Application of Modified Biochar in the Treatment of Pesticide Wastewater by Constructed Wetland
2. Materials and Methods
2.1. Modification of Biochar
- H3PO4 modification: 11.76 mL of analytically pure (85%) H3PO4 was diluted to 20% H3PO4, and 50 mL of the solution was combined with 5 g biochar in a 50 mL beaker and allowed to soak for 3 h. Then, the obtained modified biochar was washed with pure water until the eluate pH was neutral, and solid-liquid separation was carried out by a vacuum filter for each wash. Finally, the obtained modified biochar was dried at 70 °C, ground, passed through a 60-mesh sieve, and saved for later use.
- Fe loading modification: 100 mL of 0.5 mol·L−1 ferric chloride solution and 5 g of dried biochar were combined in a 100 mL beaker, and 50 mL of ferric chloride solution was added. The beaker was placed on a stirrer for rapid stirring for 12 h, washed with deionized water until the eluate pH was neutral after each wash, and solid-liquid separation was carried out using a vacuum filter. The obtained modified biochar was dried at 70 °C, ground, passed through a 60-mesh sieve, and stored for future use.
- Acid (H2SO4) or base (KOH) modification: 5 g of the prepared biochar was placed in a conical flask, and 50 mL of 10% H2SO4 or 3 mol·L−1 KOH solution was added and stirred with a magnetic stirrer at 65 °C. The modified corn stalk biochar was washed with deionized water until the pH of the leachate was neutral, and then solid-liquid separation was carried out by a vacuum filter after each wash. The obtained modified biochar was dried at 70 °C to constant weight, ground, passed through a 60-mesh sieve, and stored for future use.
2.2. Adsorption Experiment
2.2.1. Adsorption Thermodynamic Experiment
2.2.2. Adsorption Kinetic Experiments
2.2.3. Parameters of Testing Wastewater
2.3. Design and Commissioning of Simulated Constructed Wetland Device
2.4. Analysis Methods
2.5. Atrazine Determination
3. Results and Discussion
3.1. Adsorption Experiment of Modified Biochar
3.2. Change of Effluent Quality over Time in the Initial Stage of Simulated Constructed Wetland Operation
3.3. Changes in Effluent Quality over Time during the Stable Operation of Simulated Constructed Wetlands
3.4. Removal of Herbicide Atrazine and Mechanism Analysis
- The successful modification of biochar was demonstrated by the analysis results of adsorption kinetics curves and isotherm adsorption curves.
- Through the analysis and discussion of the best modification conditions, it was shown that the adsorption performance of modified biochar was better when sulfuric acid was selected as the modifier of biochar, and the modified biochar had better adsorption performance after magnetic stirring for 1 h at 65 °C.
- The test results for the removal effect of TP, TN, and COD in the constructed wetland in the later stages of the constructed wetland cultivation showed that without the addition of modified biochar, the constructed wetland had a good purification effect on the basic wastewater.
- The experimental results of adding modified biochar to the constructed wetland to simulate the removal of agricultural runoff wastewater showed that the constructed wetland with modified biochar in this design has a good adsorption and removal potential for herbicides/pesticides, results that verified the theoretical feasibility of adding sulfuric acid modified biochar to the constructed wetland for pesticide removal.
- Modified biochar and the constructed wetland formed a safe treatment system for herbicides/pesticides and other agricultural chemical pollutants in farmland runoff and wastewater; thus, the system provided a reference for the design of constructed wetlands for purifying herbicide/pesticide-containing agricultural wastewater.
Data Availability Statement
Conflicts of Interest
- Wang, Q.; Yang, Z. Industrial water pollution, water environment treatment, and health risks in China. Environ. Pollut. 2016, 218, 358–365. [Google Scholar] [CrossRef]
- Khan, M.A.; Costa, F.B.; Fenton, O.; Jordan, P.; Fennell, C.; Mellander, P.E. Using a multi-dimensional approach for catchment scale herbicide pollution assessments. Sci. Total Environ. 2020, 747, 141232. [Google Scholar] [CrossRef]
- Karpińska, J.; Kotowska, U. Removal of organic pollution in the water environment. Water 2019, 11, 2017. [Google Scholar] [CrossRef][Green Version]
- Singh, S.; Kumar, V.; Chauhan, A.; Datta, S.; Wani, A.B.; Singh, N.; Singh, J. Toxicity, degradation and analysis of the herbicide atrazine. Environ. Chem. Lett. 2018, 16, 211–237. [Google Scholar] [CrossRef]
- Burnside, O.C.; Moomaw, R.S. Sorghum growth as affected by annual applications of atrazine. Weed Sci. 1975, 23, 494–498. [Google Scholar] [CrossRef]
- Metzger, B.A.; Soltani, N.; Raeder, A.J.; Hooker, D.C.; Robinson, D.E.; Sikkema, P.H. Effect of hybrid varieties, application timing, and herbicide rate on field corn tolerance to tolpyralate plus atrazine. Weed Sci. 2019, 67, 475–484. [Google Scholar] [CrossRef]
- Xiong, X.; Chunmei, L.; Jing, S.; Hailiang, W.; Donghong, W.; Hanwen, S.; Zijian, W. Residue Characteristics and Ecological Risk Assessment of Twenty-nine Pesticides in Surface Water of Major River-Basin in China. Asian J. Ecotoxicol. 2016, 11, 347–354. [Google Scholar]
- Boopathy, R. Anaerobic degradation of atrazine. Int. Biodeterior. Biodegrad. 2017, 119, 626–630. [Google Scholar] [CrossRef]
- Ryu, H.D.; Han, H.; Park, J.H.; Kim, Y.S. New insights into the occurrence and removal of 36 pesticides in pesticide wastewater treatment plants in Korea. Chemosphere 2022, 309, 136717. [Google Scholar] [CrossRef]
- Zhu, L.M. Treatment of Herbicides Wastewater Using Electrochemical and Biological Contact Oxidation Combined Process. Master’s Thesis, Harbin Institute of Technology, Harbin, China, 2011. (In Chinese). [Google Scholar]
- Li, X.; Cheng, M.; Jiao, X.; Zhao, Z.; Zhang, Y.; Gao, X. Advances in microbial electrochemistry-enhanced constructed wetlands. World J. Microbiol. Biotechnol. 2022, 38, 1–13. [Google Scholar] [CrossRef]
- Marcińczyk, M.; Oleszczuk, P. Biochar and engineered biochar as slow-and controlled-release fertilizers. J. Clean. Prod. 2022, 339, 130685. [Google Scholar] [CrossRef]
- Zhang, C.; Chen, S.Q.; Wang, Y.; Wei, J.; Hua, Y.; La, j.; Jing, Z. Nitrogen and phosphorus Removal from constructed wetland by plant stalk carbon source. Water Purif. Technol. 2021, 40, 19–27. (In Chinese) [Google Scholar]
- Zhao, L.; Zheng, W.; Mašek, O.; Chen, X.; Gu, B.; Sharma, B.K.; Cao, X. Roles of phosphoric acid in biochar formation: Synchronously improving carbon retention and sorption capacity. J. Environ. Qual. 2017, 46, 393–401. [Google Scholar] [CrossRef]
- Peng, H.; Gao, P.; Chu, G.; Pan, B.; Peng, J.; Xing, B. Enhanced adsorption of Cu (II) and Cd (II) by phosphoric acid-modified biochars. Environ. Pollut. 2017, 229, 846–853. [Google Scholar] [CrossRef]
- Gao, Y.; Chen, Y.; Song, T.; Su, R.; Luo, J. Activated peroxymonosulfate with ferric chloride-modified biochar to degrade bisphenol A: Characteristics, influencing factors, reaction mechanism and reuse performance. Sep. Purif. Technol. 2022, 300, 121857. [Google Scholar] [CrossRef]
- Li, X.; Chu, S.; Wang, P.; Li, K.; Su, Y.; Wu, D.; Xie, B. Potential of biogas residue biochar modified by ferric chloride for the enhancement of anaerobic digestion of food waste. Bioresour. Technol. 2022, 360, 127530. [Google Scholar] [CrossRef] [PubMed]
- Chen, J.; Li, W.M.; Ding, W.C.; Wang, X.Y.; Hu, C.L. Removal of ammonia nitrogen by Fe/Mg-modified bamboo charcoal. Chin. J. Environ. Eng. 2015, 9, 5187–5192. (In Chinese) [Google Scholar]
- Özer, Ç.; İmamoğlu, M. Isolation of Nickel (II) and Lead (II) from Aqueous Solution by Sulfuric Acid Prepared Pumpkin Peel Biochar. Anal. Lett. 2022, 1–13. [Google Scholar] [CrossRef]
- Vithanage, M.; Rajapaksha, A.U.; Zhang, M.; Thiele-Bruhn, S.; Lee, S.S.; Ok, Y.S. Acid-activated biochar increased sulfamethazine retention in soils. Environ. Sci. Pollut. Res. 2015, 22, 2175–2186. [Google Scholar] [CrossRef]
- Li, R.; Wang, Z.; Guo, J.; Zhao, X.; Yan, L.; Xie, X. Adsorption characteristics suifathiazole in aqueous solution bi acid/alkali modified biochars. Acta Sci. Circumstantiae 2017, 37, 4119–4128. (In Chinese) [Google Scholar]
- Liu, N.; Liu, Y.; Zeng, G.; Gong, J.; Tan, X.; Liu, S.; Jiang, L.; Li, M.; Yin, Z. Adsorption of 17β-estradiol from aqueous solution by raw and direct/pre/post-KOH treated lotus seedpod biochar. J. Environ. Sci. 2020, 87, 10–23. [Google Scholar] [CrossRef] [PubMed]
- Luo, J.; Li, X.; Ge, C.; Müller, K.; Yu, H.; Huang, P.; Li, J.; Tsang, D.C.W.; Bolan, N.S.; Rinklebe, J.; et al. Sorption of norfloxacin, sulfamerazine and oxytetracycline by KOH-modified biochar under single and ternary systems. Bioresour. Technol. 2018, 263, 385–392. [Google Scholar] [CrossRef] [PubMed]
- Qu, J.H. Study on Removal Effect of Three Kinds of Pesticides by Constructed Wetlands. Master’s Thesis, SooChow University, Suzhou, China, 2018. (In Chinese). [Google Scholar]
- HJ-2005-2010; Technical Specifications for Constructed Wetland Sewage Treatment Engineering, 1st ed. China Environmental Press: Beijing, China, 2011; pp. 2–4.
- Zhao, J.; Kim, M.; Wang, Y. Application research of constructed wetlands for pesticide treatment. North. Hortic. 2016, 14, 198–201. (In Chinese) [Google Scholar]
- McCalla, L.; Phillips, B.M.; Anderson, B.S.; Voorhees, J.P.; Siegler, K.; Faulkenberry, K.R.; Zamudio, S.; Tjeerdema, R.S. Effectiveness of an Integrated Wetland Treatment System in Reducing Pesticide Concentrations Associated with Agricultural Runoff; Surface Water Protection Program: Sacramento, CA, USA, 2020.
- Zhao, X.; Bai, S.; Li, C.; Yang, J.; Ma, F. Bioaugmentation of atrazine removal in constructed wetland: Performance, microbial dynamics, and environmental impacts. Bioresour. Technol. 2019, 289, 121618. [Google Scholar] [CrossRef] [PubMed]
- Liu, T.; Xu, S.; Lu, S.; Qin, P.; Bi, B.; Ding, H.; Liu, Y.; Guo, X.; Liu, X. A review on removal of organophosphorus pesticides in constructed wetland: Performance, mechanism and influencing factors. Sci. Total Environ. 2019, 651, 2247–2268. [Google Scholar] [CrossRef]
- Lv, T.; Carvalho, P.N.; Zhang, L.; Zhang, Y.; Button, M.; Arias, C.A.; Weber, K.P.; Brix, H. Functionality of microbial communities in constructed wetlands used for pesticide remediation: Influence of system design and sampling strategy. Water Res. 2017, 110, 241–251. [Google Scholar] [CrossRef]
- Wang, Q.; Li, C.; Chen, C.; Chen, J.; Ma, X.; Que, X. Physiological responses of phragmites australis to atrazine exposure and their relevance for tolerance. J. Agro-Environ. Sci. 2017, 36, 1968–1977. (In Chinese) [Google Scholar]
- Du, H. Bioremediation of Atrazine Contaminated Soil Using Bioaugmentation Technology and Dynamics Analysis of Bacterial Community. Master’s Thesis, Shandong Agricultural University, Taian, China, 2012. (In Chinese). [Google Scholar]
- Kolekar, P.D.; Patil, S.M.; Suryavanshi, M.V.; Suryawanshi, S.S.; Khandare, R.V.; Govindwar, S.P.; Jadhav, J.P. Microcosm study of atrazine bioremediation by indigenous microorganisms and cytotoxicity of biodegraded metabolites. J. Hazard. Mater. 2019, 374, 66–73. [Google Scholar] [CrossRef]
- Zhang, C.; Liu, L.; Zhao, M.; Rong, H.; Xu, Y. The environmental characteristics and applications of biochar. Environ. Sci. Pollut. Res. 2018, 25, 21525–21534. [Google Scholar] [CrossRef]
- Jiang, X. Removal of Glyphosate and Sulfamethazine by Modified Biochar. Master’s Thesis, South China University of Technology, Guangzhou, China, 2018. (In Chinese). [Google Scholar]
- Zhao, L. Adsorption Behavior and Applied Research of Atrazine on Modified Biochars. Master’s Thesis, Northeast Agricultural University, Harbin, China, 2017. (In Chinese). [Google Scholar]
- Yu, H. Sorption/Desorption Characteristis and Mechanisms of Bio-Chars with Atrazine in Environment. Ph.D. Thesis, China University of Mining & Technology, Beijing, China, 2014. (In Chinese). [Google Scholar]
- Kuang, B.; Xiao, R.; Wang, C.; Zhang, L.; Wei, Z.; Bai, J.; Zhang, K.; Campos, M.; Jorquera, M.A. Bacterial community assembly in surface sediments of a eutrophic shallow lake in northern China. Ecohydrol. Hydrobiol. 2022. [Google Scholar] [CrossRef]
|Specific Surface Area (m2/g)||pH||Ash|
|Cation Exchange Capacity|
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.
© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Hu, Y.; Xiao, R.; Kuang, B.; Hu, Y.; Wang, Y.; Bai, J.; Wang, C.; Zhang, L.; Wei, Z.; Zhang, K.; Jorquera, M.A.; Acuña, J.J.; Pan, W. Application of Modified Biochar in the Treatment of Pesticide Wastewater by Constructed Wetland. Water 2022, 14, 3889. https://doi.org/10.3390/w14233889
Hu Y, Xiao R, Kuang B, Hu Y, Wang Y, Bai J, Wang C, Zhang L, Wei Z, Zhang K, Jorquera MA, Acuña JJ, Pan W. Application of Modified Biochar in the Treatment of Pesticide Wastewater by Constructed Wetland. Water. 2022; 14(23):3889. https://doi.org/10.3390/w14233889Chicago/Turabian Style
Hu, Yong, Rong Xiao, Bo Kuang, Yanping Hu, Yaping Wang, Junhong Bai, Chen Wang, Ling Zhang, Zhuoqun Wei, Kegang Zhang, Milko A. Jorquera, Jacqueliine J. Acuña, and Wenbin Pan. 2022. "Application of Modified Biochar in the Treatment of Pesticide Wastewater by Constructed Wetland" Water 14, no. 23: 3889. https://doi.org/10.3390/w14233889