DOKUZ EYLÜL UNIVERSITY
GRADUATE SCHOOL OF NATURAL AND APPLIED
SCIENCES
EFFECT OF SONICATION ON THE
TREATMENT OF TOXIC AND REFRACTORY
INDUSTRIAL WASTEWATERS
by
Rukiye ÖZTEKĐN
January, 2011
TREATMENT OF TOXIC AND REFRACTORY
INDUSTRIAL WASTEWATERS
A Thesis Submitted to the
Graduate School of Natural and Applied Sciences of Dokuz Eylül University In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Environmental Engineering, Environmental Science Program
by
Rukiye ÖZTEKĐN
January, 2011 ĐZMĐR
ii
Ph.D. THESIS EXAMINATION RESULT FORM
We have read the thesis entitled “EFFECT OF SONICATION ON THE
TREATMENT OF TOXIC AND REFRACTORY INDUSTRIAL
WASTEWATERS” completed by RUKĐYE ÖZTEKĐN under supervision of PROF. DR. DELĐA TERESA SPONZA and we certify that in our opinion it is fully adequate, in scope and in quality, as a thesis for the degree of Doctor of Philosophy.
Prof. Dr. Delia Teresa SPONZA
Supervisor
Prof. Dr. Mustafa ODABAŞI Prof. Dr. Nuri AZBAR
Thesis Committee Member Thesis Committee Member
Prof. Dr. F. Gülen E. ĐSKENDER Prof. Dr. Ayşegül PALA
Examining Committee Member Examining Committee Member
Prof. Dr. Mustafa SABUNCU Director
iii
ACKNOWLEDGEMENTS
The author greatly acknowledges the great efforts of Prof. Dr. Delia Teresa SPONZA, the author’s supervisor at this Ph.D. thesis, for her self-sacrificing helps, for continuous supervision, for always positive to boost morale, efforts for introduce the author to the World of International Science, for her great patient against all problems of the author, for her intelligently approachs to this Ph.D. thesis, for her valuable knowledges to share the author preparation of this Ph.D. thesis for valuable helps. It has been always an honor and privilege for the author to work with her.
The author wish to thanks Prof. Dr. Nuri AZBAR, Prof. Dr. Fatma Gülen EREMEKTAR ĐSKENDER, Prof. Dr. Mustafa ODABAŞI and Prof. Dr. Ayşegül PALA are this Ph.D. Thesis Examining Committee Members. It has been always an honor and privilege for the author to work with their.
This Ph.D. thesis was executed the research activities in Environmental Microbiology Laboratories at Dokuz Eylül University, Engineering Faculty, Environmental Engineering Department, Izmir-Turkey.
The author especially would like to thanks to her family for their love, for their encouragement, for always positive to boost morale, for their sincere efforts, for they always to be resolute in any case, for their spiritual supports, for their financial supports and for their great self-sacrifice in this Ph.D. thesis. It has been always an honor and privilege for the author come to exist an individual in this family. Therefore, the author would like to dedicate this Ph.D. thesis to her family and especially to her father, Muharrem ÖZTEKĐN.
iv
EFFECT OF SONICATION ON THE TREATMENT OF TOXIC AND REFRACTORY INDUSTRIAL WASTEWATERS
ABSTRACT
In the framework of this Ph.D. thesis, the treatability of toxic and refractory compounds in petrochemical (PCI), in olive mill (OMI) and in textile (TI) industry real wastewaters (wws) were investigated with sonication alone and with some additives. Sonication alone provided 96.90% PAHs, 92.48% CODdis, 94.23% TOC in PCI ww after 150 min, at 60oC, at 640 W, at 35 kHz, at 90.54 W/cm2, respectively. With only sonication 83.77% color, 61.24% phenol and 70.52% TAAs yields were observed in OMI ww while 84.92% CODdis, 83.22% TOC, 87.66% color removals were detected in TI ww for the operational conditions given above. The maximum removal efficiencies for PAHs, CODdis were 99.68%, 99.68% at NaCl=15.00 g/l, respectively, in PCI ww. The maximum removals for CODdis, color, phenol, TAAs, TFAs were 93.93%, 96.09%, 94.44%, 91.58%, 90.30% at TiO2=20.00 mg/l, at NaCl=15.00 g/l, at TiO2=20.00 mg/l, at DO=10.00 mg/l and at H2O2=2000 mg/l, respectively, in OMI ww. The maximum yields for CODdis, color, TAAs were 99.37%, 97.65%, 80.16%, at Fe+3=50.00 mg/l, at DO=10.00 mg/l, at H2O2=2000 mg/l, respectively, in TI ww.
The kinetic studies results showed that all the pollutant parameters in PCI, OMI, TI wws are sonodegraded according to the pseudo first order reaction kinetic both with only sonication and with some additives. Higher than 90.00% acute toxicity removals in PCI, OMI, TI wws were measured with Microtox (Photobacterium phosphoreum) and Daphnia magna (water flea) test organisms for the same operational conditions mentioned above. 201555.82 TL/year total cost, 0.03, 3.12 and 3.32 kWh / kg CODdis specific energies are required for sonodegradation of OMI, PCI, TI wws, respectively, with only sonication. Total costs and specific energy values were lower than other AOPs. The results of this study showed that
v
sonication can be used effectively to treat the toxic and refractory compounds in PCI, OMI, TI wws.
Keywords: Acute toxicity, ANOVA statistical analysis, color, cost analysis, olive mill, petrochemical, phenol, polycyclic aromatic hydrocarbons (PAHs), pseudo first order reaction kinetic, sonication, specific energy, textile, total aromatic amines (TAAs), total fatty acids (TFAs).
vi
SES DALGALARININ TOKSĐK VE ZOR AYRIŞABĐLEN ENDÜSTRĐYEL ATIKSULARIN ARITIMINA ETKĐSĐ
ÖZ
Bu doktora tezi kapsamında, petrokimya (PEA), zeytin altı (ZEA) ve tekstil endüstrisi (TEA) gerçek atıksularındaki toksik ve zor ayrışabilen bileşiklerin arıtılabilirliği tek başına sonikasyon prosesi ve bazı kimyasal maddelerin ilavesiyle incelenmiştir. Tek başına sonikasyon prosesi ile PEA’da 150 dakika sonikasyon süresi sonunda, 60oC’de, 640 W’lık bir güçte, 35 kHz’lik bir frekansta ve 90.54 W/cm2 ’lik bir sonikasyon şiddetinde %96.90 poliaromatik hidrokarbon (PAH), %92.48 KOĐçözünmüş ve %94.23 TOK giderme verimleri elde edilmiştir. Aynı işletme koşullarında tek başına sonikasyonla ZEA’da %83.77 renk, %61.24 fenol, %70.52 toplam aromatik aminler (TAA) giderimleri elde edilmiş, TEA’da ise %84.92 KOĐçözünmüş, %83.22 TOK, %87.66 renk giderim verimleri bulunmuştur. PEA’da, maksimum PAH ve KOĐçözünmüş giderim verimleri 15.00 g/l NaCl’de, sırasıyla, %99.68 ve %99.68 olarak bulunmuştur. ZEA’da maksimum KOĐçözünmüş, renk, fenol, TAA, toplam yağ asitleri (TYA) giderimleri, sırasıyla, %93.93, %96.09, %94.44, %91.58, %90.30 olarak 20.00 mg/l TiO2’de, 15.00 g/l NaCl’de, 20.00 mg/l TiO2’de, 10.00 mg/l çözünmüş oksijen’de ve 2000 mg/l H2O2 konsantrasyonunda bulunmuştur. TEA’da maksimum KOĐçözünmüş, renk, TAA giderimleri, sırasıyla, %99.37, %97.65, %80.16 olup Fe+3=50.00 mg/l’de, çözünmüş oksijen=10.00 mg/l’de ve H2O2=2000 mg/l’de bulunmuştur.
Kinetik çalışmalar PEA, ZEA, TEA atıksularındaki bütün kirletici parametrelerin tek başına sonikasyon prosesi kullanıldığında ve ilave bazı kimyasal maddeler olduğunda yalancı birinci derece reaksiyon kinetiğine göre parçalandığını göstermiştir. %90.00 üzerinde akut toksisite giderimleri, PEA, ZEA, TEA atıksularında Mikrotox (Photobacterium phosphoreum) ve Daphnia magna (su piresi) test organizmalarıyla yukarıda belirtilen aynı işletme koşullarında
vii
ölçülmüştür. 201555.82 TL/yıl toplam maliyet, 0.03, 3.12 ve 3.33 kWh / kg KOĐçözünmüş özgül enerjileri sırasıyla, ZEA, PEA, TEA’da tek başına sonikasyonla hesaplanmıştır. Toplam maliyetler ve özgül enerji değerleri diğer ileri arıtım yöntemlerinden (ĐAY) daha düşüktür. Bu çalışma sonuçları, sonikasyonun, PEA, ZEA, TEA atıksularındaki toksik ve zor ayrışabilen bileşiklerin arıtımında etkili bir şekilde kullanılabileceğini göstermektedir.
Anahtar Kelimeler: Akut toksisite, ANOVA istatistiksel analizi, renk, maliyet analizi, zeytin işleme, petrokimya, fenol, poliaromatik hidrokarbonlar (PAH), yalancı birinci mertebe reaksiyon kinetiği, ses dalgalarıyla arıtım, özgül enerji, tekstil, toplam aromatik aminler (TAA), toplam yağ asitleri (TYA).
viii CONTENTS
Page
THESIS EXAMINATION RESULT FORM... ... ii
ACKNOWLEDGEMENTS... ... iii
ABSTRACT... ... iv
ÖZ…… ... vi
CHAPTER ONE – INTRODUCTION ...1
1.1Introduction... ...1
1.2 The Reasons of this Ph.D. Study ...6
1.3 The Objectives of this Ph.D. Study ...8
CHAPTER TWO – PROPERTIES OF THE WASTEWATER ... 12
2.1 Properties of Petrochemical Industry Wastewater (PCI ww)... 12
2.1.1List of Significant Petrochemicals and their Derivatives... ... 14
2.1.2 Polycyclic Aromatic Hydrocarbons (PAHs)... ... 14
2.1.2.1 Chemical Structures, Properties and Health Effects of PAHs... ... 28
2.1.2.2 Production and Uses of PAHs.... ... 32
2.1.2.2.1 Naphthalene (NAP)... ... 33 2.1.2.2.2 Acenaphthylene (ACL)... 33 2.1.2.2.3 Acenaphthene (ACT)... 33 2.1.2.2.4 Fluorene (FLN)... ... 34 2.1.2.2.5 Phenanthrene (PHE)... ... 34 2.1.2.2.6 Antracene (ANT)... ... 34 2.1.2.2.7 Carbazole (CRB)... ... 35 2.1.2.2.8 Fluoranthene (FL)... ... 35 2.1.2.2.9 Pyrene (PY)... ... 35 2.1.2.2.10 Chrysene (CHR)... ... 36 2.1.2.2.11 Benzo[a]pyrene (BaP)... ... 36 2.1.2.3 Sources of PAHs.. ... 36
ix
2.1.2.3.1 Natural Sources... ... 37
2.1.2.3.2 Anthropogenic Sources... ... 37
2.2 Properties of Olive Mill Industry Wastewater (OMI ww)... ... 38
2.2.1 Phenolic Compounds... 44
2.2.2 Aromatic Amines.. ... 48
2.2.3 Fatty Acids... ... 50
2.2.4 Color... ... 54
2.3 Properties of Textile Industry Wastewater (TI ww)... ... 55
2.3.1 Acid Dyes... ... 55
2.3.2 Cationic (Basic) Dyes... ... 56
2.3.3 Disperse Dyes... ... 56 2.3.4 Direct Dyes... ... 56 2.3.5 Reactive Dyes... ... 56 2.3.6 Solvent Dyes... ... 57 2.3.7 Sulfur Dyes... ... 57 2.3.8 Vat Dyes... ... 57
2.3.9 Metylene Blue (MB) Dyestuff... ... 58
CHAPTER THREE – LITERATURE REVIEW... .... 59
3.1 Sonolysis ... 59
3.1.1 Theory... ... 59
3.1.2 First Mechanism... ... 59
3.1.3 Second Mechanism... ... 60
3.1.4 Third Mechanism... ... 60
3.1.5 Wastewater Treatment by Sonication... ... 62
3.1.5.1 Recent Advances... ... 62
3.1.5.1.1 Catalytic Sonicative Degradation of Wastewater... ... 62
3.1.5.1.2 Chemi-sonication of the Wastewater (CAVOX)... ... 62
3.1.5.1.3 Synergism of Sonication with Conventional Methods... ... 62
3.1.5.1.3.1 Photocatalytic... ... 62
3.1.5.1.3.2 Electrochemical Effects.. ... 63
3.1.5.1.3.3 Sonication-Wet Air Oxidation (SONIWO)... ... 63
x 3.2.1 Heterogeneous Sonochemistry... ... 64 3.2.2 Homogeneous Sonochemistry... ... 64 3.3 Cavitation... ... 64 3.3.1 Acoustic Cavitation... ... 64 3.3.2 Basics of Sonochemistry... ... 66 3.3.2.1 Forms of Cavitation... ... 67 3.3.2.1.1 Transient Cavitation... ... 67 3.3.2.1.2 Stable Cavitation... ... 67
3.3.2.2 Characteristics of the Ultrasonic Wave... ... 68
3.3.2.3 Nucleation, Growth and Collapse of Micro Bubbles... ... 69
3.3.3 Ultrasonic Irradiation... ... 69
3.3.4 Sonoluminescence... ... 70
3.3.4.1 Multi-bubble Sonoluminescence... ... 70
3.3.4.2 Single-bubble Sonoluminescence... ... 70
3.4 Ultrasonic Degradation... ... 71
3.5 The Advantages of Sonication Method in Wastewater Treatment... 71
3.6 Literature Review for the Treatment of PCI ww... ... 74
3.7 Literature Review for the Treatment of OMI ww... ... 78
3.8 Literature Review for the Treatment of TI ww... ... 82
CHAPTER FOUR – MATERIALS AND METHODS ... …………..93
4.1 Experimental Set up... ... 93
4.1.1 Sonicator Properties... ... 93
4.1.1.1 BANDELIN Electronic RK510 H Sonicator... ... 93
4.1.1.2 1K-MODEL Forward-Backward Moving Sonicator... ... 95
4.1.1.3 1K-MODEL Sonicator... ... 95
4.1.1.4 MINI 12 Sonicator... ... 96
4.1.1.5 VWR USC600 DF Sonicator... ... 97
4.2 Operational Conditions in PCI ww, OMI ww and TI ww... ... 97
4.2.1 Effect of Sonication Frequency, Power, Time, Volume, Temperature, Intensity, Density and Specific Energy on the PAH Removals in PCI ww and CODdis Removals in PCI ww, OMI ww and TI ww... ... 97
xi
4.2.1.1 Effect of Sonication Frequency on the PAH Removals in PCI ww
and CODdis Removals in PCI ww, OMI ww and TI ww... ... 97
4.2.1.2 Effect of Sonication Power on the PAH Removals in PCI ww and CODdis Removals in PCI ww, OMI ww and TI ww... ... 98
4.2.1.3 Effect of Sonication Time on the PAH Removals in PCI ww and CODdis Removals in PCI ww, OMI ww and TI ww... ... 98
4.2.1.4 Effect of Sonication Volume on the PAH Removals in PCI ww and CODdis Removals in PCI ww, OMI ww and TI ww... ... 98
4.2.1.5 Effect of Sonication Temperature on the PAH Removals in PCI ww and CODdis Removals in PCI ww, OMI ww and TI ww... ... 98
4.2.1.6 Effect of Sonication Intensity on the PAH Removals in PCI ww and CODdis Removals in PCI ww, OMI ww and TI ww... ... 99
4.2.1.7 Effect of Sonication Density on the PAH Removals in PCI ww and CODdis Removals in PCI ww, OMI ww and TI ww.. ... 99
4.2.1.8 Effect of Specific Energy (Es) on PAH Removals in PCI ww and CODdis Removals in PCI ww, OMI ww and TI ww... ... 100
4.2.2 Administration of Air... ... 101
4.2.3 Administration of Oxygen gas, O2(g)... ... 101
4.2.4 Administration of Nitrogen Gas, N2(g)... ... 101
4.2.5 Adjusting of pH... ... 101
4.2.6 Administration of Hydrogen Peroxide (H2O2)... ... 102
4.2.7 Administration of Titanium Dioxide (TiO2).. ... 102
4.2.8 Administration of Sodium Chloride (NaCl)... ... 102
4.2.9 Administration of Ferrous Iron Ions (Fe+2)... ... 103
4.2.10 Administration of Ferric Iron Ions (Fe+3)... ... 103
4.2.11 Administration of Bicarbonate Ions (HCO3-1).. ... 103
4.2.12 Administration of Butanol (C4H9OH).. ... 103
4.3 Analytical Procedure... ... 104
4.3.1 PAHs Measurements... ... 104
4.3.1.1 Sample Extraction and Concentrate of PAHs... ... 104
4.3.1.2 Clean Up and Fractionation... ... 104
xii
4.3.1.4 Procedural Recoveries... ... 106
4.3.1.5 Calibration Standards... ... 106
4.3.1.6 Limit of quantification (LOQ) and limit of detection (LOD) of PAHs.. ... 107
4.3.2 Total Solids (TS) and Total Suspended Solids (TSS) Measurements... 115
4.3.3 Volatile Solids (VS) and Total Volatile Suspended Solids (TVSS) Measurements... ... 115
4.3.4 pH, T(oC) and Oxidation-Reduction Potential (ORP) Measurements.. . 115
4.3.5 Total Nitrogen (Total-N) Measurements... ... 115
4.3.6 Ammonium-Nitrogen (NH4-N) Measurements... ... 115
4.3.7 Nitrite-Nitrogen (NO2-N) Measurements... ... 115
4.3.8 Nitrate-Nitrogen (NO3-N) Measurements... ... 116
4.3.9 Total Phosphorus (Total-P) Measurements... ... 116
4.3.10 Phosphate-Phosphorus (PO4-P) Measurements... ... 116
4.3.11 Sulfate (SO4) Measurements.. ... 116
4.3.12 Total Phenol (T-Ph) Measurements... ... 116
4.3.13 Biological Oxygen Demand (BOD) and Biological Oxygen Demand-5 days (BOD5) Measurements... ... 117
4.3.14 Total Organic Carbon (TOC) Measurements... ... 117
4.3.15 Chemical Oxygen Demand (COD) Measurements... ... 117
4.3.15.1 Total COD (CODt)... ... 117
4.3.15.2 Dissolved COD (CODdis).. ... 118
4.3.15.3 Soluble Inert COD... ... 118
4.3.16 Color Measurements... ... 118
4.3.17 Total Fatty Acid (TFA) Measurements ... 123
4.3.18 Determination of Aromatic Amines.. ... 124
4.3.19 Oil Measurements... ... 126
4.3.20 Polyphenol Measurements... ... 127
4.3.21 The Measurement Procedure of Sonication by-Products for PCI ww and OMI ww………... ... 128
4.3.21.1 The Measurement Procedure of Sonication by-Product for PCI ww... ... 128
xiii
4.3.21.1.1 Sample Extraction and concentrate of PAH by-Products... .. 128
4.3.21.1.2 Clean Up and Fractionation... ... 129
4.3.21.1.3 The Measurement of phenanthrenediol (by-Product of PAHs)... ... 130
4.3.21.1.4 The Measurements of Methane, CH4(g), Hydrogen, H2(g) and Carbondioxide, CO2(g) gases in PCI ww... ... 130
4.3.21.1.5 Analysis of PAH by-Products Samples with GC-MS... ... 131
4.3.21.1.6 Analysis of PAH by-Products Samples with GC-FID... ... 132
4.3.21.1.7 Analysis of PAH by-Products Samples with HPLC... ... 132
4.3.21.2 The Measurement Procedure of Sonication by-Products for OMI ww... ... 137
4.4 Properties of Chemicals used in the Analysis for PCI ww, OMI ww and TI ww…….... ... 140
4.4.1 Standard Chemicals used for Sonication by-Products of PAHs... ... 140
4.4.1.1 PAH Calibration Standards... ... 140
4.4.1.2 Sodium Sulfate Anhydrous (Na2SO4)... ... 140
4.4.1.3 n-Hexane (C6H14)... ... 140
4.4.1.4 Acetone (C3H6O)... ... 140
4.4.1.5 Silicic Acid (H2O3Si)... ... 141
4.4.1.6 Aluminium Oxide 90 Active Neutral (Al2O3 or Alumina)... ... 141
4.4.1.7 Dichloromethane (CH2Cl2)... ... 141
4.4.1.8 Petroleum Ether (Petroleum Benzine)... ... 142
4.4.1.9 Sodium Sulfate Anhydrous (Na2SO4).. ... 142
4.4.1.10 Benzoic Acid (Carboxybenzene) (C7H6O2)... ... 142
4.4.1.11 1, 2, 3–Thiadiazole–4–carboxylic Acid (C3H2N2O2S)... ... 142 4.4.1.12 1–Methylnaphthalene (C11H10)... ... 143 4.4.1.13 9–Hydroxyfluorene (C13H10O)... ... 143 4.4.1.14 9–10–Phenanthrenequinone (C14H8O2)... ... 143 4.4.1.15 4–Hydroxybenzoic Acid (C7H6O3).. ... 143 4.4.1.16 1, 4–Dioxane (C4H8O2)... ... 143 4.4.1.17 9, H–Fluorene–9, 9–dimethanol (C15H14O2)... ... 144 4.4.1.18 Dihydroxy Pyrene (C10H12O2)... ... 144
xiv
4.4.1.19 Methyl–phenanthrene (C17H16)... ... 144
4.4.1.20 2–Ethyl–phenanthrene (C16H14)... ... 144
4.4.2 Standard Chemicals used in the OMI ww and TI ww... ... 145
4.4.2.1 Benzidine (C16H20N2).. ... 145
4.4.2.2 Absolute Ethanol (C2H5OH)... ... 145
4.4.2.3 Citric Acid Anhydrous (C6H8O7)... ... 145
4.4.2.4 Sodium Hydroxide (NaOH)... ... 145
4.4.2.5 Hydrochloric Acid (HCl)... ... 146
4.4.2.6 p–Dimethileaminobenzaldehid (C9H11NO)... ... 146
4.4.3 Standard Chemicals used for Sonication by-Products of OMI ww... .... 146
4.4.3.1 2–Phenyl–phenol (C12H10O)... ... 146
4.4.3.2 3–Phenyl–phenol (C12H10O)... ... 146
4.4.4 Chemical Properties of Additives used through Sonication Process... .. 147
4.4.4.1 Nitrogen Gas, N2(g)... ... 147
4.4.4.2 Air... ... 147
4.4.4.3 Oxygen Gas, O2(g)... 147
4.4.4.4 Hydrogen Peroxide (H2O2)... ... 147
4.4.4.5 Titanium Dioxide (TiO2)... ... 147
4.4.4.6 Sodium Chloride (NaCl)... ... 148
4.4.4.7 Iron (II) Sulfate Heptahydrate (FeSO4.7H2O)... ... 148
4.4.4.8 Iron (III) Chloride Hexahydrate (FeCl3.6H2O)... ... 148
4.4.4.9 Sodium Bicarbonate (NaHCO3)... ... 148
4.4.4.10 Butanol (C4H9OH).. ... 149
4.4.4.11 Sulfuric Acid (H2SO4)... ... 149
4.4.4.12 Sodium Hydroxide (NaOH)... ... 149
4.4.5 Determination of Acute Toxicity... ... 150
4.4.5.1 Microtox Acute Toxicity Assay... ... 150
4.4.5.2 Daphnia magna Acute Toxicity Test... ... 152
4.5 Reaction Kinetics... 153
4.5.1 Pseudo Zero Order Reaction Kinetic.. ... 153
4.5.2 Pseudo First Order Reaction Kinetic... ... 154
xv 4.6 Calculation of [OH]
ss Concentrations... ... 156
4.7 Statistical Analysis... ... 157
CHAPTER FIVE - RESULTS AND DISCUSSION….. ... 158
5.1 Effect of Sonication Frequency on the PAHs and CODdis Removals... ... 158
5.2 Effect of Sonication Power on the PAHs and CODdis Removals... ... 159
5.3 Effect of Sonication Time on the PAHs and CODdis Removals... ... 160
5.4 Effect of Sonication Volume on the PAHs and CODdis Removals... ... 162
5.5 Effect of Sonication Temperature on the PAHs and CODdis Removals... ... 164
5.6 Effect of Sonication Intensity on the PAHs and CODdis Removals.. ... 165
5.7 Effect of Sonication Density on the PAHs and CODdis Removals... 167
5.8 Effect of Specific Energy (Es) on the PAHs and CODdis Removals... ... 169
5.9 Sonication of PCI ww... ... 172
5.9.1 Effect of Increasing Sonication Times on the Removals of CODdis, TOC and PAHs in PCI ww... ... 173
5.9.1.1 Effect of Increasing Sonication Times on the Removals of CODdis and TOC in PCI ww... ... 173
5.9.1.2 Effect of Increasing Sonication Times on the PAHs Removal Efficiencies in PCI ww at 25oC Ambient Conditions... ... 175
5.9.2 Effect of Increasing Sonication Temperature on the Removals of CODdis, TOC and PAHs in PCI ww... ... 186
5.9.2.1 Effect of Increasing Sonication Temperature on the Removals of CODdis and TOC in PCI ww... ... 186
5.9.2.2 Effect of Increasing Temperature on the Removal of PAHs in PCI ww at Increasing Sonication Times... ... 189
5.9.2.2.1 Produced Metabolites from PHE, PY and BghiP PAHs in PCI ww.. ... 201
5.9.3 Effect of DO Concentrations on the Removal of PAHs in PCI ww at Increasing Sonication Times and Temperatures.. ... 205
5.9.4 Effect of Aeration on the Removal of PAHs in PCI ww at Increasing Sonication Time and Temperature.. ... 214
xvi
5.9.5 Effect of N2(g) on the PAHs Removal Efficiencies in PCI ww Versus Sonication Times and Temperatures... ... 221 5.9.6 Effect of H2O2 Concentrations on the Removal of PAHs in PCI ww at
Increasing Sonication Times and Temperatures... ... 229 5.9.7 Effect of TiO2 Concentrations on the PAHs Removal Efficiencies in PCI ww at Increasing Sonication Times and Temperatures... ... 237 5.9.8 Effect of NaCl Concentrations on the PAHs Removal Efficiencies in PCI ww at Increasing Sonication Times and Temperatures... ... 245 5.9.9 Effect of Fe+2 Concentrations on the Removal of PAHs in PCI ww at
Increasing Sonication Times and Temperatures... ... 250 5.9.10 Effect of Fe+3 Concentrations on the Removal of PAHs in PCI ww at Increasing Sonication Times and Temperatures... ... 256 5.9.11 Effect of HCO3-1 Concentrations on the Removal of PAHs in PCI ww at Increasing Sonication Times and Temperatures... ... 261 5.9.12 Effect of iso-Butanol (C4H9OH) Concentrations on the Removal of PAHs in PCI ww at Increasing Sonication Times and Temperatures…... ... 268 5.9.13 Effect of S2O8-2 Concentrations on the Removal of PAHs in PCI ww in the Presence of iso-Butanol (C4H9OH)... ... 274 5.9.14 Effect of pH Values on the Removal of PAHs in PCI ww at Increasing
Sonication Times and Temperatures.. ... 277 5.10 Sonication of OMI ww... ... 283 5.10.1 Effect of Increasing Sonication Time on the Removals of CODdis and TOC in OMI ww at 25oC Ambient Conditions... ... 285 5.10.2 Effect of Increasing Sonication Time on the Removals of Color, Total
Phenol, TAAs and TFAs in OMI ww at 25oC Ambient Conditions..289 5.10.2.1 Effect of Increasing Sonication Time on the Color Removal
Efficiencies in OMI ww at 25oC Ambient Conditions. ... 289 5.10.2.2 Effect of Increasing Sonication Time on the Total Phenol Removal Efficiencies in OMI ww at 25oC Ambient Conditions... ... 290 5.10.2.3 Effect of Increasing Sonication Time on the TAAs Removal
xvii
5.10.2.4 Effect of Increasing Sonication Time on the TFAs Removal Efficiencies in OMI ww at Ambient Conditions... ... 299 5.10.3 Effect of Increasing Temperature on the Removals of CODdis and TOC
versus sonication times in OMI ww... ... 301 5.10.3.1 Effect of Increasing Sonication Time on the Removals of CODdis in the OMI ww………... 301 5.10.3.2 Effect of Increasing Temperature on the Color Removal Efficiencies in OMI ww at Increasing Sonication Times... ... 305 5.10.3.3 Effect of Increasing Temperature on the Total Phenol Removal
Efficiencies in OMI ww at Increasing Sonication Times... ... 307 5.10.3.4 Effect of Increasing Temperature on the TAAs Removal Efficiencies in OMI ww at Increasing Sonication Times... ... 312 5.10.3.5 Effect of Increasing Temperature on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times... ... 313 5.10.4 Effect of DO Concentrations on the Removals of CODdis in OMI ww…... ... 316 5.10.4.1 Effect of DO Concentrations on the Color Removal Efficiencies in OMI ww at Increasing Sonication Time and Temperature.. ... 320 5.10.4.2 Effect of DO Concentrations on the Total Phenol Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 322 5.10.4.3 Effect of DO Concentrations on the TAAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... .... 326 5.10.4.4 Effect of DO Concentrations on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... .... 328 5.10.5 Effect of N2(g) on the Removals of CODdis in OMI ww... ... 330
5.10.5.1 Effect of N2(g) on the Color Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 334 5.10.5.2 Effect of N2(g) on the Total Phenol Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 336
xviii
5.10.5.2.1 Effect of pH on the Removal of Phenol Removal Efficiencies in OMI ww in the Presence of 30 min N2(g) (6.00 mg/l N2) Sparging after 150 min Sonication at 60oC………. 337 5.10.5.3 Effect of N2(g) on the TAAs Removal Efficiencies in OMI ww at
Increasing Sonication Times and Temperatures... ... 339 5.10.5.4 Effect of N2(g) on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 341 5.10.6 Effect of H2O2 Concentrations on the Removals of CODdis in OMI ww…. ... 343 5.10.6.1 Effect of H2O2 Concentrations on the Color Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... 346 5.10.6.2 Effect of H2O2 Concentrations on the Total Phenol Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 349 5.10.6.3 Effect of H2O2 Concentrations on the TAAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... 352 5.10.6.4 Effect of H2O2 Concentrations on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. . 355 5.10.7 Effect of TiO2 Concentrations on the Removals of CODdis in OMI ww…. ... 357 5.10.7.1 Effect of TiO2 Concentrations on the Color Removal Efficiencies in
OMI ww at Increasing Sonication Times and Temperatures... .... 361 5.10.7.2 Effect of TiO2 Concentrations on the Total Phenol Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 362 5.10.7.3 Effect of TiO2 Concentrations on the TAAs Removal Efficiencies
in OMI ww at Increasing Sonication Times and Temperatures.. . 364 5.10.7.4 Effect of TiO2 Concentrations on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... .... 366 5.10.8 Effect of NaCl Concentrations on the Removals of CODdis in OMI ww.... ... 368
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5.10.8.1 Effect of NaCl Concentrations on the Color Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... 371 5.10.8.2 Effect of NaCl Concentrations on the Total Phenol Removal
Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 372 5.10.8.3 Effect of NaCl Concentrations on the TAAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... 374 5.10.8.4 Effect of NaCl Concentrations on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... 376 5.10.9 Effect of Fe+2 Concentrations on the Removals of CODdis in OMI ww... ... 378 5.10.9.1 Effect of Fe+2 Concentrations on the Color Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 380 5.10.9.2 Effect of Fe+2 Concentrations on the Total Phenol Removal
Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 383 5.10.9.3 Effect of Fe+2 Concentrations on the TAAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 384 5.10.9.4 Effect of Fe+2 Concentrations on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... .... 386 5.10.10 Effect of Fe+3 Concentrations on the Removals of CODdis in OMI
ww.... ... 388 5.10.10.1 Effect of Fe+3 Concentrations on the Color Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures…….. ... 390 5.10.10.2 Effect of Fe+3 Concentrations on the Total Phenol Removal
Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 392 5.10.10.3 Effect of Fe+3 Concentrations on the TAAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures..….... ... 393
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5.10.10.4 Effect of Fe+3 Concentrations on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures..….... ... 395 5.10.11 Effect of HCO3-1 Concentrations on the Removals of CODdis in OMI
ww……… ... 397 5.10.11.1 Effect of HCO3-1 Concentrations on the Color Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 399 5.10.11.2 Effect of HCO3-1 Concentrations on the Total Phenol Removal
Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 402 5.10.11.3 Effect of HCO3-1 Concentrations on the TAAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 404 5.10.11.4 Effect of HCO3-1 Concentrations on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 406 5.10.12 Effect of C4H9OH (1-Butanol) Concentrations on the Removals of CODdis in OMI ww.. ... 408 5.10.12.1 Effect of C4H9OH Concentrations on the Color Removal
Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 410 5.10.12.2 Effect of C4H9OH Concentrations on the Total Phenol Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 413 5.10.12.3 Effect of C4H9OH Concentrations on the TAAs Removal
Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 415 5.10.12.4 Effect of C4H9OH Concentrations on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 417 5.10.13 Effect of pH Values on the Removals of CODdis in OMI ww... ... 419
xxi
5.10.13.1 Effect of pH Values on the Color Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 422 5.10.13.2 Effect of pH Values on the Total Phenol Removal Efficiencies in
OMI ww at Increasing Sonication Times and Temperatures. .... 424 5.10.13.3 Effect of pH Values on the TAAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 427 5.10.13.4 Effect of pH Values on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... ... 429 5.10.14 Effect of Aeration on the Removals of CODdis in OMI ww.. ... 431
5.10.14.1 Effect of Aeration on the Color Removal Efficiencies in OMI ww at Increasing Sonication Time and Temperature.. ... 434 5.10.14.2 Effect of Aeration on the Total Phenol Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures... .. 436 5.10.14.3 Effect of Aeration on the TAAs Removal Efficiencies in OMI ww
at Increasing Sonication Times and Temperatures.. ... 437 5.10.14.4 Effect of Aeration on the TFAs Removal Efficiencies in OMI ww at Increasing Sonication Times and Temperatures.. ... 439 5.11 Sonication of TI ww... ... .442 5.11.1 Effect of Increasing Sonication Time on the Removals of CODdis and TOC in TI ww at 25oC Ambient Conditions... ... 443 5.11.2 Effect of Increasing Sonication Time on the Removals of Color and TAAs in TI ww at 25oC Ambient Conditions... ... 446 5.11.2.1 Effect of Increasing Sonication Time on the Color Removal Efficiencies in TI ww at 25oC in Ambient Conditions in TI ww... ... 446 5.11.2.2 Effect of Increasing Sonication Time on the TAAs Removal
Efficiencies in TI ww at 25oC Ambient Conditions.. ... 449 5.11.3 Effect of Increasing Temperature on the Removals of CODdis and TOC versus sonication times in TI ww.. ... 453 5.11.3.1 Effect of Increasing Sonication Time on the Removals of CODdis in the TI ww…….... ... 453
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5.11.3.2 Effect of Increasing Temperature on the Color Removal Efficiencies in TI ww at Increasing Sonication Time... ... 458 5.11.3.3 Effect of Increasing Temperature on the TAAs Removal
Efficiencies in TI ww at Increasing Sonication Times... ... 460 5.11.4 Effect of pH Values on the Removals of CODdis in TI ww... ... 462 5.11.4.1 Effect of pH Values on the Color Removal Efficiencies in TI ww at Increasing Sonication Time and Temperature.. ... 465 5.11.4.2 Effect of pH Values on the TAAs Removal Efficiencies in TI ww at Increasing Sonication Time and Temperature... ... 469 5.11.5 Effect of DO Concentrations on the Removals of CODdis in TI ww.. . 471
5.11.5.1 Effect of DO Concentrations on the Color Removal Efficiencies in TI ww at Increasing Sonication Time and Temperature... 475 5.11.5.2 Effect of DO Concentrations on the TAAs Removal Efficiencies in
TI ww at Increasing Sonication Times and Temperatures... ... 478 5.11.6 Effect of Aeration on the Removals of CODdis in TI ww... ... 480 5.11.6.1 Effect of Aeration on the Color Removal Efficiencies in TI ww at Increasing Sonication Time and Temperature.. ... 483 5.11.6.2 Effect of Aeration on the TAAs Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... ... 485 5.11.7 Effect of N2(g) on the Removals of CODdis in TI ww... ... 487
5.11.7.1 Effect of N2(g) on the Color Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... ... 489 5.11.7.2 Effect of N2(g) on the TAAs Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... ... 491 5.11.8 Effect of H2O2 Concentrations on the Removals of CODdis in TI ww..493
5.11.8.1 Effect of H2O2 Concentrations on the Color Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... .... 497 5.11.8.2 Effect of H2O2 Concentrations on the TAAs Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... .... 500 5.11.9 Effect of TiO2 Concentrations on the Removals of CODdis in TI ww...502
xxiii
5.11.9.1 Effect of TiO2 Concentrations on the Color Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... 504 5.11.9.2 Effect of TiO2 Concentrations on the TAAs Removal Efficiencies
in TI ww at Increasing Sonication Times and Temperatures... .... 506 5.11.10 Effect of NaCl Concentrations on the Removals of CODdis in TI ww….... ... 508 5.11.10.1 Effect of NaCl Concentrations on the Color Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... .. 511 5.11.10.2 Effect of NaCl Concentrations on the TAAs Removal Efficiencies
in TI ww at Increasing Sonication Times and Temperatures... .. 513 5.11.11 Effect of Fe+2 Concentrations on the Removals of CODdis in TI ww….... ... 515 5.11.11.1 Effect of Fe+2 Concentrations on the Color Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... .. 519 5.11.11.2 Effect of Fe+2 Concentrations on the TAAs Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... .. 521 5.11.12 Effect of Fe+3 Concentrations on the Removals of CODdis in TI ww….... ... 523 5.11.12.1 Effect of Fe+3 Concentrations on the Color Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... .. 527 5.11.12.2 Effect of Fe+3 Concentrations on the TAAs Removal Efficiencies
in TI ww at Increasing Sonication Times and Temperatures... .. 529 5.11.13 Effect of HCO3-1 Concentrations on the Removals of CODdis in TI ww..….... ... 531 5.11.13.1 Effect of HCO3-1 Concentrations on the Color Removal
Efficiencies in TI ww at Increasing Sonication Times and Temperatures... ... 535 5.11.13.2 Effect of HCO3-1 Concentrations on the TAAs Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures... ... 537 5.11.14 Effect of C4H9OH Concentrations on the Removals of CODdis in TI
xxiv
5.11.14.1 Effect of C4H9OH Concentrations on the Color Removal Efficiencies in TI ww at Increasing Sonication Times and Temperatures.. ... 542 5.11.14.2 Effect of C4H9OH Concentrations on the TAAs Removal
Efficiencies in TI ww at Increasing Sonication Times and Temperatures... ... 545 5.12 Reaction Kinetic of PAHs.. ... 548 5.12.1 Reaction Kinetic of PAHs at 35 kHz Frequency and at a Temperature of 60oC….... ... 548 5.12.2 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 6.00 mg/l DO…….. ... 554 5.12.3 PAHs Removal Kinetic at 35 kHz and at 60oC in the Presence of 6.00 mg/l NaCl….... ... 556 5.12.4 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 6.00
mg/l Al2O3….. ... 559 5.12.5 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of CaCl2. ... 563 5.12.6 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of pH... ... 566 5.12.7 Reaction Kinetic of PAHs at Different Experimental Conditions. ... 569
5.12.7.1 Reaction Kinetic of PAHs at 35 kHz and at 60oC ... 569 5.12.7.2 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 10.00 mg/l DO... ... 572 5.12.7.3 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 1 hour Aeration. ... 574 5.12.7.4 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of
30 min N2(g) (6.00 mg/l N2) Sparging... 576 5.12.7.5 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 2000 mg/l H2O2... ... 578 5.12.7.6 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 20.00 mg/l TiO2... ... 581
xxv
5.12.7.7 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 15.00 g/l NaCl….. ... 583 5.12.7.8 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of
20.00 mg/l Fe+2... ... 585 5.12.7.9 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 50.00 mg/l Fe+3.. ... 587 5.12.7.10 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence of 2.00 g/l C4H9OH.. ... 589 5.12.7.11 Reaction Kinetic of PAHs at 35 kHz and at 60oC in the Presence
of pH=7.0... ... 591 5.13 PAHs Removal Mechanisms... ... 593 5.13.1 Mechanisms of PAHs Sonication at 35 kHz Frequency and at 60oC in the Presence of 6.00 mg/l NaCl.. ... 593 5.13.2 PAHs Mechanisms at 35 kHz Frequency and 60oC Temperature in the
Presence of 6.00 mg/l Al2O3... ... 600 5.13.3 Mechanisms of PAHs Sonication at 35 kHz Frequency and at 60oC Temperature.. ... 605 5.13.4 Mechanisms of PAHs Sonication at 35 kHz Frequency after 150 min Sonication in the Presence of 6.00 mg/l DO.. ... 608 5.14 Reaction Kinetic of OMI ww... ... 615 5.14.1 Reaction Kinetic of OMI ww at 35 kHz and at 60oC in the Presence of
10.00 mg/l DO... ... 615 5.14.2 Reaction Kinetic of OMI ww at 35 kHz and at 60oC in the Presence of 2000 mg/l H2O2.. ... 624 5.14.3 Reaction Kinetic of OMI ww at 35 kHz and at 60oC in the Presence of
20.00 mg/l TiO2 ... 629 5.14.4 Reaction Kinetic of OMI ww at 35 kHz and at 60oC in the Presence of 15.00 mg/l NaCl... 633 5.15 Reaction Kinetic of TI ww... ... 640 5.15.1 Reaction Kinetic of TI ww at 35 kHz and at 60oC in the Presence of 2000 mg/l H2O2….. ... 640
xxvi
5.15.2 Reaction Kinetic of TI ww at 35 kHz and at 60oC in the Presence of 20.00 mg/l TiO2.. ... 650 5.15.3 Reaction Kinetic of TI ww at 35 kHz and at 60oC in the Presence of
15.00 g/l NaCl….. ... 658 5.15.4 Reaction Kinetic of TI ww at 35 kHz and at 60oC in the Presence of 20.00 mg/l Fe+2... ... 663 5.16 Acute Toxicity Evaluations in PCI ww.. ... 668 5.16.1 Effect of Increasing Sonication Time on the Acute Toxicity Removal Efficiencies in PCI ww at Ambient Conditions.. ... 668 5.16.1.1 Effect of Increasing Sonication Time on the Microtox Acute Toxicity Removal Efficiencies in PCI ww at Ambient Conditions.... ... 678 5.16.1.2 Effect of Increasing Sonication Time on Daphnia magna Acute Toxicity Removal Efficiencies in PCI ww at Ambient Conditions.... ... 682 5.16.2 Effect of Increasing Temperature on the Removal of Acute Toxicity in PCI ww at Increasing Sonication Time.. ... 686 5.16.2.1 Effect of Increasing Temperature on the Removal of Microtox Acute Toxicity in PCI ww at Increasing Sonication Time... ... 686 5.16.2.2 Effect of Increasing Temperature on the Removal of Daphnia
magna Acute Toxicity in PCI ww at Increasing Sonication Time….. ... 690 5.16.3 Effect of H2O2 Concentrations on the Removal of Acute Toxicity in PCI ww at Increasing Sonication Time and Temperature.. ... 694 5.16.3.1 Effect of H2O2 Concentrations on the Removal of Microtox Acute
Toxicity in PCI ww at Increasing Sonication Time and Temperature... ... 694 5.16.3.2 Effect of H2O2 Concentrations on the Removal of Daphnia magna Acute Toxicity in PCI ww at Increasing Sonication Time and Temperature.. ... 699 5.16.3.3 Direct Effects of H2O2 Concentrations on the Acute Toxicity of
xxvii
5.16.4 Effect of TiO2 Concentrations on the Acute Toxicity Removal Efficiencies in PCI ww at Increasing Sonication Time and Temperature... ... 705 5.16.4.1 Effect of TiO2 Concentrations on the Microtox Acute Toxicity
Removal Efficiencies in PCI ww at Increasing Sonication Time and Temperature.. ... 705 5.16.4.2 Effect of TiO2 Concentrations on the Daphnia magna Acute Toxicity Removal Efficiencies in PCI ww at Increasing Sonication Time and Temperature……. ... 709 5.16.4.3 Direct Effects of TiO2 Concentrations on the Acute Toxicity of Microtox and Daphnia magna in PCI ww... ... 714 5.16.5 Effect of NaCl Concentrations on the Acute Toxicity Removal Efficiencies in PCI ww at Increasing Sonication Time and Temperature.. ... 715 5.16.5.1 Effect of NaCl Concentrations on the Microtox Acute Toxicity Removal Efficiencies in PCI ww at Increasing Sonication Time and Temperature... ... 715 5.16.5.2 Effect of NaCl Concentrations on the Daphnia magna Acute Toxicity Removal Efficiencies in PCI ww at Increasing Sonication Time and Temperature….... ... 717 5.16.5.3 Direct Effects of NaCl Concentrations on the Acute Toxicity of
Microtox and Daphnia magna in PCI ww... ... 720 5.16.6 Effect of Fe+2 Concentrations on the Removal of Acute Toxicity in PCI ww at Increasing Sonication Time and Temperature. ... 721 5.16.6.1 Effect of Fe+2 Concentrations on the Removal of Microtox Acute
Toxicity in PCI ww at Increasing Sonication Time and Temperature.. ... 721 5.16.6.2 Effect of Fe+2 Concentrations on the Removal of Daphnia magna Acute Toxicity in PCI ww at Increasing Sonication Time and Temperature ... 723 5.16.6.3 Direct Effects of Fe+2 Concentrations on the Acute Toxicity of
xxviii
5.16.7 Effect of Fe+3 Concentrations on the Removal of Acute Toxicity in PCI ww at Increasing Sonication Time and Temperature.. ... 726 5.16.7.1 Effect of Fe+3 Concentrations on the Removal of Microtox Acute
Toxicity in PCI ww at Increasing Sonication Time and Temperature. ... 726 5.16.7.2 Effect of Fe+3 Concentrations on the Removal of Daphnia magna Acute Toxicity in PCI ww at Increasing Sonication Time and Temperature.. ... 728 5.16.7.3 Direct Effects of Fe+3 Concentrations on the Acute Toxicity of
Microtox and Daphnia magna in PCI ww.. ... 730 5.16.8 PAH Toxicities, Interspecies Correlation and Sensitivities... ... 731 5.16.9 Correlation of Acute Toxicities with Physicochemical Properties of PAHs after 150 min Sonication at 30oC ... 735 5.17 Acute Toxicity Evaluations in OMI ww... ... 739
5.17.1 Effect of Increasing Sonication Time on the Acute Toxicity Removal Efficiencies in OMI ww at Ambient Conditions. ... 739 5.17.1.1 Effect of Increasing Sonication Time on the Microtox Acute Toxicity Removal Efficiencies in OMI ww at Ambient Conditions... ... 739 5.17.1.2 Effect of Increasing Sonication Time on the Daphnia magna Acute
Toxicity Removal Efficiencies in OMI ww at Ambient Conditions... ... 743 5.17.2 Effect of Increasing Temperature on the Removal of Acute Toxicity in OMI ww at Increasing Sonication Time. ... 747 5.17.2.1 Effect of Increasing Temperature on the Removal of Microtox
Acute Toxicity in OMI ww at Increasing Sonication Time.. ... 747 5.17.2.2 Effect of Increasing Temperature on the Removal of Daphnia magna Acute Toxicity in OMI ww at Increasing Sonication Time.... ... 751 5.17.3 Effect of H2O2 Concentrations on the Removal of Acute Toxicity in OMI ww at Increasing Sonication Time and Temperature ... 755
xxix
5.17.3.1 Effect of H2O2 Concentrations on the Removal of Microtox Acute Toxicity in OMI ww at Increasing Sonication Time and Temperature... ... 755 5.17.3.2 Effect of H2O2 Concentrations on the Removal of Daphnia magna
Acute Toxicity in OMI ww at Increasing Sonication Time and Temperature... ... 759 5.17.3.3 Direct Effects of H2O2 Concentrations on the Acute Toxicity of Microtox and Daphnia magna in OMI ww... ... 763 5.17.4 Effect of TiO2 Concentrations on the Acute Toxicity Removal
Efficiencies in OMI ww at Increasing Sonication Time and Temperature... ... 764 5.17.4.1 Effect of TiO2 Concentrations on the Microtox Acute Toxicity Removal Efficiencies in OMI ww at Increasing Sonication Time and Temperature... ... 764 5.17.4.2 Effect of TiO2 Concentrations on the Daphnia magna Acute Toxicity Removal Efficiencies in OMI ww at Increasing Sonication Time and Temperature…... ... 769 5.17.4.3 Direct Effects of TiO2 Concentrations on the Acute Toxicity of Microtox and Daphnia magna in OMI ww... ... 774 5.17.5 Effect of NaCl Concentrations on the Acute Toxicity Removal
Efficiencies in OMI ww at the Sonication Time and Temperature.. . 775 5.17.5.1 Effect of NaCl Concentrations on the Microtox Acute Toxicity Removal Efficiencies in OMI ww at the Sonication Time and Temperature ... 775 5.17.5.2 Effect of NaCl Concentrations on the Daphnia magna Acute
Toxicity Removal Efficiencies in OMI ww at the Sonication Time and Temperature. ... 777 5.17.5.3 Direct Effects of NaCl Concentrations on the Acute Toxicity of Microtox and Daphnia magna in OMI ww.. ... 779 5.17.6 Effect of Fe+2 Concentrations on the Removal of Acute Toxicity in OMI ww at Increasing Sonication Time and Temperature.. ... 781
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5.17.6.1 Effect of Fe+2 Concentrations on the Removal of Microtox Acute Toxicity in OMI ww at Increasing Sonication Time and Temperature... ... 781 5.17.6.2 Effect of Fe+2 Concentrations on the Removal of Daphnia magna
Acute Toxicity in OMI ww at Increasing Sonication Time and Temperature... ... 783 5.17.6.3 Direct Effects of Fe+2 Concentrations on the Acute Toxicity of Microtox and Daphnia magna in OMI ww.. ... 785 5.17.7 Effect of Fe+3 Concentrations on the Removal of Acute Toxicity in OMI
ww at Increasing Sonication Time and Temperature... ... 786 5.17.7.1 Effect of Fe+3 Concentrations on the Removal of Microtox Acute Toxicity in OMI ww at Increasing Sonication Time and Temperature... ... 786 5.17.7.2 Effect of Fe+3 Concentrations on the Removal of Daphnia magna
Acute Toxicity in OMI ww at Increasing Sonication Time and Temperature... ... 788 5.17.7.3 Direct Effects of Fe+3 Concentrations on the Acute Toxicity of Microtox and Daphnia magna in OMI ww... ... 790 5.17.8 OMI ww Toxicities, Interspecies Correlation and Sensitivities... ... 792 5.18 Acute Toxicity Evaluations in TI ww... ... 795
5.18.1 Effect of Increasing Sonication Time on the Acute Toxicity Removal Efficiencies in TI ww at Ambient Conditions.. ... 795 5.18.1.1 Effect of Increasing Sonication Time on the Microtox Acute Toxicity Removal Efficiencies in TI ww at Ambient Conditions.….. ... 795 5.18.1.2 Effect of Increasing Sonication Time on the Daphnia magna Acute
Toxicity Removal Efficiencies in TI ww at Ambient Conditions…... ... 799 5.18.2 Effect of Increasing Temperature on the Removal of Acute Toxicity in TI ww at Increasing Sonication Time.. ... 803 5.18.2.1 Effect of Increasing Temperature on the Removal of Microtox
xxxi
5.18.2.2 Effect of Increasing Temperature on the Removal of Daphnia magna Acute Toxicity in TI ww at Increasing Sonication Time. 807 5.18.3 Effect of H2O2 Concentrations on the Removal of Acute Toxicity in TI
ww at Increasing Sonication Time and Temperature. ... 811 5.18.3.1 Effect of H2O2 Concentrations on the Removal of Microtox Acute Toxicity in TI ww at Increasing Sonication Time and Temperature... ... 811 5.18.3.2 Effect of H2O2 Concentrations on the Removal of Daphnia magna Acute Toxicity in TI ww at Increasing Sonication Time and Temperature.. ... 815 5.18.3.3 Direct Effects of H2O2 Concentrations on the Acute Toxicity of Microtox and Daphnia magna in TI ww... ... 819 5.18.4 Effect of TiO2 Concentrations on the Acute Toxicity Removal Efficiencies in TI ww at Increasing Sonication Time and Temperature... ... 820 5.18.4.1 Effect of TiO2 Concentrations on the Microtox Acute Toxicity Removal Efficiencies in TI ww at Increasing Sonication Time and Temperature.. ... 820 5.18.4.2 Effect of TiO2 Concentrations on the Daphnia magna Acute Toxicity Removal Efficiencies in TI ww at Increasing Sonication Time and Temperature... ... 825 5.18.4.3 Direct Effects of TiO2 Concentrations on the Acute Toxicity of Microtox and Daphnia magna in TI ww. ... 829 5.18.5 Effect of NaCl Concentrations on the Acute Toxicity Removal Efficiencies in TI ww at Increasing Sonication Time and Temperature... ... 831 5.18.5.1 Effect of NaCl Concentrations on the Microtox Acute Toxicity Removal Efficiencies in TI ww Increasing Sonication Time and Temperature.. ... 831 5.18.5.2 Effect of NaCl Concentrations on the Removal of Daphnia magna Acute Toxicity in TI ww at Increasing Sonication Time and Temperature... ... 833
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5.18.5.3 Direct Effects of NaCl Concentrations on the Acute Toxicity of Microtox and Daphnia magna in TI ww. ... 835 5.18.6 Effect of Fe+2 Concentrations on the Removal of Acute Toxicity in TI
ww at Increasing Sonication Time and Temperature.. ... 836 5.18.6.1 Effect of Fe+2 Concentrations on the Removal of Microtox Acute Toxicity in TI ww at Increasing Sonication Time and Temperature.. ... 836 5.18.6.2 Effect of Fe+2 Concentrations on the Removal of Daphnia magna Acute Toxicity in TI ww at Increasing Sonication Time and Temperature ... 838 5.18.6.3 Direct Effects of Fe+2 Concentrations on the Acute Toxicity of Microtox and Daphnia magna in TI ww. ... 840 5.18.7 Effect of Fe+3 Concentrations on the Removal of Acute Toxicity in TI ww at Increasing Sonication Time and Temperature.. ... 841 5.18.7.1 Effect of Fe+3 Concentrations on the Removal of Microtox Acute Toxicity in TI ww at Increasing Sonication Time and Temperature.. ... 841 5.18.7.2 Effect of Fe+3 Concentrations on the Removal of Daphnia magna Acute Toxicity in TI ww at Increasing Sonication Time and Temperature... ... 843 5.18.7.3 Direct Effects of Fe+3 Concentrations on the Acute Toxicity of
Microtox and Daphnia magna in TI ww ... 845 5.18.8 TI ww Toxicities, Interspecies Correlation and Sensitivities.. ... 846 5.19 Cost and Specific Energy Estimation ... 849
5.19.1 Cost Estimation Methodology ... 849 5.19.2 The Calculation of Energy Requirement in Sonication Reactor... ... 853
5.19.2.1 The Calculation of Energy Requirement in Sonication Reactor for PCI ww…... ... 853 5.19.2.2 The Calculation of Energy Requirement in Sonication Reactor for OMI ww…... ... 854 5.19.2.3 The Calculation of Energy Requirement in Sonication Reactor
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5.19.3 General Calculation of Capital Cost in Sonication Reactor ... 855 5.19.3.1 General Calculation of Capital Cost in Sonication Reactor for PCI ww... ... 856 5.19.3.2 General Calculation of Capital Cost in Sonication Reactor for OMI
ww…….. ... 856 5.19.3.3 General Calculation of Capital Cost in Sonication Reactor for TI ww ... 856 5.19.4 The Compaırison of Cost for AOPs in Different Litearature Studies.. 858 5.19.5 Capital Cost Calculations for US System.. ... 860 5.19.6 Operating and Maintenance (O & M) Cost Calculations for Sonication Process.. ... 862 5.19.6.1 Labor Cost for Sonication Process.. ... 862 5.19.6.2 Analytical Costs for Sonication Process. ... 865 5.19.6.3 Chemical Costs for Sonication Process ... 867
5.19.6.3.1 The Annual Chemical Cost for O2(g) during Sonication Process... ... 867 5.19.6.3.2 The Annual Chemical Cost for N2(g) during Sonication Process... ... 867 5.19.6.3.3 The Annual Chemical Cost for H2O2 during Sonication Process... ... 868 5.19.6.3.4 The Annual Chemical Cost for TiO2 during Sonication
Process... ... 868 5.19.6.3.5 The Annual Chemical Cost for NaCl during Sonication Process... ... 868 5.19.6.3.6 The Annual Chemical Cost for Fe+2 during Sonication
Process. ... 869 5.19.6.3.7 The Annual Chemical Cost for Fe+3 during Sonication Process... ... 870 5.19.6.3.8 The Annual Chemical Cost for HCO3-1 during Sonication Process... ... 871 5.19.6.3.9 The Annual Chemical Cost for C4H9OH during Sonication
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5.19.6.3.10 The Annual Chemical Cost for H2SO4 during Sonication Process. ... 872 5.19.6.3.11 The Annual Chemical Cost for NaOH during Sonication
Process... ... 872 5.19.6.4 Electrical Cost for US System.. ... 875 5.19.6.5 Part Replacement Cost for Sonication Process.. ... 879 5.19.7 General Procedure for Calculation of Electric Energy per Order (EE / O) or Electrical Energy per Unit Mass (EE / M).. ... 883 5.19.7.1 EE/O Calculation for US System.. ... 883
5.19.7.1.1 EE/O Calculation for US System in PCI ww.. ... 884 5.19.7.1.2 EE/O Calculation for US System in OMI ww... ... 884 5.19.7.1.3 EE/O Calculation for US System in TI ww. ... 885 5.19.7.2 EE/M Calculation for US System. ... 885
5.19.7.2.1 EE/M Calculation for US System in PCI ww... ... 886 5.19.7.2.2 EE/M Calculation for US System in OMI ww.. ... 886 5.19.7.2.3 EE/M Calculation for US System in TI ww ... 887 5.19.8 Specific Energy Calculations for US System.. ... 887 5.19.8.1 The Specific Energy (Es) Calculation for US System in PCI ww…... ... 888 5.19.8.2 The Specific Energy (Es) Calculation for US System in OMI
ww... ... 888 5.19.8.3 The Specific Energy (Es) Calculation for US System in TI ww....889 5.19.9 The Cost Comparison of Anaerobic, Aerobic, UV, O3 and Sonication
Treatment.. ... 889 5.19.10 Conclusions. ... 894 CHAPTER SIX - CONCLUSIONS AND RECOMMENDATIONS………….897
6.1 Conclusions.. ... 897 6.1.1 The Removal of Toxic and Refractory Compounds in PCI ww, OMI ww and TI ww during Sonication Process with only Sonication... ... 897 6.1.1.1 The Removal of Toxic and Refractory Compounds in PCI ww during Sonication Process with only Sonication... ... 897
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6.1.1.2 The Removal of Toxic and Refractory Compounds in OMI ww during Sonication Process with only Sonication... ... 898 6.1.1.3 The Removal of Toxic and Refractory Compounds in TI ww during
Sonication Process with only Sonication.. ... 898 6.1.2 The Removal of Toxic and Refractory Compounds in PCI ww, OMI ww and TI ww during Sonication Process with the Addition of Some Chemicals. ... 898 6.1.2.1 CODdis, TOC and Total PAHs removal effıcıencıes in PCI ww during Sonication Process with the Addition of Some Chemicals...898 6.1.2.2 The Removal Efficiencies of CODdis, TOC, Color, Total Phenol,
TAAs and TFAs in OMI ww during Sonication Process with the Addition of Some Chemicals…. ... 900 6.1.2.3 The Removal Efficiencies of CODdis, TOC, Color and TAAs in TI
ww during Sonication Process with the Addition of Some Chemicals.. ... 902 6.1.3 Microtox and Daphnia magna Acute Toxicity Removal Efficiencies in PCI ww, OMI ww and TI ww with only Sonication Process. ... 903 6.1.3.1 Acute Toxicity Removal Efficiencies in Microtox and Daphnia magna Tests for PCI ww during Sonication Process when Some Chemical Additives were not Used…... ... 903 6.1.3.2 Microtox and Daphnia magna Acute Toxicicty Removal Efficiencies in OMI ww during Sonication Process with only Sonication. ... 904 6.1.3.3 Microtox and Daphnia magna Acute Toxicicty Removal Efficiencies
in OMI ww during Sonication Process with only Sonication ... 904 6.1.4 Microtox and Daphnia magna Acute Toxicity Removal Efficiencies in PCI ww, OMI ww and TI ww during Sonication Process with the Addition of Some Chemicals. ... 904 6.1.4.1 Microtox and Daphnia magna Acute Toxicity Removal Efficiencies in PCI ww during Sonication Process with the Addition of Some Chemicals ... 904
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6.1.4.2 Microtox and Daphnia magna Acute Toxicity Removal Efficiencies in OMI ww during Sonication Process with the Addition of Some Chemicals... 906 6.1.4.3 Microtox and Daphnia magna Acute Toxicity Removal Efficiencies
in TI ww during Sonication Process with the Addition of Some Chemicals.. ... 907 6.1.5 Evaluation of Reaction Kinetics in PCI ww, OMI ww and TI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals…. ... 909 6.1.5.1 Evaluation of Reaction Kinetics in PCI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals... ... 909 6.1.5.2 The Evaluation of Reaction Kinetics in OMI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals ... 909 6.1.5.3 The Evaluation of Reaction Kinetics in TI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals ... 910 6.1.6 Mechanism of Sonication in PCI ww, OMI ww and TI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals. ... 910 6.1.6.1 Mechanism of Sonication in PCI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals. ... 910 6.1.6.2 Mechanism of Sonication in OMI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals.. 911 6.1.6.3 Mechanism of Sonication in TI ww during Sonication Process with
only Sonication and with the Addition of Chemicals... ... 911 6.1.7 The Evaluation of by-Products Removal Efficiencies in PCI ww and OMI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals ... 912 6.1.7.1 The Evaluation of by-Products Removal Efficiencies in PCI ww
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6.1.7.2 The Evaluation of by-Products Removal Efficiencies in PCI ww during Sonication Process with the Addition of Some Chemicals…... ... 912 6.1.7.3 The Evaluation of by-Products Removal Efficiencies in OMI ww
during Sonication Process with only Sonication.. ... 913 6.1.8 The Evaluation of Specific Energies in CODdis ( Es ), Electric Energy per Unit Volume in CODdis (EE/O) and Electrical Energy per Unit Mass in CODdis (EE/M) Values in PCI ww, OMI ww and TI ww during Sonication Process with only Sonication. ... 913 6.1.8.1 The Evaluation of Specific Energies in CODdis ( Es ), Electric Energy per Unit Volume in CODdis (EE/O) and Electrical Energy per Unit Mass in CODdis (EE/M) Values in PCI ww during Sonication Process with only Sonication.. ... 913 6.1.8.2 The Evaluation of Specific Energies in CODdis ( Es ), Electric Energy
per Unit Volume in CODdis (EE/O) and Electrical Energy per Unit Mass in CODdis (EE/M) Values in OMI ww during Sonication Process with only Sonication.. ... 914 6.1.8.3 The Evaluation of Specific Energies in CODdis ( Es ), Electric Energy per Unit Volume in CODdis (EE/O) and Electrical Energy per Unit Mass in CODdis (EE/M) Values in TI ww during Sonication Process with only Sonication. ... 915 6.1.9 The Evaluation of Costs in PCI ww, OMI ww, TI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals.... ... 916 6.1.9.1 The Evaluation of Costs in PCI ww, OMI ww and TI ww during
Sonication Process with only Sonication... ... 916 6.1.9.2 The Evaluation of Costs in PCI ww, OMI ww and TI ww during Sonication Process with the Addition of Some Chemicals.. ... 917 6.1.10 The Disscussions of Specific Energy and Cost in PCI ww, OMI ww and TI ww during Sonication Process with only Sonication and with the Addition of Some Chemicals. ... 917
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6.1.11 The Comparison of Anaerobic, Aerobic, Ultraviolet (UV), Ozone (O3) and Sonication Treatment Processes... ... 918 6.2 Recommendations... ... 921 REFERENCES ... 923 APPENDICES ... 987 List of Tables ... ….987 List of Figures... .1030 List of Appendices ... .1061
1
CHAPTER ONE INTRODUCTION
1.1 Introduction
The chemical and biological effects of ultrasound were first reported by Alfred Lee Loomis as early as 1927 (Suslick, 1989). In recent years, ultrasound irradiation has received increasing attention for the destruction of organic pollutants in waters and wastewaters (Thompson & Doraiswamy, 1999). The process comprises cyclic formation, growth and subsequent collapse of microbubbles occurring in extremely small intervals of time, and release of large quantities of energy over a small location. Sonochemical degradation in aqueous phase involves several reaction pathways and zones such as pyrolysis inside the bubble and/or at the bubble–liquid interface and hydroxyl radical-mediated reactions at the bubble–liquid interface and/or in the liquid bulk (Thompson & Doraiswamy, 1999, 2000). The relative importance of the various mechanisms involved primarily depends on the physicochemical properties of the pollutants in question; the process is more selective towards hydrophobic and volatile species that can be degraded easily via pyrolytic reactions, while hydrophilic and less volatile compounds are degraded slowly via hydroxyl radical-induced reactions (Suslick, 1989).
Numerous works have demonstrated the efficiency of ultrasounds toward the degradation of a wide variety of organic compounds including estrogens [for instance, 17b-estradiol (b-E2), estrone (E1), 17a-ethynylestradiol (EE2)], endocrine-disrupting chemicals (EDCs) (such as bisphenol A), pharmaceuticals, vegetable oils, nitroorganics (NOCs), trihalomethanes (THMs), aliphatic hydrocarbons, naphthenic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) organochlorine pesticides (OCPs), sugars, tannins, pectin, lipids, polyphenols and polyalcohols, etc. present in relatively dilute aqueous solution and it appears that the applications of this novel means of reaction in environmental remediation and pollution prevention is unlimited (Adewuyi, 2001; Beens et al., 2000; Colussi et al.,
2
1996, 1999; David et al., 1998; Drijvers et al., 1999; Kotronarou et al., 1991; Mason, 1998; Mason et al., 2003; Okuno et al., 2000; Pétrier et al., 1994, 1998; Psillakis et al., 2004; Sanchez-Prado et al., 2008; Serpone et al. 1994; Torres et al., 2007, 2008a, 2008b; Vassilakis et al., 2004).
The intensification of the organic matter solubilization induced by the ultrasonic action, can lead to an increase of the bioavailability of some micropollutants to the degrader consortium (Tiehm & Neis, 1999, 2005; Tiehm, 2001). Nevertheless, it is of great interest to study such ubiquitous compounds (PAHs, THMs, OCPs, EDCs, NOCs, etc.), because they are widespread in all parts of the environment; air, water, soils and sediments (Beens et al., 2000; Broman et al., 1991; Colussi et al., 1999; Jones et al., 1989; Marvin et al., 2000; Menzie et al., 1992).
An important refractory family compounds in petrochemical industry wastewater (PCI ww) are the PAHs, which have a hydrophobic character, a low water solubility and less volatile with increasing molecular weight that limit their biodegradation, their hazard potential can be relatively high, thus making their presence in the water cycle both an acute and a chronic risk to human health and environmental quality (Suslick et al., 1986; Wheat & Tumeo, 1997). Most of the time, compounds studied are hydroxylated and/or halogenated substituted aromatics or hydrocarbons, having a water solubility in a mg/l range. Only a few works concern the degradation of compounds such as PAHs [anthracene (ANT), benzo[k]fluoranthene (BkF), pyrene (PY), benzo[a]pyrene (BaP), etc.] in PCI ww for which solubilities are in the ng/ml range (Cataldo, 2000; David & Riguier, 2009; Laughrey et al., 2001; Little et al., 2002; Meckes et al., 1996; Psillakis et al., 2003, 2004; Taylor Jr. et al., 1999; Wheat & Tumeo, 1997). These compounds have been listed by the United States Environmental Protection Agency (US. EPA) and the European Unions European Economic Community (EU EEC) since 1979 and 1980, respectively, as priority pollutants (Banjoo & Nelson, 2005; Callahan et al., 1979; EU EEC, 1994; Taylor Jr. et al., 1999; US EPA Pollution Control Agency, 2006; Wheat & Tumeo, 1997). Due to associated health concerns, some PAHs are possible or probable human carcinogen such as BaP and all PAHs having four condensed rings (Kim Oanh et al.,
2002). The distribution, fate and destruction of these pollutants are then of special significance, especially in water. PAHs are ubiquitous environmental pollutants with mutagenic properties, which have not been included in the Turkish guidelines for treated waste monitoring programmes (Papadaki et al., 2004).
As a consequence of their strongly hydrophobic properties and their resistance to biodegradation, PAHs are not always quantitatively removed from wastewaters by activated sludge treatments, which very efficiently relocate them into treated effluents. In recent years, considerable interest has been shown in the application of ultrasound as an AOPs for the treatment of hazardous contaminants, such as PAHs in water (Huang et al., 2002; Laughrey et al., 2001; Suslick, 2000). The sonication process is capable of effectively degrading PAHs present in dilute solutions, typically in the micro and nano ranges. PAHs were degradated to less toxic and less carcinogenic products and by-products with addition some catalysts during ultrasonic treatment. However, it is notable that none of the studies report the use of ultrasound for the removal of more hydrophobic PAHs compounds typically found in effluents of PCI ww.
In Izmir-Turkey, the petrochemical industry treatment plant wastewaters are treated with conventional activated sludge systems and approximately seventeen hydrophilic, less and more hydrophobic PAHs [naphthalene (NAP), acenaphthylene (ACL), acenaphthene (ACT), fluorene (FLN), phenanthrene (PHE), ANT, carbazole (CRB), fluoranthene (FL), PY, benz[a]anthracene (BaA), chrysene (CHR), benz[b]fluoranthene (BbF), BkF, BaP, indeno[1,2,3-cd]pyrene (IcdP), dibenzo[a,h]anthracene (DahA) and benzo[g,h,i]perylene (BghiP)]are released into receiving bodies, since low COD (56.00%) and PAHs (39.00–42.00%) removal efficiencies are observed. Aerobic activated treatment systems are not equipped for PAHs removal efficiently. PAHs residues have been frequently detected in rivers and lakes that receive sewage and industrial effluents supplied by those surface waters (Psillakis et al., 2004).
