.18     1Conc.: concentration    2STD: standard deviation, n=2    197  Table C.8. 10 Experimental data of pyrene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at room temperature, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbent   pH Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2     DDAB-MC 3 1.0003 0.12 0.08 9.99 99.9 0.04 0.04     5.5 1.0005 0.12 0.085 9.99 99.9 0.035 0.05     6.5 1.0002 0.27 0.275 9.97 99.7 0.005 0.28     9 1.0006 0.04 0.075 9.99 99.9 0.035 0.11     11 1.0005 0.05 0.1 9.99 99.9 0.05 0.15     1Conc.: concentration    2STD: standard deviation, n=2    198  C.9 Effect of Temperatures on PAH Adsorptions Table C. 9. 1 Experimental data of anthracene for CPC-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 50 µg/L  Adsorbents   Temperature  (℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2   CPC-MC 4 1.0004 0.43 0.40 5.0 99.2 0.04 0.36 20 1.0008 1.09 1.05 4.9 97.9 0.05 1.08 0.97 35 1.0001 1.47 1.43 4.9 97.2 0.05 1.38 1Conc.: concentration    2STD: standard deviation, n=2, or 3  Table C. 9. 2 Experimental data of fluoranthene for CPC-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbents   Temperature  (℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2   CPC-MC 4 1.0004 0.42 0.30 10.0 99.7 0.1 0.18 20 1.0008 1.02 1.34 9.9 98.7 0.3 1.69 1.3 35 1.0001 1.42 1.42 9.9 98.6  1.42 1Conc.: concentration     2STD: standard deviation, n=2, or 3    199  Table C. 9. 3 Experimental data of fluorene for CPC-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L  Adsorbents   Temperature  (℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2    CPC-MC 4 1.0004 3.24 2.89 9.7 97.1 0.4 2.53 20 1.0008 7.17 6.35 9.4 93.7 0.8 5.35 6.52 35 1.0001 11.51 10.22 9.0 89.8 1.3 8.92 1Conc.: concentration     2STD: standard deviation, n=2, or 3  Table C. 9. 4 Experimental data of phenanthrene for CPC-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature  (℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD    CPC-MC 4 1.0004 1.4 1.40 9.9 98.6 0.01 1.39 20 1.0008 2.54 2.91 9.7 97.1 0.3 3.22 2.98 35 1.0001 4.48 4.35 9.6 95.7 0.1 4.21 1Conc.: concentration    2STD: standard deviation, n=2, or 3        200  Table C. 9. 5 Experimental data of pyrene for CPC-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature  (℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2     CPC-MC 4 1.0004 0.22 0.22 10.0 99.8 0.01 0.21 20 1.0008 0.68 0.93 9.9 99.1 0.24 1.25 0.86 35 1.0001 1.12 1.10 9.9 98.9 0.02 1.08 1Conc.: concentration     2STD: standard deviation, n=2, or 3   Table C. 9. 6 Experimental data of anthracene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 50 µg/L Adsorbents   Temperature ℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2     DDAB-MC 4 1.0005 0.38 0.29 5.0 99.4 0.12 0.37 0.13 20 1.0003 0.66 0.53 4.9 98.9 0.13 0.65 0.41 0.39 35 1.0001 0.71 0.70 4.9 98.6 0.02 0.68 1Conc.: concentration     2STD: standard deviation, n=2, 3 or 4        201  Table C. 9. 7 Experimental data of fluoranthene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature ℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2   DDAB-MC 4 1.0005 0.39 0.31 10.0 99.7 0.2 0.54 0.01 20 1.0003 0.63 0.60 9.9 99.4 0.2 0.64 0.32 0.79 35 1.0001 0.82 0.81 9.9 99.2 0.01 0.8 1Conc.: concentration    2STD: standard deviation, n=2, 3 or 4   Table C. 9. 8 Experimental data of fluorene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature ℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2    DDAB-MC 4 1.0005 2.65 2.34 9.8 97.7 0.6 2.850 1.51 20 1.0003 4.23 3.97 9.6 96.0 0.5 4.07 4.46 3.13 35 1.0001 6.87 6.89 9.3 93.1 0.02 6.9 1Conc.: concentration      2STD: standard deviation, n=2, 3 or 4    202  Table C. 9. 9 Experimental data of phenanthrene for DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature ℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2    DDAB-MC 4 1.0005 1.11 0.91 9.9 99.1 0.3 1.17 0.45 20 1.0003 1.09 1.15 9.9 98.8 0.1 1.09 1.21 1.22 35 1.0001 2.07 2.07 9.8 97.9 0 2.07 1Conc.: concentration     2STD: standard deviation, n=2, 3 or 4   Table C. 9. 10 Experimental data of pyrene on DDAB-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature ℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2   DDAB-MC 4 1.0005 0.26 0.11 10.0 99.9 0.1 0.06 0.02 20 1.0003 0.27 0.31 10.0 99.7 0.03 0.28 0.32 0.35 35 1.0001 0.5 0.50 9.9 99.5 0 0.5 1Conc.: concentration    2STD: standard deviation, n=2, 3 or 4    203  Table C. 9. 11 Experimental data of anthracene on HDTMA-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour Adsorbents   Temperature  (℃) Adsorbent (g) Initial Solution Conc.1 Co (µg/L) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2   HDTMA-MC 4 1.0005 50 0.99 1.40 4.9 97.2 0.4 50 1.81 20 1.0009 50 2.53 2.40 4.8 95.2 0.1 50 2.38 50 2.29 35 1.0002 50 2.99 2.99 4.7 94.0  1Conc.: concentration     2STD: standard deviation, n=2, or 3    Table C. 9. 12 Experimental data of fluoranthene on HDTMA-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature  (℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2   HDTMA-MC 4 1.0005 1.78 1.43 9.9 98.6 0.3 1.08 20 1.0009 3.18 2.85 9.7 97.1 0.3 2.91 2.47 35 1.0002 3.13 3.13 9.7 96.9  1Conc.: concentration     2STD: standard deviation, n=2, or 3     204  Table C. 9. 13 Experimental data of fluorene on HDTMA-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature  (℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2   HDTMA-MC 4 1.0005 2.65 6.29 9.4 93.7 3.6 9.92 20 1.0009 17.24 15.68 8.4 84.3 1.3 15.84 13.97 35 1.0002 19.78 19.78 8.0 80.2  1Conc.: concentration     2STD: standard deviation, n=2, or 3    Table C. 9. 14 Experimental data of phenanthrene on HDTMA-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature  (℃) Adsorbent (g) Initial Solution Conc.1 Co (µg/L) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2    HDTMA-MC 4 1.0005 100 2.91 3.50 9.6 96.5 0.6 100 4.08 20 1.0009 100 6.94 6.34 9.4 93.7 0.6 100 6.6 100 5.49 35 1.0002 100 8.06 8.06 9.2 91.9  1Conc.: concentration     2STD: standard deviation, n=2, or 3       205  Table C. 9. 15 Experimental data of pyrene on HDTMA-MC adsorbent at 1 g to 100 mL of mixed PAHs solution sorption ratio at pH 6.5, and sorption time of 24 hour with initial concentration of 100 µg/L Adsorbents   Temperature  (℃) Adsorbent (g) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2   HDTMA-MC 4 1.0005 1.36 1.25 9.9 98.8 0.1 1.13 20 1.0009 2.78 2.53 9.7 97.5 0.2 2.6 2.2 35 1.0002 2.88 2.88 9.7 97.1  1Conc.: concentration     2STD: standard deviation, n=2, or 3     206  C.10 Removal of PAHs from Landfill Leachate  Table C.10.1 Experimental data of anthracene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio in deionized water and landfill leachate at room temperature, and sorption time of 24 hour Adsorbents   Media solution Adsorbent (g) Initial Solution Conc.1 Co (µg/L) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC Deionized water 1.0009 50 1.08 1.025 4.9 98.0 0.1 50 0.97 50 1.09 CPC-MC  Landfill Leachate 1.0003 50.1 1.15 1.08 4.9 97.8 1.08 50.1 1.21 DDAB-MC Deionized water 1.0004 50 0.41 0.4 5.0 99.2 0.4 50 0.39 50 0.66 DDAB-MC Landfill Leachate 1.0005 50.1 0.66 0.515 5.0 99.0 0.05 50.1 0.57 1Conc.: concentration     2STD: standard deviation, n=2, or 3  Table C.10.2 Experimental data of fluoranthene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio in deionized water and landfill leachate at room temperature, and sorption time of 24 hour Adsorbents   Media solution Adsorbent (g) Initial Solution Conc.1 Co (µg/L) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC Deionized water 1.0009 100 1.69 1.495 9.8 98.5 0.2 100 1.3 100 1.02 CPC-MC  Landfill Leachate 1.0003 100.1 1.45 1.43 9.9 98.6 0.1 100.1 1.61 DDAB-MC Deionized water 1.0004 100 0.32 0.555 9.9 99.4 0.2 100 0.79 100 0.63 DDAB-MC Landfill Leachate 1.0005 100.1 0.5 0.38 10.0 99.6 0.02 100.1 0.46 1Conc.: concentration     2STD: standard deviation, n=2, or 3  207  Table C.10.3 Experimental data of fluorene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio in deionized water and landfill leachate at room temperature, and sorption time of 24 hour Adsorbents   Media solution Adsorbent (g) Initial Solution Conc.1 Co (µg/L) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC Deionized water 1.0009 100 5.35 5.935 9.4 94.1 0.6 100 6.52 100 7.17 CPC-MC  Landfill Leachate 1.0003 100.5 4.73 4.335 9.6 95.7 0.1 100.5 4.94 DDAB-MC Deionized water 1.0004 100 4.46 3.795 9.6 96.2 0.7 100 3.13 100 4.23 DDAB-MC Landfill Leachate 1.0005 100.5 2.41 2.06 9.8 98.0 0.2 100.5 2.71 1Conc.: concentration     2STD: standard deviation, n=2, or 3   Table C.10.4 Experimental data of phenanthrene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio in deionized water and landfill leachate at room temperature, and sorption time of 24 hour Adsorbents   Media solution Adsorbent (g) Initial Solution Conc.1 Co (µg/L) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC Deionized water 1.0009 100 3.22 3.1 9.7 96.9 0.1 100 2.98 100 2.54 CPC-MC  Landfill Leachate 1.0003 100.4 3.18 2.86 9.8 97.2 0.1 100.4 3.33 DDAB-MC Deionized water 1.0004 100 1.21 1.215 9.9 98.8 0.01 100 1.22 100 1.09 DDAB-MC Landfill Leachate 1.0005 100.4 1.41 1 9.9 99.0 0.01 100.4 1.39 1Conc.: concentration     2STD: standard deviation, n=2, or 3   208  Table C.10.5 Experimental data of pyrene for different adsorbents at 1 g to 100 mL of mixed PAHs solution sorption ratio in deionized water and landfill leachate at room temperature, and sorption time of 24 hour  Adsorbents   Media solution Adsorbent (g) Initial Solution Conc.1 Co (µg/L) Equilibrated Conc. Ce (µg/L) Average Conc. Ce (µg/L) Adsorptivity qe (µg/g) Removal% R% STD2 CPC-MC Deionized water 1.0009 100 1.25 1.055 9.9 98.9 0.2 100 0.86 100 0.68 CPC-MC  Landfill Leachate 1.0003 100.07 1.44 1.455 9.9 98.5 0.1 100.07 1.61 DDAB-MC Deionized water 1.0004 100 0.32 0.335 10.0 99.7 0.02 100 0.35 100 0.27 DDAB-MC Landfill Leachate 1.0005 100.07 0.49 0.415 10.0 99.6 0.01 100.07 0.48 1Conc.: concentration     2STD: standard deviation, n=2, or 3     209  Appendix D   Equations D.1 Coulomb's Law  Based on Coulomb's law as discussed by Berg, et al. (2007), the energy of electrostatic interaction is as follows: 𝐸𝐸 = 𝐾𝐾𝐾𝐾1𝐾𝐾2𝐷𝐷×𝑟𝑟       (1)  E is energy between the two objects; q1 is the charge on the clinoptilolite (e: 1.602×10−19 coulombs); q2 is the charge on the nitrogen of surfactant; D is the dielectric constant; r is the distance between the two atoms (Ao); K is a proportionality constant (k = 332 kcal/mole, or 1389 kJ/mole). D.2 Thermodynamic Sorption Properties  To elevate the effect of temperature on PAHs adsorption on adsorbent, the Van’t Hoff equation is used (Gupta and Gupta 2016; Zhang et al. 2014) .  𝑘𝑘𝑑𝑑 = 𝐾𝐾𝑒𝑒𝐶𝐶𝑒𝑒       (2)  ∆𝐺𝐺ᵒ = −𝑅𝑅𝑆𝑆𝑅𝑅𝑅𝑅(𝑘𝑘𝑑𝑑)    (3)  ln(𝑘𝑘𝑑𝑑 ) = ∆𝑆𝑆°𝑅𝑅 − ∆𝐻𝐻°𝑅𝑅𝑅𝑅     (4) Kd is the adsorption-desorption distribution coefficient; Ce is the surfactant concentration at equilibrium (mg/L); qe is the amount of cationic surfactant adsorbed at the equilibrium (mg/g).  R is the universal gas constant (8.314 J/molK); T is the absolute temperature (K); ΔG° is the free energy of adsorption (kJ/mol); ∆𝐻𝐻° is enthalpy (kJ/mol); ΔS° is entropy change.  210  

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