摘要
污水在處理過程中可生成並釋放CO2，在厭氧處理與污泥消化程序會產生CH4，污水中所含的溶解性氮則可經由生物轉化生成N2O等溫室氣體。由於全球暖化對環境的嚴重衝擊，減少來自污水處理過程溫室氣體的逸散排放，並確認影響其逸散機制的影響因子，確有其必要性及重要的環境價值。本研究探討高雄市仁武工業區的石化污水處理廠，本研究選用兩種不同方法在污水處理場的操作單元進行溫室氣體採樣及分析，這些單元包含以污水處理為主的調和池、初沉池、曝氣池、終沉池及以污泥處理為主的厭氧消化池、好氧消化池。採樣過程在處理單元液面上方，利用浮動氣罩直接採集液面逸散之溫室氣體，降低監測點與液面間因氣體擾動等因素產生之誤差，並在浮動氣罩上方連接監測管至Teflon採樣管線，進行液面上方溫室氣體濃度的即時線上量測(in-situ on-line monitoring)，以監測數據進一步應用於估算溫室氣體排放總量，排放因子和排放通量。此外，以實驗室規模生物反應器現地實驗以瞭解好氧處理單元在不同操作條件下，包含顆粒狀活性炭(GAC)與污泥濃度、停留時間、與曝氣強度的改變對廢水處理過程中溫室氣體逸散及廢水處理效能之影響，並估算液能，瞭解隨著不同操作條件變化下不同溫室氣體質傳潛勢之變化。
結果顯示在不同處理單元及三種不同操作方式中溫室氣體排放。在冬季CO2，CH4及N2O排放總量分別為223.3 ± 15.53 kgCO2e d-1，28.22 ± 9.62 kgCO2e d-1， and 491.7 ± 96.85 kgCO2e d-1，在夏季CO2，CH4及N2O排放總量分別為258.41 ± 8.92 kgCO2e d-1, 37.74 ± 6.12 kgCO2e d-1, and 427.03 ± 33.37 kgCO2e d-1，從結果得知石化業污水處理場溫室氣體排放較高的處理單元有調勻池、曝氣池及終沉池等。以實驗室規模進行現地好氧處理模擬實驗中發現，降低曝氣量會使CO2及N2O排放濃度增加，並同時造成較高的溫室氣體質傳速率，而在實場中增加曝氣量，可使CO2及N2O排放濃度在有限之廢水處理效能影響下降低以減少的溫室氣體排放；污泥濃度變化雖然也可減少曝氣池溫室氣體排放濃度但可能部分影響實場廢水處理之效能；而在改變停留時間之過程則觀察到明顯增加之溫室氣體排放濃度排放及其總逸散量。

ABSTRACT
In conventional wastewater treatment processes, carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) are formed and/or emitted through energy consumption, anaerobic reactions and sludge digestion, and biotransformation of dissolved nitrogen-containing compounds in water, respectively. Due to substantial impact of global warming on the environment, it is important to reduce the emissions of GHG such as CO2, CH4, and N2O from wastewater treatment processes and to understand influential factors to develop effective and efficient control strategies in the future. In this study, a petrochemical wastewater treatment plant in the Ren-Da Industrial Complex located in the north of Kaohsiung City, Taiwan was selected. Two different approaches, the continuous in-situ monitoring by an on-site measuring equipment and sampling with a floating chamber equipped with an infrared gas analyzer was employed to investigate the greenhouse gas emissions from wastewater surface in different treatment units. The monitored concentrations were further applied to estimate the total GHG emission, emission factors, and emission fluxes. In addition, lab-scale bioreactor experiments were conducted in batch to understand the effects of various operational parameters on the greenhouse gas emissions in the aerobic biological granular activated carbon (GAC) treatment process of the WWTP. The concentration variation data acquired in the experiments were further used to estimate the mass transfer rates coefficients, and fluxes between the air and water phases, fugacity and possible variations of air-phase concentrations with time.
The results showed different characteristics with respect to the emissions of three greenhouse gases in different treatment units in the wastewater of interest. In winter, the total emissions of CO2, CH4, and N2O were 223.3 ± 15.53 kgCO2e d-1, 28.22 ± 9.62 kgCO2e d-1, and 491.7 ± 96.85 kgCO2e d-1, respectively. In summer, the emissions of CO2, CH4, and N2O were 258.41 ± 8.92 kgCO2e d-1, 37.74 ± 6.12 kgCO2e d-1, and 427.03 ± 33.37 kgCO2e d-1, respectively. The equalization tank, the aeration tank, and the final settling tank constituted the highest GHG emitted from the treatment units of the WWTP. The lab-scale experiments simulating the aerobic biological process showed that, reducing the aeration rate in the experiments conducted increased the emission concentration of N2O and CO2, respectively, which also led to high mass transfer rates. Although the concentrations of specific greenhouse gases were elevated by reducing the aeration rate, but this could reduce the energy consumption of the WWTP, causing the reduction of aeration rate at the aeration tank as one of the possible strategies to reduce the associated greenhouse gas emissions. The effects of changing the sludge concentration ratio within a limited range from the original concentration to avoid adversely affecting the treatment performance of the process might also possibly reduce the GHG concentration in aeration tank to avoid adversely affecting the performance of the treatment process. Reducing the SRT affects the GHG concentrations as high GHG concentrations are emitted when the SRT was reduced.
These findings suggested that the results acquired from the continuous monitoring and lab-scale simulation experiments could be further used to develop life cycle assessment models and hence can establish novel technical strategies with expected profits of lower greenhouse gas emissions and lower treatment costs.

Abstract i
Content iii
List of Figures vi
List of Tables ix
CHAPTERONE- Research Background and Objectives 1
　1.1 Nature of Greenhouse Gases (GHGs) 1
　　1.1.1 Current Trends of GHGs 1
　　1.1.2 Petrochemical Industry 3
　　1.1.3 Greenhouse Gases and the International Protocol 3
　　1.1.4 Taiwan and the International Protocols 4
　1.2 Research Objectives 5
CHAPTER TWO- Literature Review 7
　2.1 Greenhouse Gases from Wastewater Treatment Plants 8
　　2.1.1 Carbon Dioxide 8
　　2.1.2 Methane 9
　　2.1.3 Nitrous Oxide 10
　2.2 Greenhouse Gas Emissions from Different Sources 13
　2.3 Greenhouse Gas Emissions from Wastewater Treatment Plants 14
　2.4 Types of Industrial Wastewater Treatment 16
　2.5 Characteristics of Petrochemical Wastewater 17
　2.6 Petrochemical Wastewater Treatment Units 18
　2.7 GHG measurement and monitoring 20
　2.8 Possible Strategies of Wastewater Plants for Greenhouse Gas emissions Reduction 21
CHAPTER 3- Materials and Methods 24
　3.1 Introduction 24
　3.2 GHG Emission Monitoring in a Full-scale WWTP 25
　　3.2.1 Field Site Description 25
　　3.2.2 Monitoring and Analysis 27
　3.3 Emission Flux, Emission Factors, and Total Emission of GHGs 28
　　3.3.1 Emission Flux 28
　　3.3.2 Emission Factors 28
　　3.3.3 Emission Estimation 29
　3.4. GHG Emission Monitoring in a Lab-scale Batch Bioreactors 29
　　3.4.1 Description of Aeration Tank 29
　　3.4.2 Experimental Setup and Sampling 30
　　3.4.3 GHG Analyses in the Gas and Liquid Phases 33
　3.5 Multimedia Fugacity Model 35
　3.6 Mass Transfer Potentials 37
　　3.6.1 Mass Transfer Coefficients 38
　　3.6.2 Mass Transfer Flux 39
　　3.6.3 Variations of GHG Concentrations in the Air Phase 39
CHAPTER FOUR- Results and Discussion 41
　4.1 Introduction 41
　　4.1.1 GHG Emission Concentrations from the Examined WWTP in the 41
　　4.1.2 GHG Emission Factors from Each Treatment Unit 42
　　4.1.3 Total GHG Emission Generated by Each Treatment Unit 44
　4.2 Laboratory-scale Simulation Experiments of the Aerobic biological Treatment Processes 46
　　4.2.1 Impact of Variation of Operating Parameters on Seasonal GHG Emission 47
　　　4.2.1.1 Effects of Sludge Concentration at Different Ratios in the Winter Season 47
　　　4.2.1.2 Effects of Sludge Concentration at Different Ratios in the Summer Season 49
　　　4.2.1.3 Effects of Contact Time in the Winter Season 52
　　　4.2.1.4 Effects of Contact Time in the Summer Season 55
　　　4.2.1.5 Effects of Aeration Rate in the Winter Season 57
　　　4.2.1.6 Effects of Aeration Rates in the Summer Season 60
　4.3 Variations of GHG Concentrations in the Air Phase 62
　　4.3.1 Effects of Sludge Concentration Ratio in the Winter Season 63
　　4.3.2 Effects of Sludge Concentration Ratio in the Summer Season 65
　　4.3.3 Effects of the Contact Time in the Winter Season 67
　　4.3.4 Effects of the Contact time in the Summer Season 69
　　4.3.5 Effects of the Aeration Rate in the Winter Season 72
　　4.3.6 Effects of the Aeration rate in the Summer Season 74
　4.4 Fugacity-Fates of GHGs through Aerobic Biological Treatment Processes 76
　　4.4.1 Effects of Sludge Concentration Ratio 76
　　4.4.2 Effects of Contact Time 78
　　4.4.3 Effects of Aeration Rate 80
　4.5 Mass Transfer Rates between Air and Water Phases and its Effects on the Variation in the Operation Conditions 82
　4.6 Correlation Analysis among the Operating Parameters in the Lab-Scale Simulation Experiment in the Aeration Tank 85
　4.7 Strategies to Minimize the GHG Emissions in the Aerobic Biological Treatment Process 86
CHAPTER FIVE- Findings and Future Works 91
　5.1 Findings 91
　5.2 Future Works 93
REFERENCES 94
APPENDIX A 102

Aboobakar A, Cartmell E, Stephenson T, Jones M, Vale P, and Dotro G (2013). Nitrous oxide emissions and dissolved oxygen profiling in a full-scale nitrifying activated sludge treatment plant. Water Res; 47:524–34.
Ahn, J.H., Kim, S., Park, H., Katehis, D., Pagilla, K. and Chandran, K. (2010a) Spatial and temporal variability in atmospheric nitrous oxide generation and emission from full-scale biological nitrogen removal and non-BNR processes. Water Environment Research 82(12), 2362-2372.
Al.Coelho, A.V. Castro, M. Dezotti, and G.L. Sant’Anna Jr. Treatment of petroleum refinery sourwater by advanced oxidation processes (2006). Journal of Hazardous Materials, B137 pp. 178–184.
Basheer Hasan Diya’uddeen, Wan Mohd Ashri Wan Daud, and A.R. Abdul Aziz (2011). Treatment technologies for petroleum refinery effluents: A review. Process Safety and Environmental Protection Vol. 89, (2011), pp 95–105.
Bogner J., Hashimoto S., Diaz C., Mareckova K., Diaz L., Kjeldsen P., Monni S., Faaij A., Qingxian G., Tianzhu Z., Ahmed M.A., Sutamihardja R.T.M and Gregory R. (2008) Mitigation of global greenhouse gas emissions from waste: conclusions and strategies from the intergovernmental panel on climate change (IPCC) fourth assessment report, working group III (mitigation). Waste Management; Research 26:11-32.
Cakir F.Y and Stenstrom M.K. (2005) Greenhouse gas production: A comparison between aerobic and anaerobic wastewater treatment technology. Water Research 39:4197-4203.
Chayan kumer Saha (2011). Mass Transfer processes of odorants in aerial boundary layers.
Colliver, B.B. and Stephenson, T. (2000) Production of nitrogen oxide and dinitrogen oxide by autotrophic nitrifiers. Biotechnology Advances 18(3), 219-232.
Czepiel, P., Crill, P., and Harriss, R. (1993). Methane Emissions from Municipal Wastewater Treatment Processes. Environmental Science Technology, 27, pp. 2472-2477.
Daelman, M.R.J., van Voorthuizen, E.M., van Dongen, U.G.J.M., Volcke, E.I.P. and van Loosdrecht, M.C.M. (2012) Methane emission during municipal wastewater treatment. Water Research 46(11), 3657-3670.
Daelman, M.R., van Voorthuizen, E.M., van Dongen, L.G., Volcke, E.I., and van Loosdrecht, M.C. (2013). Methane and nitrous oxide emissions from municipal wastewater treatment – results from a long-term, 67 study. Water Science Technology (10), pp. 2350–2355.
Daeseung Kyung, Minsun Kim, Jin Chang, and Woojin Lee (2015). Estimation of greenhouse gas emissions from a hybrid wastewater treatment plant. Journal of Cleaner Production 95 (2015) 117e123.
Desloover, J., De Clippeleir, H., Boeckx, P., Du Laing, G., Colsen, J., Verstraete, W. and Vlaeminck, S.E. (2011) Floc-based sequential partial nitritation and anammox at full-scale with contrasting N2O emissions. Water Research 45(9), 2811-2821.
El-Fadel, M., and Massoud, M. (2001). Methane emissions from wastewater management. Environmental Pollution, 114, pp. 177–185.
Energy Information Administration (EIA). (2003). Emission of Greenhouse gases in the United States. DOE/EIA-0573.
Fred, T., Heinonen, M., Sundell, L. and Toivikko, S. (2009) Air emissions at large municipal wastewater treatment plants in Finland for national E-PRTR reporting register. Water Practice & Technology 4(2).
Foley, J., de Haas, D., Yuan, Z., and Lant, P. (2010a). Nitrous oxide generation in full-scale biological nutrient removal wastewater treatment plants. Water Research, 44, pp. 831–844.
Guisasola, A., de Haas, D., Keller, J. and Yuan, Z. (2008) Methane formation in sewer systems. Water Research 42(6-7), 1421-1430.
Hanaki, K., Hong, Z. and Matsuo, T. (1992) Production of nitrous oxide gas during denitrification of wastewater. Water Science and Technology 26(5-6), 1027-1036.
Incropera, DeWitt, Bergman and Lavine (2007).Fundamentals of Heat and Mass Transfer, sixth edn, John Wiley & Sons.
IPCC (2006). Guidelines for National Greenhouse Gas Inventories. Cambridge: Cambridge University Press, Cambridge, UK.
IPCC, (2013): Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change [Stocker, T.F., D. Qin, G.-K. Plattner, M. Tignor, S.K. Allen, J. Boschung, A. Naues, Y. Xia, V. Bex and P.M. Midgley (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, pp 1535.
Jeff Foley and Paul Lant (2009). Direct Methane and Nitrous Oxide emissions from full-scale wastewater treatment systems. WSAA Occasional Paper No.24.
Kampschreur, M.J., Temmink, H., Kleerebezem, R., Jetten, M.S.M. and van Loosdrecht, M.C.M. (2009) Nitrous oxide emission during wastewater treatment. Water Research 43(17), 4093-4103.
Kampschreur, M.J., Kleerebezem, R., de Vet, W.W.J.M. and van Loosdrecht, M.C.M. (2011) Reduced iron induced nitric oxide and nitrous oxide emission. Water Research 45(18), 5945-5952.
Kaohsiung Environmental Protection Agency (2010): Innovative Climate City Kaohsiung, Taiwan.
Kimochi, Y., Inamori, Y., Mizuochi, M., Xu, K.-Q., Matsumura, M., 1998. Nitrogen removal and N2O emission in a full-scale domestic wastewater treatment plant with intermittent aeration. Journal of Fermentation and Bioengineering 86 (2), 202–206.
Law, Y., Ye, L., Pan, Y., and Yuan, Z. (2012). Nitrous oxide emissions from wastewater treatment processes. Philosophical Transactions of the Royal Society B, 367, pp. 1265–1277.
Lewis WK, and Whitman WG (1924) Principles of gas absorption. Ind. Eng. Chem. 16:1215–1220.
Li-Yang Zhan, Li-Qi Chen, Jie-Xia Zhang, and Qi Lin (2013) A system for the automated static headspace analysis of dissolved N2O in seawater. International Journal of Environmental Analytical Chemistry, 93:8, 828-842.
M. Al Zarooni, and W. Elshorbagy. Characterization and assessment of Al Ruwais refinery wastewater. Journal of Hazardous Materials, A136 (2006), pp. 398–405.
M. Bani Shahabadi, L. Yerushalmi, and F. Haghighat (2009). Impact of process design on greenhouse gas (GHG) generation by wastewater treatment plants. Water Research 43 2679–2687.
Mohareb A.K., Warith M., and Narbaitz R.M. (2004) Strategies for the municipal solid waste sector to assist Canada in meeting its Kyoto Protocol commitments. Environmental Reviews 12:71-95.
Monteith, H. D., Sahely, H. R., MacLean, H. L., and Bagley, D. M. (2005). A rational procedure for estimation of greenhouse-gas emissions from municipal wastewater treatment plants. Water Environment Research, 77(4), 390-403.
Mohareb, A. K., Warith, M. A., and Diaz, R. (2008). Modelling greenhouse gas emissions for municipal solid waste management strategies in ottawa, ontario, canada. Resources, Conservation and Recycling, 52(11), 1241-1251.
National Oceanic & Atmospheric Administration (2015). Earth System Research Laboratory
Norbertus J. R. Kraakman & Jose Rocha-Rios & Mark C. M. van Loosdrecht (2011) Review of mass transfer aspects for biological gas treatment. Appl Microbiol Biotechnol DOI 10.1007/s00253-011-3365-5.
NRC (2010). Advancing the Science of Climate Change. National Research Council. The National Academies Press, Washington, DC, USA.
O'Connor, D.J., and Dobbins, W.E (1958). Mechanism of reaeration in natural streams: American Society of Civil Engineers Proceedings, Transactions. Vol 123, pp 641-666.
Omid Ashrafi, Laleh Yerushalmi, and Fariborz Haghighat (2013). Greenhouse gas emission by wastewater treatment plants of the pulp and paper industry – Modeling and simulation. International Journal of Greenhouse Gas Control. Vol 17, pp 462–472.
R.M. Pérez, G. Cabrera, J.M. Gómez, A. Ábalos, D. Cantero. Combined strategy for the precipitation of heavy metals and biodegradation of petroleum in industrial wastewaters Journal of Hazardous Materials, 182 (2010), pp. 896–902.
Rittmann, B.E. and McCarty, P.L. Environmental Biotechnology (2001): Principles and Applications, McGraw-Hill
Rodriguez-Caballero a, I. Aymerich a, M. Poch b, and M. Pijuan (2014). Evaluation of process conditions triggering emissions of green-house gases from a biological wastewater treatment system. Sci. of the Total Environ. 493 384–391.
Shahabadi, B. M., Yerushalmi, L., and Haghighat, F. (2010). Estimation of greenhouse gas generation in wastewater treatment plants - model development and application. Chemosphere, 78(9), 1085-1092.
Schreiber, F., Wunderlin, P., Udert, K.M. and Wells, G.F. (2012) Nitric oxide and nitrous oxide turnover in natural and engineered microbial communities: biological pathways, chemical reactions and novel technologies. Frontiers in microbiology 3.
Stephenson, R., Price, K., and Hoy, P. (2007). How Micro Sludge can lower greenhouse gases at wastewater treatment plants. IEEE EIC Climate Change Technology Conference, EICCCC.
Taiwan Environmental Protection Agency (Taiwan EPA): Global Atmospheric Protection.
Tchobanoglous, G., Burton, F. L. and Stensel, H. D. 2003. Wastewater Engineering Treatment and Reuse. 4th Edn. Metcalf and Eddy. Inc. McGraw-Hill Company.
Wilke CR, and Chang P. (1955). Correlation of diffusion coefficients in dilute solutions. AICHE J 1:264–270.
Wunderlin, P., Mohn, J., Joss, A., Emmenegger, L. and Siegrist, H. (2012) Mechanisms of N2O production in biological wastewater treatment under nitrifying and denitrifying conditions. Water Research 46(4), 1027-1037.
Ye, L., Ni, B.-J., Law, Y., Byers, C. and Yuan, Z. (2014) A novel methodology to quantify nitrous oxide emissions from full-scale wastewater treatment systems with surface aerators. Water Research 48, 257-268.
Yerushalmi L., Bani Shahabadi M., and Haghighat F. (2011) Effect of process parameters on greenhouse gas generation by wastewater treatment plants. Water Environment Research 83:440-449.
Ying hao Yu (2008) Application of a methanotrophic immobilized soil bioreactor to trichloroethylene degradation. PhD Dissertation, Canada
Yoshida, H., Clavreul, J., Scheutz, C., & Christensen, T. H. (2014). Influence of data collection schemes on the Life Cycle Assessment of a municipal wastewater treatment plant. Water Research. doi:10.1016/j.watres.