玉米芯对磺胺甲恶唑和甲氧苄啶的吸附效果及机制

张艳杰; 董伟羊; 王欢; 闫国凯; 常洋; 王海燕; 凌宇

doi:10.12153/j.issn.1674-991X.20220375

玉米芯对磺胺甲恶唑和甲氧苄啶的吸附效果及机制

doi: 10.12153/j.issn.1674-991X.20220375

张艳杰^{1, 2,},
董伟羊²,
王欢²,
闫国凯²,
常洋²,
王海燕^{1, 2, ,},
凌宇^{1, 2}

1.
环境基准与风险评估国家重点实验室, 中国环境科学研究院
2.
环境污染控制工程技术研究中心, 中国环境科学研究院

基金项目: 国家重点研发计划项目（2019YFC0408602）；中央财政科技计划结余经费专项（2021-JY-33）

详细信息

作者简介:
张艳杰（1998—），女，硕士研究生，主要研究方向为水污染控制理论与技术，zyj2950236115@163.com

通讯作者:
王海燕（1976—）女，研究员，博士，主要从事水污染防控原理与技术研究，wanghy@craes.org.cn

中图分类号: X703
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出版历程
- 收稿日期: 2022-04-22

Adsorption effect and mechanism of sulfamethoxazole and trimethoprim on corncob

ZHANG Yanjie^{1, 2
,},
DONG Weiyang²,
WANG Huan²,
YAN Guokai²,
CHANG Yang²,
WANG Haiyan^{1, 2
, ,},
LING Yu^{1, 2}

1.
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences
2.
Research Center of Environmental Pollution Control Technology, Chinese Research Academy of Environmental Sciences

摘要

摘要:
为探究农业废物是否能吸附去除抗生素以及不同抗生素之间是否存在相互作用，通过对玉米芯的理化特征分析、傅里叶红外光谱分析、吸附动力学和吸附等温线分析，研究了玉米芯对磺胺甲恶唑（SMX）和甲氧苄啶（TMP）的吸附效果及机制。结果表明：在只含有单一抗生素（初始浓度为 10mg/L）、温度为25 ℃、玉米芯浓度为25 g/L的体系中，玉米芯对SMX和TMP吸附量分别为131.18和358.75 mg/kg；在同时含有SMX和TMP的体系中（初始浓度均为 10mg/L），玉米芯对其的吸附量分别为131.02和358.74 mg/kg，SMX和TMP之间为非交互吸附过程。在2种体系中，SMX和TMP的吸附均较好地符合准二级反应动力学方程，Langmuir和Freundlich等温线较好地拟合了SMX的吸附过程，而Freundlich等温线对TMP的拟合效果较好。SMX吸附主要为静电作用、π-π堆积作用，且以静电作用为主；TMP吸附主要通过疏水分配、π-π堆积作用和氢键作用。
- 玉米芯 /
- 吸附 /
- 磺胺甲恶唑(SMX) /
- 甲氧苄啶(TMP) /
- π-π堆积作用
Abstract:
To explore whether agricultural wastes can adsorb antibiotics and whether there is an interaction between different antibiotics, the physicochemical characteristics analysis of corncob, Fourier Infrared Spectroscopy analysis, adsorption kinetics, and adsorption isotherms analysis were used to study the adsorption effect and mechanism of sulfamethoxazole (SMX) and trimethoprim (TMP) on corncob. The results showed that SMX and TMP adsorption capacities on corncob were 131.18 and 358.75 mg/kg in the system with single antibiotic （the initial concentration was 10 mg/L） at 25 ℃ and corncob concentration of 25 g/L , and they were 131.02 and 358.74 mg/kg in the coexistence system with both SMX and TMP（the initial concentration both were 10 mg/L）, respectively. There was non-interactive adsorption between SMX and TMP in the coexistence system. The adsorption kinetics of SMX and TMP were better represented by the pseudo-second-order kinetic model in the two systems. Both Langmuir and Freundlich isotherms were well fitted with the SMX adsorption process, and the adsorption of TMP was described well by the Freundlich isotherm. SMX was mainly adsorbed by electrostatic interaction and π-π stacking mechanism, and the electrostatic interaction played the main role. The adsorption of TMP was mainly due to the hydrophobic distribution, π-π stacking, and hydrogen bonding.
- corncob /
- adsorption /
- sulfamethoxazole (SMX) /
- trimethoprim (TMP) /
- π-π stacking mechanism

HTML全文

图 1 玉米芯的理化特征

Figure 1. Physicochemical characteristics of corncob

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图 2 玉米芯对一元和二元溶质体系中SMX和TMP在不同时刻的吸附量

Figure 2. Adsorption capacity of SMX and TMP on corncob in single and binary solute systems at different time

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图 3 玉米芯对一元和二元溶质体系中SMX和TMP的动力学模型拟合

Figure 3. Adsorption kinetics fitting of SMX and TMP on corncob in single and binary solute systems

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图 4 玉米芯对一元和二元溶质体系中SMX和TMP的吸附等温线

Figure 4. Adsorption isotherms of SMX and TMP on corncob in single and binary solute systems

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图 5 吸附平衡时玉米芯对一元和二元溶质体系中SMX和TMP的去除率和去除量

Figure 5. Removal rate and removal amount of SMX and TMP on corncob in single and binary solute systems at adsorption equilibrium

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图 6 玉米芯吸附抗生素前后的红外光谱

Figure 6. Infrared spectra of corncob before and after antibiotic adsorption

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表 1 SMX和TMP的基本理化性质

Table 1. Basic physicochemical properties of SMX and TMP

抗生素	分子式	分子量	化学物质登录号（CAS）	辛醇-水分配系数（lg K_ow）	酸度系数（pKa）
SMX^[21-22]	C₁₀H₁₁N₃O₃S	253.278	723-46-6	0.89	1.6、5.7
TMP^[22]	C₁₄H₁₈N₄O₃	290.318	738-70-5	0.91~1.26	6.8

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表 2 玉米芯吸附一元和二元溶质体系中SMX和TMP的动力学参数

Table 2. Kinetic parameters for adsorption of SMX and TMP on corncob in single and binary solute systems

体系	q_e,exp/(mg/kg)	准一级反应动力学模型			准二级反应动力学模型			颗粒内扩散模型
体系	q_e,exp/(mg/kg)	q_e/(mg/kg)	k₁/min^-1	R²	q_e/(mg/kg)	k₂/〔kg/(mg·min)〕	R²	k_d/〔mg/(kg·min^1/2)〕	c	R²
一元SMX	131.18	130.75	0.0450	0.96	135.37	0.0009	0.99	3.55	76.81	0.51
一元TMP	358.75	357.07	1.5682	0.96	357.95	0.0116	0.92	1.20	344.01	0.01
二元SMX	131.02	126.22	0.1142	0.99	141.64	0.0010	0.99	10.86	26.86	0.63
二元TMP	358.74	356.10	1.5407	0.71	360.22	0.0113	0.96	1.54	344.51	0.12
注：q_e,exp为吸附动力学试验中的平衡吸附量。

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表 3 玉米芯对一元和二元溶质体系中SMX和TMP的等温线拟合参数

Table 3. Fitting parameters of adsorption isotherms of SMX and TMP on corncob in single and binary solute systems

体系	Langmuir等温线			Freundlich等温线
体系	q_m/(mg/kg)	K_L/(L/mg)	R²	K_F/{mg/〔kg·(L/mg)^1/n〕}	1/n	R²
一元SMX	1669.77	0.014	0.99	27.10	0.87	0.99
一元TMP	−963.02	−4.415	0.84	282.39	1.27	0.99
二元SMX	1281.69	0.017	0.99	24.28	0.89	0.99
二元TMP	−767.75	−3.993	0.76	258.12	1.63	0.98

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参考文献(50)

[1]	ANJALI R, SHANTHAKUMAR S. Insights on the current status of occurrence and removal of antibiotics in wastewater by advanced oxidation processes[J]. Journal of Environmental Management,2019,246:51-62.
[2]	BARAN W, ADAMEK E, JAJKO M, et al. Removal of veterinary antibiotics from wastewater by electrocoagulation[J]. Chemosphere,2018,194:381-389. doi: 10.1016/j.chemosphere.2017.11.165
[3]	胡双庆, 张玉, 沈根祥.抗生素磺胺嘧啶和磺胺甲恶唑在土壤中的淋溶行为研究[J]. 环境科学研究,2022,35(2):470-477. doi: 10.13198/j.issn.1001-6929.2021.08.18 HU S Q, ZHANG Y, SHEN G X. Leaching behavior of antibiotics sulfadiazine and sulfamethoxazole in soil[J]. Research of Environmental Sciences,2022,35(2):470-477. doi: 10.13198/j.issn.1001-6929.2021.08.18
[4]	ZHAO Y X, ZHANG C G, YANG Z F, et al. Global trends and prospects in the removal of pharmaceuticals and personal care products: a bibliometric analysis[J]. Journal of Water Process Engineering,2021,41:102004. doi: 10.1016/j.jwpe.2021.102004
[5]	PHOON B L, ONG C C, MOHAMED SAHEED M S, et al. Conventional and emerging technologies for removal of antibiotics from wastewater[J]. Journal of Hazardous Materials,2020,400:122961. doi: 10.1016/j.jhazmat.2020.122961
[6]	SUN Q, LI M Y, MA C, et al. Seasonal and spatial variations of PPCP occurrence, removal and mass loading in three wastewater treatment plants located in different urbanization areas in Xiamen, China[J]. Environmental Pollution,2016,208:371-381. doi: 10.1016/j.envpol.2015.10.003
[7]	VOOLAID V, DONNER E, VASILEIADIS S, et al. Bacterial diversity and antibiotic resistance genes in wastewater treatment plant influents and effluents[M]//Antimicrobial resistance in wastewater treatment processes. Hoboken, NJ, USA: John Wiley & Sons, Inc. , 2017: 157-178.
[8]	WANG J L, CHU L B. Biological nitrate removal from water and wastewater by solid-phase denitrification process[J]. Biotechnology Advances,2016,34(6):1103-1112. doi: 10.1016/j.biotechadv.2016.07.001
[9]	闫苗苗, 张海涵, 钊珍芳, 等.生物脱氮技术中好氧反硝化细菌的代谢及应用研究进展[J]. 环境科学研究,2020,33(3):668-676. doi: 10.13198/j.issn.1001-6929.2019.09.04 YAN M M, ZHANG H H, ZHAO Z F, et al. Research progress of metabolism and application of aerobic denitrifying bacteria in biological denitrification technology[J]. Research of Environmental Sciences,2020,33(3):668-676. doi: 10.13198/j.issn.1001-6929.2019.09.04
[10]	WEN Y, CHEN Y, ZHENG N, et al. Effects of plant biomass on nitrate removal and transformation of carbon sources in subsurface-flow constructed wetlands[J]. Bioresource Technology,2010,101(19):7286-7292. doi: 10.1016/j.biortech.2010.04.068
[11]	CHEN Y, WEN Y, CHENG J, et al. Effects of dissolved oxygen on extracellular enzymes activities and transformation of carbon sources from plant biomass: implications for denitrification in constructed wetlands[J]. Bioresource Technology,2011,102(3):2433-2440. doi: 10.1016/j.biortech.2010.10.122
[12]	YANG Z C, ZHOU Q, SUN H M, et al. Metagenomic analyses of microbial structure and metabolic pathway in solid-phase denitrification systems for advanced nitrogen removal of wastewater treatment plant effluent: a pilot-scale study[J]. Water Research,2021,196:117067. doi: 10.1016/j.watres.2021.117067
[13]	FENG L J, CHEN K, HAN D D, et al. Comparison of nitrogen removal and microbial properties in solid-phase denitrification systems for water purification with various pretreated lignocellulosic carriers[J]. Bioresource Technology,2017,224:236-245. doi: 10.1016/j.biortech.2016.11.002
[14]	常洋, 王海燕, 储昭升, 等.硫碳比对芦苇碳源-硫耦合表面流湿地脱氮的影响[J]. 环境科学研究,2017,30(11):1783-1792. CHANG Y, WANG H Y, CHU Z S, et al. Influence of sulfur-to-carbon ratio on nitrogen removal by Phragmites australis and sulfur combined surface flow construction wetland[J]. Research of Environmental Sciences,2017,30(11):1783-1792.
[15]	SUN H M, WANG T, YANG Z C, et al. Simultaneous removal of nitrogen and pharmaceutical and personal care products from the effluent of waste water treatment plants using aerated solid-phase denitrification system[J]. Bioresource Technology,2019,287:121389. doi: 10.1016/j.biortech.2019.121389
[16]	YANG X L, XU J Y, SONG H L, et al. Enhanced removal of antibiotics in wastewater by membrane bioreactor with addition of rice straw[J]. International Biodeterioration & Biodegradation,2020,148:104868.
[17]	WANG X M, XING L J, QIU T L, et al. Simultaneous removal of nitrate and pentachlorophenol from simulated groundwater using a biodenitrification reactor packed with corncob[J]. Environmental Science and Pollution Research International,2013,20(4):2236-2243. doi: 10.1007/s11356-012-1092-9
[18]	SI Z H, SONG X S, WANG Y H, et al. Intensified heterotrophic denitrification in constructed wetlands using four solid carbon sources: denitrification efficiency and bacterial community structure[J]. Bioresource Technology,2018,267:416-425. doi: 10.1016/j.biortech.2018.07.029
[19]	WANG H S, FENG C P, DENG Y. Effect of potassium on nitrate removal from groundwater in agricultural waste-based heterotrophic denitrification system[J]. Science of the Total Environment,2020,703:134830. doi: 10.1016/j.scitotenv.2019.134830
[20]	XU Z X, SHAO L, YIN H L, et al. Biological denitrification using corncobs as a carbon source and biofilm carrier[J]. Water Environment Research,2009,81(3):242-247. doi: 10.2175/106143008X325683
[21]	MARTÍNEZ-COSTA J I, MALDONADO RUBIO M I, LEYVA-RAMOS R. Degradation of emerging contaminants diclofenac, sulfamethoxazole, trimethoprim and carbamazepine by bentonite and vermiculite at a pilot solar compound parabolic collector[J]. Catalysis Today,2020,341:26-36. doi: 10.1016/j.cattod.2018.07.021
[22]	ZHANG R C, YANG Y K, HUANG C H, et al. UV/H₂O₂ and UV/PDS treatment of trimethoprim and sulfamethoxazole in synthetic human urine: transformation products and toxicity[J]. Environmental Science & Technology,2016,50(5):2573-2583.
[23]	AHSAN M A, ISLAM M T, HERNANDEZ C, et al. Adsorptive removal of sulfamethoxazole and bisphenol A from contaminated water using functionalized carbonaceous material derived from tea leaves[J]. Journal of Environmental Chemical Engineering,2018,6(4):4215-4225. doi: 10.1016/j.jece.2018.06.022
[24]	MA H, LI J B, LIU W W, et al. Novel synthesis of a versatile magnetic adsorbent derived from corncob for dye removal[J]. Bioresource Technology,2015,190:13-20. doi: 10.1016/j.biortech.2015.04.048
[25]	KANG J, LIU H J, ZHENG Y M, et al. Application of nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, UV-Visible spectroscopy and kinetic modeling for elucidation of adsorption chemistry in uptake of tetracycline by zeolite beta[J]. Journal of Colloid and Interface Science,2011,354(1):261-267. doi: 10.1016/j.jcis.2010.10.065
[26]	SING K S W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Provisional)[J]. Pure and Applied Chemistry,1982,54(11):2201-2218. doi: 10.1351/pac198254112201
[27]	TAN G Q, YUAN H Y, LIU Y, et al. Removal of lead from aqueous solution with native and chemically modified corncobs[J]. Journal of Hazardous Materials,2010,174(1/2/3):740-745.
[28]	KYZAS G Z, LAZARIDIS N K, MITROPOULOS A C. Removal of dyes from aqueous solutions with untreated coffee residues as potential low-cost adsorbents: equilibrium, reuse and thermodynamic approach[J]. Chemical Engineering Journal,2012,189/190:148-159. doi: 10.1016/j.cej.2012.02.045
[29]	NIELSEN L, BANDOSZ T J. Analysis of sulfamethoxazole and trimethoprim adsorption on sewage sludge and fish waste derived adsorbents[J]. Microporous and Mesoporous Materials,2016,220:58-72. doi: 10.1016/j.micromeso.2015.08.025
[30]	ARYEE A A, HAN R P. A novel biocomposite based on peanut husk with antibacterial properties for the efficient sequestration of trimethoprim in solution: batch and column adsorption studies[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2022,635:128051. doi: 10.1016/j.colsurfa.2021.128051
[31]	NIELSEN L, BANDOSZ T J. Analysis of the competitive adsorption of pharmaceuticals on waste derived materials[J]. Chemical Engineering Journal,2016,287:139-147. doi: 10.1016/j.cej.2015.11.016
[32]	ZHANG Y L, LIN S S, DAI C M, et al. Sorption-desorption and transport of trimethoprim and sulfonamide antibiotics in agricultural soil: effect of soil type, dissolved organic matter, and pH[J]. Environmental Science and Pollution Research International,2014,21(9):5827-5835. doi: 10.1007/s11356-014-2493-8
[33]	KOČÁREK M, KODEŠOVÁ R, VONDRÁČKOVÁ L, et al. Simultaneous sorption of four ionizable pharmaceuticals in different horizons of three soil types[J]. Environmental Pollution,2016,218:563-573. doi: 10.1016/j.envpol.2016.07.039
[34]	MARTÍNEZ-COSTA J I, LEYVA-RAMOS R, PADILLA-ORTEGA E, et al. Antagonistic, synergistic and non-interactive competitive sorption of sulfamethoxazole-trimethoprim and sulfamethoxazole-cadmium (Ⅱ) on a hybrid clay nanosorbent[J]. Science of the Total Environment,2018,640/641:1241-1250. doi: 10.1016/j.scitotenv.2018.05.399
[35]	DODD M C, HUANG C H. Transformation of the antibacterial agent sulfamethoxazole in reactions with chlorine: kinetics, mechanisms, and pathways[J]. Environmental Science & Technology,2004,38(21):5607-5615.
[36]	PAMPHILE N, LIU X J, YU G W, et al. Synthesis of a novel core-shell-structure activated carbon material and its application in sulfamethoxazole adsorption[J]. Journal of Hazardous Materials,2019,368:602-612. doi: 10.1016/j.jhazmat.2019.01.093
[37]	KODEŠOVÁ R, GRABIC R, KOČÁREK M, et al. Pharmaceuticals' sorptions relative to properties of thirteen different soils[J]. Science of the Total Environment,2015,511:435-443. doi: 10.1016/j.scitotenv.2014.12.088
[38]	MANJUNATH S V, SINGH BAGHEL R, KUMAR M. Antagonistic and synergistic analysis of antibiotic adsorption on Prosopis juliflora activated carbon in multicomponent systems[J]. Chemical Engineering Journal,2020,381:122713. doi: 10.1016/j.cej.2019.122713
[39]	BEKÇI Z, SEKI Y, YURDAKOÇ M K. Equilibrium studies for trimethoprim adsorption on montmorillonite KSF[J]. Journal of Hazardous Materials,2006,133(1/2/3):233-242.
[40]	OTTMAR K J, COLOSI L M, SMITH J A. Sorption of statin pharmaceuticals to wastewater-treatment biosolids, terrestrial soils, and freshwater sediment[J]. Journal of Environmental Engineering,2010,136(3):256-264. doi: 10.1061/(ASCE)EE.1943-7870.0000125
[41]	赵敏. 改性生物炭对磷酸盐和六价铬的吸附特性研究[D]. 广州: 华南理工大学, 2021.
[42]	程德义, 杜超, 黄兆琴, 等.巯基化稻壳炭吸附废水中Zn(Ⅱ)试验研究[J]. 环境工程技术学报,2018,8(5):519-526. CHENG D Y, DU C, HUANG Z Q, et al. Adsorption of Zn(Ⅱ) from wastewater by sulfhydryl rice husk carbon[J]. Journal of Environmental Engineering Technology,2018,8(5):519-526.
[43]	STYLIANOU M, CHRISTOU A, MICHAEL C, et al. Adsorption and removal of seven antibiotic compounds present in water with the use of biochar derived from the pyrolysis of organic waste feedstocks[J]. Journal of Environmental Chemical Engineering,2021,9(5):105868. doi: 10.1016/j.jece.2021.105868
[44]	连斌, 吴骥子, 赵科理, 等.铁锰氧化物-微生物负载生物质炭材料对镉和砷的吸附机制[J]. 环境科学,2022,43(3):1584-1595. LIAN B, WU J Z, ZHAO K L, et al. Novel insight into the adsorption mechanism of Fe-Mn oxide-microbe combined biochar for Cd(Ⅱ) and As(Ⅲ)[J]. Environmental Science,2022,43(3):1584-1595.
[45]	翟辉, 孙红霞, 李义连, 等.微量As(Ⅲ)在粘土矿物上的吸附模拟实验研究[J]. 农业环境科学学报,2008,27(6):2246-2250. doi: 10.3321/j.issn:1672-2043.2008.06.021 ZHAI H, SUN H X, LI Y L, et al. The study for sorption of trace arsenite on clay minerals[J]. Journal of Agro-Environment Science,2008,27(6):2246-2250. doi: 10.3321/j.issn:1672-2043.2008.06.021
[46]	SEWU D D, BOAKYE P, WOO S H. Highly efficient adsorption of cationic dye by biochar produced with Korean cabbage waste[J]. Bioresource Technology,2017,224:206-213. doi: 10.1016/j.biortech.2016.11.009
[47]	南志江, 蒋煜峰, 毛欢欢, 等.玉米秸秆生物炭对灰钙土吸附金霉素的影响[J]. 环境科学,2021,42(12):5896-5904. NAN Z J, JIANG Y F, MAO H H, et al. Effect of corn stalk biochar on the adsorption of aureomycin from sierozem[J]. Environmental Science,2021,42(12):5896-5904.
[48]	XU G Q, WANG L H, LIU J L, et al. FTIR and XPS analysis of the changes in bamboo chemical structure decayed by white-rot and brown-rot fungi[J]. Applied Surface Science,2013,280:799-805. doi: 10.1016/j.apsusc.2013.05.065
[49]	李志琳, 解宇峰, 程德义, 等.氨化改性小麦秸秆对水体Cd²⁺的吸附性能研究[J]. 环境工程技术学报,2019,9(5):566-572. doi: 10.12153/j.issn.1674-991X.2019.04.010 LI Z L, XIE Y F, CHENG D Y, et al. Adsorption properties of ammonia-modified wheat straw on aquatic cadmium[J]. Journal of Environmental Engineering Technology,2019,9(5):566-572. doi: 10.12153/j.issn.1674-991X.2019.04.010
[50]	MA H, LI J B, LIU W W, et al. Hydrothermal preparation and characterization of novel corncob-derived solid acid catalysts[J]. Journal of Agricultural and Food Chemistry,2014,62(23):5345-5353. ⊗ doi: 10.1021/jf500490m