Study of nutrients recovery from poultry wastewater by modified biochar for soil application

VIETNAM NATIONAL UNIVERSITY HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY -o0o - NGUYEN LAN THANH STUDY OF NUTRIENTS RECOVERY FROM POULTRY WASTEWATER BY MODIFIED BIOCHAR FOR SOIL APPLICATION NGHIÊN CỨU THU HỒI CHẤT DINH DƯỠNG TỪ NƯỚC THẢI CHĂN NUÔI BẰNG BIOCHAR BIẾN TÍNH ĐỊNH HƯỚNG PHÂN BĨN Major: Environmental Engineering Major code: 8520320 MASTER’S THESIS HO CHI MINH CITY, July 2023 THIS THESIS IS COMPLETED AT HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY – VNU-HCM Supervisor: Dr Vo Thanh Hang Examiner 1: Assoc Prof Ph.D Nguyen Tan Phong Examiner 2: Dr Huynh Thi Ngoc Han This master’s thesis is defended at HCM City University of Technology, VNU- HCM City on 29th July 2023 Master’s Thesis Committee: Chairman: Assoc Prof Ph.D Dang Viet Hung Member : Assoc Prof Ph.D Dang Vu Bich Hanh Examiner: Assoc Prof Ph.D Nguyen Tan Phong Examiner: Dr Huynh Thi Ngoc Han Secretary: Dr Le Thi Huynh Tram Approval of the Chairman of Master’s Thesis Committee and Dean of Faculty of Environment and Natural Resources after the thesis being corrected (If any) CHAIRMAN OF THESIS COMMITTEE HEAD OF FACULTY OF ENVIRONMENT AND NATURAL RESOURCES VIETNAM NATIONAL UNIVERSITY - HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY SOCIALIST REPUBLIC OF VIETNAM Independence – Freedom - Happiness THE TASK SHEET OF MASTER’S THESIS Full name: Nguyen Lan Thanh Student ID: 2070577 Date of birth: 13/10/1998 Major: Environmental Engineering Place of birth: HCM city Major ID: 8520320 I THESIS TITLE (In Vietnamese): Nghiên cứu thu hồi chất dinh dưỡng từ nước thải chăn nuôi biochar biến tính định hướng phân bón II THESIS TITLE (In English): Study of nutrients recovery from poultry wastewater by modified biochar for soil application III TASKS AND CONTENTS: - Content 1: Biochar preparation and modification - Content 2: Evaluating factors effect on synthetic wastewater - Content 3: Evaluating factors effect on poultry wastewater - Content 4: Evaluating the slow-released ability of biochar fertilizer - Content 5: Soil application IV THESIS START DAY: (master’s thesis decision date) 14/02/2022 V THESIS COMPLETION DAY: (master’s thesis decision date) 12/06/2023 VI SUPERVISOR: Dr Vo Thanh Hang Ho Chi Minh City, date …,…2023 SUPERVISOR (Full name and signature) HEAD OF DEPARTMENT (Full name and signature) DEAN OF FACULTY OF ENVIRONMENT AND NATURAL RESOURCES (Full name and signature) ACKNOWLEDGEMENT I would like to express my heartfelt gratitude and appreciation to everyone who has helped me along the way to finishing this thesis Due to a lack of time and knowledge, some of the information in this thesis cannot be sufficient and complete; please be understanding for my shortcoming First and foremost, I want to express my gratitude to Dr Vo Thanh Hang, Assoc Prof Ph.D Nguyen Nhat Huy, M.Sc Lam Pham Thanh Hien, M.Sc Vo Thi Thanh Thuy for their guidance, patience, and invaluable insights throughout the entire research process Their knowledge, encouragement, and constructive criticism were instrumental in shaping the direction and quality of this thesis I am also eternally thankful to our laboratory 710 H2 group members, who has shared their knowledge and provided a stimulating academic environment Their dedication to learning and research has had a significant impact on my intellectual development Furthermore, I would like to acknowledge my friends and family for their unwavering support, encouragement, and understanding throughout this challenging but rewarding academic endeavor Their faith in my abilities and consistent motivation has been critical to my success Lastly, I would like to acknowledge the countless individuals who have contributed in numerous ways, whether through discussions, assistance, or moral support Your contributions may not be mentioned individually, but they have played a key role in shaping my academic and personal growth To all those mentioned and those who remain unnamed, I am profoundly grateful for your support and belief in me This thesis would not have been possible without your contributions Ho Chi Minh City, July 2023 Nguyen Lan Thanh i ABSTRACT In this research, we propose and evaluate a novel approach for the treatment of poultry wastewater using a composite adsorbent derived from agricultural waste and water supply sludge The ultimate objective is to transform the treated wastewater into a viable fertilizer suitable for agricultural applications The modified biochar, a key component of the adsorbent, was synthesized by incorporating crop residues, water treatment plant sludge, and magnesium salt The resulting biochar was subjected to a comprehensive characterization process encompassing scanning electron microscopy, energy-dispersive X-ray spectroscopy, Brunauer-Emmett-Teller analysis, and X-ray diffraction Subsequently, the adsorption performance of the modified biochar was assessed with respect to ammonia and phosphate removal, employing both synthetic and actual poultry wastewater samples The study also investigated the influence of various experimental parameters, including the nitrogen-to-phosphorus (N/P) ratio, initial concentrations of ammonium and phosphate, pH, and the quantity of biochar, on the adsorption capacity of ammonia and phosphate The outcomes of the experimental design revealed that the optimal conditions yielded remarkable adsorption capacities of 60.64 mgNH4+-N/g and 66.24 mgPO43 P/g These conditions encompassed an N/P ratio of 1.25, an initial concentration of 90 mg/L, a pH level of 6, and a biochar mass of 0.105 g The optimum value was applied for produced biochar as a fertilizer and assessed for slow-released ability The pink swamp mallow was treated with biochar, chemical and untreated for control sample We cannot conclude the slow-released ability of this biochar, but the plant with biochar treated develop normally like the others ii TÓM TẮT LUẬN VĂN THẠC SĨ Trong nghiên cứu này, đề xuất đánh giá phương pháp để xử lý nước thải gia cầm cách sử dụng chất hấp phụ tổng hợp có nguồn gốc từ chất thải nông nghiệp bùn nước cấp Mục tiêu cuối sử dụng nguồn dinh dưỡng có sẵn nước thải trở thành phân bón ứng dụng cho nơng nghiệp Than sinh học biến tính, tổng hợp cách kết hợp phế phẩm nông nghiệp, bùn nhà máy xử lý nước muối magie Than sinh học thu được phân tích tính chất phương pháp đại bao gồm kính hiển vi điện tử quét, quang phổ tia X phân tán lượng, phân tích Brunauer-Emmett-Teller nhiễu xạ tia X Sau đó, hiệu suất hấp phụ than sinh học biến tính đánh giá hiệu suất loại bỏ amoni phốt phát mẫu nước giả thải mẫu thực tế Nghiên cứu đánh giá ảnh hưởng thơng số thí nghiệm khác nhau, bao gồm tỷ lệ nitơ-phốt (N/P), nồng độ ban đầu amoni phốt phát, độ pH lượng than sinh học đến khả hấp phụ amonia phốt phát Kết thiết kế thực nghiệm cho thấy điều kiện tối ưu cho khả hấp phụ vượt trội 60,64 mgNH4+-N/g 66.24 mgPO43 P/g Những điều kiện bao gồm tỷ lệ N/P 1.25, nồng độ ban đầu 90 mg/L, độ pH khối lượng than sinh học 0.105 g Giá trị tối ưu áp dụng cho than sinh học sản xuất làm phân bón đánh giá khả nhả chậm Cây sâm bố bón phân từ than sinh học, so sánh với phân hóa học mẫu đối chứng Kết luận, than sinh học chưa thể đánh giá khả nhả chậm, sâm bố sử dụng than sinh học có tốc độ phát triển tính chất hai loại đối chứng iii THE COMMITMENT OF THE THESIS’ AUTHOR I hereby declare that this thesis is solely my original work and that the content presented within it is entirely accurate The data and tables used for analysis and guidance in this study have been sourced from various references, and proper attributions are provided in the references or footnotes immediately beneath the respective tables Moreover, to provide additional clarification for the analyzed and referenced arguments, explanatory documents are included in the appendix, along with annotated data sources Ho Chi Minh City, July 2023 Nguyen Lan Thanh iv TABLE OF CONTENT ACKNOWLEDGEMENT i ABSTRACT ii TÓM TẮT LUẬN VĂN THẠC SĨ iii THE COMMITMENT OF THE THESIS’ AUTHOR iv TABLE OF CONTENT v ACRONYMS viii LIST OF FIGURES ix LIST OF TABLES xi CHAPTER INTRODUCTION 1.1 Motivation 1.2 Research’s aim and content 1.2.1 Research’s aim 1.2.2 Research’s content 1.3 Research’s subject and scope 1.3.1 Research’s subject 1.3.2 Research’s scope 1.4 Scientific contribution and prospective application 1.4.1 Scientific contribution 1.4.2 Prospective application CHAPTER LITERATURE REVIEW 2.1 Overview of animal agriculture 2.2 Environmental affection 2.2.1 Polluted by solid waste 2.2.2 Polluted by wastewater 2.3.1 Mechanical treatment method 12 2.3.2 Physicochemical treatment method 13 2.3.3 Biological processes 14 2.3.4 Brief conclusion 14 2.4 Adsorbent material 15 2.4.1 Adsorption procedure 15 2.4.2 Adsorbent materials 15 2.5 2.5.1 Biochar 16 Definitions 16 v 2.5.2 Biochar properties 17 2.5.3 Application of biochar 20 2.5.4 Biochar production 21 2.5.7 Application in Viet Nam 29 2.6 Agricultural waste 30 2.6.1 Definition 30 2.6.2 Animal agriculture waste 30 2.6.3 Crop residues 31 2.6.4 The reality of crop residues in Vietnam 31 2.7 Sludge 33 2.7.1 Definition of sludge 33 2.7.2 The negative effect of sludge 36 2.7.3 Sludge treatment method 37 2.8 Review studies in Vietnam and international 39 2.8.1 In Vietnam 39 2.8.2 International 40 2.8.3 Brief conclusion 41 CHAPTER MATERIALS AND METHODS 43 3.1 Equipment and material 43 3.2 Material preparation 44 3.2.1 Biochar preparation 44 3.2.2 Sludge preparation 45 3.4 Adsorption experiment 46 3.4.1 Evaluating adsorption of biochar and sludge on synthetic wastewater 46 3.4.2 Evaluating adsorption of biochar and sludge on real wastewater 46 3.4.3 Evaluating slow – release 47 3.4.4 Soil application 48 3.5 Analyzing method 48 3.5.1 Ammonium analyzing method 48 3.5.2 Phosphate analyzing method 49 3.6 Calculation 51 3.6.1 Removal efficiency 51 3.6.2 Adsorption capacity 51 CHAPTER RESULTS AND DISCUSSION 54 4.1 The preliminary results 54 vi 4.2 Biochar characterization 56 4.2.1 Surface morphology and pore structure of 10% Mg-biochar 56 4.2.2 Compositions and structure of modified biochar 57 4.3 Optimization 62 4.3.1 Model fitting and statical analysis 62 4.3.2 Interactive effect of variable on models 66 4.4 Optimization results 71 4.4.1 Application on sythetic wastwater 71 4.4.2 Application on actual wastewater 72 4.5 Slow-release experiment 74 4.5.1 Slow release in water 74 4.5.1 Slow release in soil 76 4.6 Soil application 77 4.7 Cost for g of modified biochar 82 CHAPTER CONCLUSION AND RECOMMENDATION 84 5.1 Conclusion 84 5.2 Recommendation 84 PUBLICATIONS 86 REFERENCES 119 APPENDIX I 130 APPENDIX II 133 APPENDIX III 134 VITA 135 vii no 07, pp 151–159, 2021 [20] H Huang, Y Chen, Y Jiang, and L Ding, “Treatment of swine wastewater combined with MgO-saponification wastewater by struvite precipitation technology,” Chem Eng J., vol 254, pp 418–425, Oct 2014 [21] J La, T Kim, J K Jang, and I S Chang, “Ammonia nitrogen removal and recovery from swine wastewater by microwave radiation,” Environ Eng Res., vol 19, no 4, pp 381–385, 2014 [22] Y Lin, M Guo, N Shah, and D C Stuckey, “Economic and environmental evaluation of nitrogen removal and recovery methods from wastewater,” Bioresour Technol., vol 215, pp 227–238, Sep 2016 [23] L Minh Triet, Xử lý nước thải đô thị & cơng nghiệp - Tính tốn thiết kế cơng trình Nhà xuất Đại học Quốc gia thành phố Hồ Chí Minh, 2008 [24] X L Trinh, Tinh toan thiet ke cac cong trinh xu ly nuoc thai, vol 15, no Ha Noi: Nhà xuất xây dựng, 2009 [25] H Kurama, J Poetzschke, and R Haseneder, “The application of membrane filtration for the removal of ammonium ions from potable water,” Water Res., vol 36, pp 2905–2909, 2002 [26] M Mondor, L Masse, D Ippersiel, F Lamarche, and D I Massé, “Use of electrodialysis and reverse osmosis for the recovery and concentration of ammonia from swine manure,” Bioresour Technol., vol 99, no 15, pp 7363–7368, Oct 2008 [27] S Sengupta, T Nawaz, and J Beaudry, “Nitrogen and Phosphorus Recovery from Wastewater,” Current Pollution Reports, vol 1, no Springer, pp 155–166, 01Sep-2015 [28] P F Strom, “Technologies to Remove Phosphorus from Wastewater,” Rutgers Univ Environ Sci., vol 1, no 8, pp 1–6, 2006 121 [29] A Folino, D A Zema, and P S Calabrò, “Environmental and economic sustainability of swine wastewater treatments using ammonia stripping and anaerobic digestion: A short review,” Sustain., vol 12, no 12, p 4971, Jun 2020 [30] Minnesota Pollution Control Agency, “Phosphorus Treatment and Removal Technologies,” MPCA, vol 1, no 6, pp 1–5, 2006 [31] J E Kogel, C N Trivedi, M J Barker, and T S Krukowski, Industrial minerals & rocks: commodities, markets, and uses, 7th ed., vol 44, no 03 Colardo, USA: Society for Mining, Metallurgy and Exploration Inc., 2006 [32] V K Gupta, P J M Carrott, M M L Ribeiro Carrott, and Suhas, “Low-Cost adsorbents: Growing approach to wastewater treatmenta review,” Crit Rev Environ Sci Technol., vol 39, no 10, pp 783–842, 2009 [33] S M Yakout, A El, H M Daifullah, and S A El-Reefy, “Pore Structure Characterization of Chemically Modified Biochar Derived From Rice Straw,” Environ Eng Manag J., vol 14, no 2, pp 473–480, 2015 [34] K Weber and P Quicker, “Properties of biochar,” Fuel, vol 217, no September 2017, pp 240–261, 2018 [35] F Verheijen, S Jeffery, A C Bastos, M Van Der Velde, and I Diafas, “Biochar Application to Soils: A Critical Scientific Review of Effects on Soil Properties, Processes and Functions,” Environment, vol 8, no 4, p 144, 2010 [36] J Lehmann and S Joseph, Biochar for environmental management: Science and technology, 1st ed London: Earthscan, 2012 [37] X Wang, Z Guo, Z Hu, and J Zhang, “Recent advances in biochar application for water and wastewater treatment: A review,” PeerJ, vol 8, p e9164, May 2020 [38] L T Nhung, “Đánh giá nhu cầu đào tạo nghề sử phế thải nông nghiệp sản xuất nông nghiệp bon thấp,” LCASP, vol 1, no 5, pp 1–5, 2015 122 [39] V Feodorov, “Modern Technologies of Treatment and Stabilization for Sewage Sludge from Water Treatment Plant,” Agric Agric Sci Procedia, vol 10, pp 417– 430, 2016 [40] T M P Đỗ, T T T Phan, and X L Nguyễn, “Đặc Điểm Hóa Lý Của Than Sinh Học Từ Vỏ Sầu Riêng Và Vỏ Mít,” Can Tho Univ J Sci., vol 59, no Environment and Climate change, pp 221–228, Mar 2023 [41] N M Hoa, “Khảo Sát Khả Năng Hấp Phụ Đạm Bởi Biochar,” Tạp chí Khoa học Đại học Cần Thơ, vol 29, pp 52–59, 2013 [42] B.-S Trinh, P Thi Kieu Chinh, and H Đoan Tram, “Color removal efficiency of rice husk biochar modified with magnetized iron oxides and nano zero valent iron for decolorization of dyeing wastewater,” Sci Technol Dev J - Sci Earth Environ., vol 3, no 2, pp 105–114, Jan 2020 [43] C Fang, T Zhang, P Li, R F Jiang, and Y C Wang, “Application of magnesium modified corn biochar for phosphorus removal and recovery from swine wastewater,” Int J Environ Res Public Health, vol 11, no 9, pp 9217–9237, 2014 [44] K Xu, F Lin, X Dou, M Zheng, W Tan, and C Wang, “Recovery of ammonium and phosphate from urine as value-added fertilizer using wood waste biochar loaded with magnesium oxides,” J Clean Prod., vol 187, pp 205–214, 2018 [45] Q Yin, B Zhang, R Wang, and Z Zhao, “Biochar as an adsorbent for inorganic nitrogen and phosphorus removal from water: a review,” Environ Sci Pollut Res., vol 24, no 34, pp 26297–26309, 2017 [46] S Vinitnantharat, S Kositchaiyong, and S Chiarakorn, “Removal of fluoride in aqueous solution by adsorption on acid activated water treatment sludge,” Appl Surf Sci., vol 256, no 17, pp 5458–5462, Jun 2010 [47] L Vinet and A Zhedanov, “A ‘missing’ family of classical orthogonal polynomials,” J Phys A Math Theor., vol 44, no 8, p 160, 2011 123 [48] E J Holcomb, “A technique for determining potassium release from a slow-release fertilizer1,” Commun Soil Sci Plant Anal., vol 12, no 3, pp 271–277, 1981 [49] M E Trenkel, “Slow and Controlled-Release and stabilized Fertilizers,” J Chem Inf Model., vol 53, no 9, pp 1689–1699, 2013 [50] J Terligen, M Hojjatie, and F Carney, “Review of Analytical Methods for Slowand Controlled- Release Fertilizers,” Int Fertil Assoc., vol 20, no 72, pp 1–20, 2020 [51] M B Shakoor, Z L Ye, and S Chen, “Engineered biochars for recovering phosphate and ammonium from wastewater: A review,” Sci Total Environ., vol 779, p 146240, 2021 [52] C Santhosh et al., “Synthesis and characterization of magnetic biochar adsorbents for the removal of Cr(VI) and Acid orange dye from aqueous solution,” Environ Sci Pollut Res., vol 27, no 26, pp 32874–32887, Sep 2020 [53] L He, D Wang, Z Wu, Y Lv, and S Li, “Magnesium-modified biochar was used to adsorb phosphorus from wastewater and used as a phosphorus source to be recycled to reduce the ammonia nitrogen of piggery digestive wastewater,” J Clean Prod., vol 360, p 132130, Aug 2022 [54] Y Yao, B Gao, J Chen, and L Yang, “Engineered biochar reclaiming phosphate from aqueous solutions: Mechanisms and potential application as a slow-release fertilizer,” Environ Sci Technol., vol 47, no 15, pp 8700–8708, Aug 2013 [55] M Kończak and M Huber, “Application of the engineered sewage sludge-derived biochar to minimize water eutrophication by removal of ammonium and phosphate ions from water,” J Clean Prod., vol 331, p 129994, Jan 2022 [56] K Xu, J Li, M Zheng, C Zhang, T Xie, and C Wang, “The precipitation of magnesium potassium phosphate hexahydrate for P and K recovery from synthetic urine,” Water Res., vol 80, pp 71–79, 2015 124 [57] C A Takaya, L A Fletcher, S Singh, U C Okwuosa, and A B Ross, “Recovery of phosphate with chemically modified biochars,” J Environ Chem Eng., vol 4, no 1, pp 1156–1165, 2016 [58] Y H Jiang et al., “Characteristics of nitrogen and phosphorus adsorption by Mgloaded biochar from different feedstocks,” Bioresour Technol., vol 276, pp 183– 189, Mar 2019 [59] H Xi et al., “Concurrent removal of phosphate and ammonium from wastewater for utilization using Mg-doped biochar/bentonite composite beads,” Sep Purif Technol., vol 285, p 120399, Mar 2022 [60] Y Zhang, Z Li, and I B Mahmood, “Recovery of NH 4+ by corn cob produced biochars and its potential application as soil conditioner,” Front Environ Sci Eng., vol 8, no 6, pp 825–834, Mar 2014 [61] Q He, X Li, and Y Ren, “Analysis of the simultaneous adsorption mechanism of ammonium and phosphate on magnesium-modified biochar and the slow release effect of fertiliser,” Biochar, vol 4, no 1, pp 1–16, Dec 2022 [62] L M Deem and S E Crow, “Biochar,” Ref Modul Earth Syst Environ Sci., vol 10, no 16, pp 1–5, 2017 [63] M M Thant Zin and D J Kim, “Simultaneous recovery of phosphorus and nitrogen from sewage sludge ash and food wastewater as struvite by Mg-biochar,” J Hazard Mater., vol 403, no August 2020, p 123704, 2021 [64] V G Le et al., “Struvite recovery from swine wastewater using fluidized-bed homogeneous granulation process,” J Environ Chem Eng., vol 9, no 3, Jun 2021 [65] A A Kubar et al., “The recovery of phosphate and ammonium from biogas slurry as value-added fertilizer by biochar and struvite co-precipitation,” Sustain., vol 13, no 7, pp 7–12, 2021 [66] X Li, X Zhao, X Zhou, and B Yang, “Phosphate recovery from aqueous solution 125 via struvite crystallization based on electrochemical-decomposition of nature magnesite,” J Clean Prod., vol 292, Apr 2021 [67] Q He, X Li, and Y Ren, “Analysis of the simultaneous adsorption mechanism of ammonium and phosphate on magnesium-modified biochar and the slow release effect of fertiliser,” Biochar, vol 4, no 1, pp 1–16, 2022 [68] J Zhang and Q Wang, “Sustainable mechanisms of biochar derived from brewers’ spent grain and sewage sludge for ammonia-nitrogen capture,” J Clean Prod., vol 112, pp 3927–3934, 2016 [69] R Li et al., “Enhancing phosphate adsorption by Mg/Al layered double hydroxide functionalized biochar with different Mg/Al ratios,” Sci Total Environ., vol 559, pp 121–129, Jul 2016 [70] G Cai and Z long Ye, “Concentration-dependent adsorption behaviors and mechanisms for ammonium and phosphate removal by optimized Mg-impregnated biochar,” J Clean Prod., vol 349, p 131453, May 2022 [71] E Company, M Farrés, J Colprim, and A Magrí, “Exploring the recovery of potassium-rich struvite after a nitrification-denitrification process in pig slurry treatment,” Sci Total Environ., vol 847, Nov 2022 [72] A Salimova, J Zuo, F Liu, Y Wang, S Wang, and K Verichev, “Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars,” Front Environ Sci Eng., vol 14, no 3, pp 1–13, 2020 [73] Z Ajmal, A Muhmood, R Dong, and S Wu, “Probing the efficiency of magnetically modified biomass-derived biochar for effective phosphate removal,” J Environ Manage., vol 253, no September 2019, p 109730, 2020 [74] B Micháleková-Richveisová, V Frišták, M Pipíška, L Ďuriška, E MorenoJimenez, and G Soja, “Iron-impregnated biochars as effective phosphate sorption materials,” Environ Sci Pollut Res., vol 24, no 1, pp 463–475, Jan 2017 126 [75] Y Dai, W Wang, L Lu, L Yan, and D Yu, “Utilization of biochar for the removal of nitrogen and phosphorus,” J Clean Prod., vol 257, 2020 [76] H Zhang, R P Voroney, and G W Price, “Effects of temperature and processing conditions on biochar chemical properties and their influence on soil C and N transformations,” Soil Biol Biochem., vol 83, pp 19–28, Apr 2015 [77] Z Zhang, L Yan, H Yu, T Yan, and X Li, “Adsorption of phosphate from aqueous solution by vegetable biochar/layered double oxides: Fast removal and mechanistic studies,” Bioresour Technol., vol 284, pp 65–71, Jul 2019 [78] Z Wang et al., “Effects of Nitrogen Addition on Soil Microbial Functional Diversity and Extracellular Enzyme Activities in Greenhouse Cucumber Cultivation,” Agriculture, vol 12, no 9, p 1366, 2022 [79] L Fang, J shan Li, S Donatello, C R Cheeseman, C S Poon, and D C W Tsang, “Use of Mg/Ca modified biochars to take up phosphorus from acid-extract of incinerated sewage sludge ash (ISSA) for fertilizer application,” J Clean Prod., vol 244, p 118853, Jan 2020 [80] B Wang et al., “Environmental-friendly coal gangue-biochar composites reclaiming phosphate from water as a slow-release fertilizer,” Sci Total Environ., vol 758, p 143664, Mar 2021 [81] C Wang, R Sun, and R Huang, “Highly dispersed iron-doped biochar derived from sawdust for Fenton-like degradation of toxic dyes,” J Clean Prod., vol 297, p 126681, May 2021 [82] P M Melia, R Busquets, P S Hooda, A B Cundy, and S P Sohi, “Driving forces and barriers in the removal of phosphorus from water using crop residue, wood and sewage sludge derived biochars,” Sci Total Environ., vol 675, pp 623–631, Jul 2019 [83] C Afagwu, M Mahmoud, S Alafnan, A Alqubalee, A ElHusseiny, and S Patil, 127 “Pore Volume Characteristics of Clay-Rich Shale: Critical Insight into the Role of Clay Types, Aluminum and Silicon Concentration,” Arab J Sci Eng., vol 47, no 9, pp 12013–12029, Apr 2022 [84] Y Zhang et al., “The pore size distribution and its relationship with shale gas capacity in organic-rich mudstone of Wufeng-Longmaxi Formations, Sichuan Basin, China,” J Nat Gas Geosci., vol 1, no 3, pp 213–220, Jun 2016 [85] K S W Sing and R T Williams, “Physisorption hysteresis loops and the characterization of nanoporous materials,” Adsorpt Sci Technol., vol 22, no 10, pp 773–782, Nov 2004 [86] L Jia, B Niu, X Jing, and Y Wu, “Equilibrium and hysteresis formation of water vapor adsorption on microporous adsorbents: Effect of adsorbent properties and temperature,” J Air Waste Manag Assoc., vol 72, no 2, pp 176–186, 2022 [87] R Chandra Muduli and P Kale, “Chemically modified surface of silicon nanostructures to enhance hydrogen uptake capabilities,” Int J Hydrogen Energy, vol 6, no 3, pp 10–25, Jul 2022 [88] S Sun, F Liang, L Tang, J Wu, and C Ma, “Microstructural investigation of gas shale in Longmaxi Formation, Lower Silurian, NE Sichuan Basin, China,” Energy Explor Exploit., vol 35, no 4, pp 406–429, Jul 2017 [89] P Liang, H Yu, J Huang, Y Zhang, and H Cao, “The Review on Adsorption and Removing Ammonia Nitrogen with Biochar on its Mechanism,” MATEC Web Conf., vol 67, pp 1–11, 2016 [90] M Zhang et al., “Evaluating biochar and its modifications for the removal of ammonium, nitrate, and phosphate in water,” Water Res., vol 186, 2020 [91] Z L Ye, S H Chen, M Lu, J W Shi, L F Lin, and S M Wang, “Recovering phosphorus as struvite from the digested swine wastewater with bittern as a magnesium source,” Water Sci Technol., vol 64, no 2, pp 334–340, Jul 2011 128 [92] W Zheng, M Guo, T Chow, D N Bennett, and N Rajagopalan, “Sorption properties of greenwaste biochar for two triazine pesticides,” J Hazard Mater., vol 181, no 1–3, pp 121–126, Apr 2010 [93] K W Jung and K H Ahn, “Fabrication of porosity-enhanced MgO/biochar for removal of phosphate from aqueous solution: Application of a novel combined electrochemical modification method,” Bioresour Technol., vol 200, pp 1029– 1032, Jan 2016 [94] Z Wang et al., “Biochar produced from oak sawdust by Lanthanum (La)-involved pyrolysis for adsorption of ammonium (NH4+), nitrate (NO3-), and phosphate (PO43-),” Chemosphere, vol 119, pp 646–653, Jan 2015 [95] D V Sarkhot, T A Ghezzehei, and A A Berhe, “Effectiveness of Biochar for Sorption of Ammonium and Phosphate from Dairy Effluent,” J Environ Qual., vol 42, no 5, pp 1545–1554, Sep 2013 [96] Q Yin, B Zhang, R Wang, and Z Zhao, “Phosphate and ammonium adsorption of sesame straw biochars produced at different pyrolysis temperatures,” Environ Sci Pollut Res., vol 25, no 5, pp 4320–4329, Nov 2018 129 APPENDIX I Table S1 Experimental conditions and results of central composite design Run A: pH B: N/P 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 6 7 8 8 7 7 7 1.5 1.25 1.25 1.5 1.75 1.75 1.75 1.5 1.25 1.25 1.5 1.25 1.75 1.75 1.5 1.25 1.5 1.25 1.5 1.5 1.75 1.5 1.5 1.5 1.25 1.75 1.5 1.75 C: Biochar dosage mg/100mL 110 115 105 110 105 115 115 100 105 105 110 110 105 115 105 110 115 110 115 110 120 110 115 110 110 110 115 105 110 105 D: Initial concentration mg/L 80 70 90 80 70 90 90 80 90 70 80 80 70 70 90 80 70 60 90 80 80 80 70 80 100 80 90 70 80 90 130 Qe Ammonium mg/g 52.3636 35.31 64.381 47.2727 36.8 49.0435 49.0435 60.96 57.981 36.8 52.3636 50.3273 45.8667 31.6522 59.0476 50.3273 36.5217 28.25 54.887 44.7273 44.2667 48.2909 29.7043 47.2727 62.6545 48.2909 53.913 34.6667 47.2727 57.981 Qe Phosphate mg/g 45.3939 45.6393 65.8799 44.9765 35.0758 42.6623 42.862 48.51 65.224 50.6418 67.17 44.246 50.8605 31.7262 47.7093 44.1416 45.4397 33.7945 61.0496 34.9424 41.2285 44.4547 31.2272 44.5591 60.44 44.4547 60.2511 34.46 44.7678 47.8187 Table S2 The experiment results of adsorbent types No Qe (mg/g) BS CS TS RS B C T R PO43- 47.39 33.80 49.35 34.81 41.27 11.62 41.27 4.12 NH4+ 34.50 39.17 35.43 40.10 28.90 25.17 31.70 29.83 PO43- 46.38 46.67 46.34 45.76 41.65 1.67 37.25 11.24 NH4+ 39.17 36.37 34.50 40.10 29.83 25.17 32.63 27.03 PO43- 47.63 47.82 48.01 47.48 46.82 18.31 42.04 19.84 NH4+ 38.23 38.23 36.37 41.03 29.83 26.10 29.83 28.90 3- 36.39 41.27 48.68 37.39 - - - - NH4+ 44.77 44.77 43.83 48.50 - - - - PO43- 47.13 42.76 47.90 42.68 43.25 10.53 40.19 11.73 NH4+ 37.30 37.92 35.43 40.41 29.52 25.48 31.39 28.59 PO4 Average Table S3 The experiment results for actual wastewater Biochar dosage g/100 mL 0.1 Inlet conc NH4+ Inlet conc PO43- NH4+Qe mg/g PO43- Qe mg/g NH4+ H% PO43- H% 112 76.13 47.41 63.55 42.33 83.47 0.2 102.48 70.39 11.70 28.62 22.23 88.53 0.4 92.96 64.65 8.12 15.07 30.85 93.20 0.6 92.96 64.65 3.05 5.19 29.16 82.22 0.8 92.96 64.65 1.96 3.15 42.17 97.32 1.2 126 52.06 0.09 1.93 0.89 92.95 1.4 126 52.06 0.44 1.51 4.89 84.90 1.6 126 52.06 0.53 1.42 6.67 91.11 1.8 126 52.06 0.16 1.07 2.22 77.54 131 Table S4 The experiment of slow released test Time 24 168 192 216 240 Time 24 168 192 Time 24 48 72 168 Ammonium 11.2 7.84 12.88 11.2 15.12 19.6 Ammonium 16.80 63.84 50.40 Ammonium 44.8 38.64 47.6 37.8 Phosphate 22.23 2.25 3.74 5.81 14.31 23.49 Phosphate 3.74 2.60 0.42 Phosphate 21.99627937 22.9146131 18.43773617 23.83294683 Table S5 The results of pink swamp mallow height Weeks Biochar 20 21 21 22 20 25 23 27 27 27.5 27.5 - Chemical 18 26 27.5 27 27 27 27 27 - Non 18 18 18 18 21 24.5 24.5 24 23 25 25.5 - Weeks 12 13 14 15 16 17 18 19 20 21 22 23 Biochar 27.5 27 22 22 26 30 28 29.5 34 40 Chemical 28 32 30 24 24 22 0 0 0 Non 28 27 30 28 29.5 29 31 33 27 31 18.5 18.5 18.5 28.5 22.5 132 10 11 - 37.5 39.5 APPENDIX II Fig S1 Heated oven Fig S2 Drying oven Fig S3 Sample fridge Fig S4 Lab shaker Fig S5 Distillation Fig S6 Vacuum filter Fig S5 Moisture drying scale Fig S6 Scale with odd numbers Fig S7 Scale with odd numbers 133 APPENDIX III Fig S1 MgCl2 solution soaking Fig S2 After evaporated 80oC Fig S3 After heated 550oC Fig S4 Water leachate model Fig S5 Soil leachate model Fig S6 Sand leachate model Fig S7 Biochar-sludge in net bag Fig S8 Pink swamp mallow roots Fig S9 Extraction from plant roots 134 VITA Full name: Nguyen Lan Thanh Date of birth: 13/10/1998 Place of birth: Ho Chi Minh City Adress: 904/27 Nguyen Duy, Ward 12, District 8, Ho Chi Minh City 2016 Bachelor of Engineering in Degree Environmental Engineering, Ho Chi Minh University of Technology 2020 Master of Engineering in Degree Environmental Engineering, Ho Chi Minh University of Technology 2022 Researcher of post-harvest Technology, Sub-Institute of Agricultural Engineering and Post-harvest Technology 135