Adsorption Behavior and Influencing Factors of Sulfamethoxazole and Carbamazepine on Porous Media

ZHANG Wei; ZHANG Shuyuan; KONG Xiangke; XU Ruifeng; HAN Mei; LIU Shenghua; ZENG Shaojian; WU Lin

doi:10.15898/j.ykcs.202407110154

Rock and Mineral Analysis > 2024 > In Press, Accepted Manuscript > DOI: 10.15898/j.ykcs.202407110154

ZHANG Wei，ZHANG Shuyuan，KONG Xiangke，et al. Adsorption Behavior and Influencing Factors of Sulfamethoxazole and Carbamazepine on Porous Media[J]. Rock and Mineral Analysis，2024，44（1）：1−13. DOI: 10.15898/j.ykcs.202407110154

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Adsorption Behavior and Influencing Factors of Sulfamethoxazole and Carbamazepine on Porous Media

ZHANG Wei^{1, 2, 3,},
ZHANG Shuyuan^{1, 3},
KONG Xiangke^{1, 2, 3, ,},
XU Ruifeng^{1, 2, 3},
HAN Mei¹,
LIU Shenghua^{1, 2},
ZENG Shaojian⁴,
WU Lin⁵

1.
Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences, Xiamen 361021, China
2.
Key Laboratory of Groundwater Remediation of Hebei Province and China Geological Survey, Shijiazhuang 050061, China
3.
Fujian Provincial Key Laboratory of Water Cycling and Eco-Geological Processes, Xiamen 361021, China
4.
Xiamen Environmental Monitoring Station, Xiamen 361021, China
5.
College of Water Resources, North China University of Water Resources and Electric Power, Zhengzhou 450046, China

More Information

Received Date: July 10, 2024
Revised Date: September 11, 2024
Accepted Date: September 13, 2024
Available Online: October 20, 2024

Abstract

HIGHLIGHTS
(1) Adsorption processes of SMX and CBZ by pore media follow Lagergren model and Langmuir model and belongs to single molecular layer chemisorption.

(2) The adsorption capacity of SMX in silt that existed mainly in anionic form increases with the increase of pH value (5.0～9.0), while the adsorption capacity of CBZ in molecular form does not change significantly with the change of pH.

(3) The coexistence of dissolved humic acid (8～50mg/L) inhibits the adsorption of SMX and CBZ. The adsorption capacity of SMX and CBZ increases with the increase of organic matter and iron oxide content in porous media.

ABSTRACT

This study results show that the adsorption processes of SMX and CBZ by pore media follow Lagergren model and Langmuir model. The adsorption process can be characterized by rapid adsorption and slow equilibrium and it is a monomolecular layer chemical adsorption. The adsorption of SMX is a spontaneous exothermic process, while the adsorption of CBZ is an endothermic process. Under the experimental conditions, the maximum adsorption capacity of SMX and CBZ of silt with small particle size, high organic matter content and large specific surface area is 3.0 times and 2.3 times of that of fine sand, respectively. The adsorption of SMX is mainly affected by the electrostatic attraction of mineral surface and the distribution of organic matter, while CBZ is more controlled by the distribution. The adsorption capacity of SMX in silt that existed mainly in anionic form increases with the increase of pH value (5.0～9.0), while the adsorption capacity of CBZ in molecular form does not change significantly with the change of pH. The coexistence of dissolved humic acid (8～50mg/L) inhibits the adsorption of SMX and CBZ. The adsorption capacity of SMX and CBZ increases with the increase of organic matter and iron oxide content in porous media. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202407110154.
- sulfamethoxazole,
- carbamazepine,
- porous media,
- adsorption,
- influencing factor
BRIEF REPORT
Significance: Sulfamethoxazole (SMX) and carbamazepine (CBZ)，as representatives of pharmaceutically active compoundss (PhACs)，have attracted much attention. Adsorption plays a pivotal role in determining the migration of PhACs in environments. However，there is a lack of systematical analyses of the adsorption patterns of SMX and CBZ on porous media and the influence of environmental factors on adsorption. These limit the understanding of the potential environmental risks of SMX and CBZ. Explore the adsorption mechanism of SMX and CBZ on the porous medium，and identify the influence of solution pH，DHA content，and soil mineral composition on their adsorption. The results of these studies provide a scientific basis for elucidating the adsorption behavior of SMX and CBZ in soil and water environment.

METHODS: The adsorption kinetics，isothermal adsorption characteristics and environmental influencing factors (pH，DHA and mineral composition) of SMX on two typical pore media such as silty soil and fine sand were carried out in batch experiments. A series of kinetic and equilibrium adsorption models were used to simulate the experimental results and reveal the fundamental mechanisms.

Data and Results: The adsorption capacity of SMX and CBZ on porous media increases with time，and then reaches equilibrium，showing the characteristics of rapid adsorption and slow equilibrium (Fig.1). The Lagergren pseudo-second-order kinetic equation can well fit the adsorption process of SMX and CBZ on different porous media (R² is greater than 0.99)，and the fitted equilibrium adsorption capacity is basically the same as the experimental adsorption capacity (Table 3). Langmuir model can well describe the isothermal adsorption process of SMX and CBZ in silt and fine sand，and the maximum adsorption capacities of silt for SMX and CBZ are 0.566μg/g and 3.146μg/g，respectively，and 0.367μg/g for SMX and 1.566μg/g for CBZ in fine sand. The adsorption of SMZ and CBZ on porous media is a monomolecular layer chemical adsorption.

　　At the experimental temperature (15～35℃)，the Gibbs free energy delta (G) is less than 0，indicating that the adsorption reaction of SMX and CBZ by fine sand is spontaneous. The adsorption enthalpy change (ΔH) of SMX is less than 0，indicating that the adsorption of SMX by fine sand is an exothermic process，and the temperature rise has an inhibitory effect on the adsorption of SMX on fine sand. The enthalpy change (ΔH) of CBZ is greater than 0，indicating that the adsorption of fine sand to CBZ is an endothermic process，and the temperature rise can promote the reaction.

　　The adsorption capacity of SMX on silt and fine sand decreases with the increase of solution pH (from 5.0 to 9.0)，while the adsorption capacity of CBZ changes slightly with pH variation (Fig.3). The addition of dissolved HA in the solution can change the functional group structure and distribution on the surface of silt，thus affecting the adsorption process of SMX and CBZ on silt. With the increase of DHA concentration in solution (0-50mg/L)，the adsorption processes of SMX and CBZ on the porous medium show a significant downward trend (Fig.4). The adsorption of SMX and CBZ are inhibited with the coexistence of DHA in the solution. With the increase of the montmorillonite and ferric oxide addition in the solution，the adsorption capacity of SMX and CBZ significantly increases (Fig.6). In addition to the electrostatic interactions and van der Waals forces，iron oxide surfaces can also form complexes by interacting with functional groups of SMX and CBZ.

　　The adsorption processes of SMX and CBZ by pore media conform to Lagergren pseudo-second-order kinetic model and is mainly controlled by chemical adsorption. The adsorption process can be characterized by rapid absorption and slow equilibrium. The SMX and CBZ adsorption data are well fitted with Langmuir adsorption isotherm model，indicating that the adsorption is a monomolecular layer chemical adsorption. Thermodynamic analysis shows that the adsorption of SMX is a spontaneous exothermic process，while the adsorption of CBZ is an endothermic process. The adsorption capacity of SMX in silt increases with the increase of pH value，while the adsorption capacity of CBZ does not change significantly with the change of pH. The coexistence of DHA inhibits the adsorption of SMX and CBZ on porous media. The adsorption capacity of SMX and CBZ increases with the increase of organic matter and iron oxide content in porous media.

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References

[1]	Wang H, Xi H, Xu L L, et al. Ecotoxicological effects, environmental fate and risks of pharmaceutical and personal careproducts in the water environment: A review[J]. Science of the Total Environment, 2021, 78: 147819. doi: 10.1016/j.scitotenv.202l.147819.
[2]	吴林, 李峰, 杜蓓蓓. 药物及个人护理品在土壤中的淋溶迁移性评价[J]. 环境科学与技术, 2015, 38(5): 163−167. doi: 10.3969/j.issn.1003-6504.2015.05.032 Wu L, Li F, Du B B. Evaluation of leachability of pharmaceuticals and personal care products in soils[J]. Environmental Science & Technology, 2015, 38(5): 163−167. doi: 10.3969/j.issn.1003-6504.2015.05.032
[3]	Li H, Cai Y, Gu Z, et al. Accumulation of sulfonamide resistance genes and bacterial community function prediction in microbial fuel cell-constructed wetland treating pharmaceutical wastewater[J]. Chemosphere, 2020, 248: 126014. doi: 10.1016/j.chemosphere.2020.126014
[4]	Zhang Y N, Zhang T T, Liu H Y, et al. Simulated sunlight-induced inactivation of tetracycline resistant bacteria and effects of dissolved organic matter[J]. Water Research, 2020, 185: 116241. doi: 10.1016/j.watres.2020.116241
[5]	郭子宁, 王旭升, 向师正, 等. 再生水入渗区典型抗生素分布特征与地下水微生物群落影响因素研究[J]. 岩矿测试, 2022, 41(3): 451−462. doi: 10.15898/j.cnki.11-2131/td.202111040163 Guo Z N, Wang X S, Xiang S Z, et al. Distribution characteristics of typical antibiotics in reclaimed water infiltration area and influencing factors of groundwater microbial community[J]. Rock and Mineral Analysis, 2022, 41(3): 451−462. doi: 10.15898/j.cnki.11-2131/td.202111040163
[6]	Kovačević S, Radišić M, Laušević M, et al. Occurrence and behavior of selected pharmaceuticals during riverbank filtration in the republic of Serbia[J]. Environmental Science and Pollution Research, 2017, 24(2): 2075−2088. doi: 10.1007/s11356-016-7959-4
[7]	Cao S S, Duan Y P, Tu Y J, et al. Pharmaceuticals and personalcare products in a drinking water resource of Yangtze River Delta ecology and greenery integration development demonstration zone China: Occurrence and human health risk assessment[J]. Science of the Total Environment, 2020, 721:137624
[8]	牛颖, 安圣, 陈凯, 等. 2012—2021年中国地下水抗生素污染现状及分析技术研究进展[J]. 岩矿测试, 2023, 42(1): 39−58. doi: 10.15898/j.cnki.11-2131/td.202210120192 Niu Y, An S, Chen K, et al. A review of current status and analysis methods of antibiotic contamination in groundwater in China (2012—2021)[J]. Rock and Mineral Analysis, 2023, 42(1): 39−58. doi: 10.15898/j.cnki.11-2131/td.202210120192
[9]	Adeleye A S, Xue J, Zhao Y X, et al. Abundance, fate, and effects of pharmaceuticals and care products in aquatic personal environments[J]. Journal of Hazardous Materials, 2022, 424(Pt B):127284.
[10]	Yuan Q L, Li Z P, Li L C, et al. Pharmaceuticals and personal care products transference-transformation in aquifer system[J]. Journal of Groundwater Science and Engineering, 2020, 8(4): 358−365. doi: 10.19637/j.cnki.2305-7068.2020.04.007
[11]	巢铸, 夏鹏, 司静宜, 等. 我国淡水中卡马西平的水质基准初探及生态风险评估[J/OL]. 环境工程(2023-01-19).https://kns.cnki.net/kcms/detail//11.2097.x.20230117.1619.006.html. Chao Z, Xia P, Si J Y, et al. Preliminary study on water quality criteria and ecological risk assessment of carbamazepine in freshwater in China[J/OL]. Environ-mental Engineering (2023-01-19).https://kns.cnki.net/kcms/detail//11.2097.x.20230117.1619.006.html.
[12]	马琳, 李广贺. 地下水中新型污染物的赋存与分布特征[C]//昆明: 中国环境科学学会学术年会论文集, 2013: 3701−3705. Ma L, Li G H. Occurrence and distribution characteristics of new pollutants in groundwater[C]//Kunming: Proceedings of the Annual Conference of the Chinese Society of Environmental Sciences, 2013: 3701−3705.
[13]	Wang J L, Zhang C, Xiong L, et al. Changes of antibiotic occurrence and hydrochemistry in groundwater under the influence of the South-to-North Water Diversion (the Hutuo River, China)[J]. Science of the Total Environment, 2022, 832: 154779. doi: 10.2139/ssrn.3997719
[14]	李烨. 抗生素电离形态对其植物吸收的影响[D]. 大连: 大连理工大学, 2020. Li Y. Effect of ionization speciation on the plant uptake of antibiotics[D]. Dalian: Dalian University of Technology, 2020.
[15]	Cai N, Larese-Casanova P. Application of positively-charged ethylenediamine-functionalized graphene for the sorption of anionic organic contaminants from water[J]. Journal of Environmental Chemical Engineering, 2016, 4(3): 2941−2951. doi: 10.1016/j.jece.2016.06.004
[16]	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
[17]	D’alessio M, Durso L M, Miller D N, et al. Environmental fate and microbial effects of monensin, lincomycin, and sulfamethazine residues in soil[J]. Environmental Pollution, 2019, 246: 60−68. doi: 10.1016/j.envpol.2018.11.093
[18]	Cuprys A, Pulicharla R, Lecka J, et al. Ciprofloxacin-metal complexes-stability and toxicity tests in the presence of humic substances[J]. Chemosphere, 2018, 202: 549−559. doi: 10.1016/j.chemosphere.2018.03.117
[19]	王东升, 李鑫. 不同质地土壤中四环素类抗生素的吸附解吸特性研究[J]. 安全与环境学报, 2017, 17(1): 227−231. doi: 10.13637/j.issn.1009-6094.2017.01.044 Wang D S, Li X. Adsorption and desorption features of tetracycline antibiotics in different texture soils[J]. Journal of Safety and Environment, 2017, 17(1): 227−231. doi: 10.13637/j.issn.1009-6094.2017.01.044
[20]	梁雨, 何江涛, 张思. DOM不同相对分子质量组分在无机矿物上的吸附及其对卡马西平吸附的影响实验[J]. 环境科学, 2018, 39(5): 2219−2229. doi: 10.13227/j.hjkx.201708012 Liang Y, He J T, Zhang S. Adsorption of dissolved organic matter with different relative molecular masses on inorganic minerals and its influence on carbamazepine adsorption behavior[J]. Environmental Science, 2018, 39(5): 2219−2229. doi: 10.13227/j.hjkx.201708012
[21]	孔晨晨, 张世文, 聂超甲, 等. 农用地土壤抗生素组成特征与积累规律[J]. 环境科学, 2019, 40(4): 1981−1989. doi: 10.13227/j.hjkx.201809018 Kong C, Zhang S W, Nie C J, et al. Composition, characteristics, and aceumulation of antibiotics in the soil in agricultural land[J]. Environmental Science, 2019, 40(4): 1981−1989. doi: 10.13227/j.hjkx.201809018
[22]	曹文庚, 王妍妍, 张亚南, 等. 含微塑料地下水的污染现状、环境风险及其发展趋势[J/OL]. 中国地质(2024-01-30).https://link.cnki.net/urlid/11.1167.P.20240130.1025.004. Cao W G, Wang Y Y, Zhang Y N, et al. Pollution status, environmental risk and development trend of groundwater containing microplastics[J/OL]. Geology in China (2024-01-30).https://link.cnki.net/urlid/11.1167.P.20240130.1025.004
[23]	Reguyal F, Sarmah A K. Adsorption of sulfame-thoxazole by magnetic biochar: Effects of pH, ionic strength, natural organic matter and 17α-ethinylestradiol[J]. Science of the Total Environment, 2018, 628/629: 722−730. doi: 10.1016/j.scitotenv.2018.01.323
[24]	Martinez-Costa J I, Maldonado-Rubio M I, Leyva R 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
[25]	梁建军, 何芹, 郑怀礼, 等. 卡马西平印迹吸附剂的分子模拟与吸附机理[J]. 分析化学, 2019, 47(6): 846−854. doi: 10.19756/i.issn.0253-3820.191084 Liang J J, He Q, Zheng H L, et al. Molecular simulation and adsorption mechanism of carbamazepine imprinted adsorbent[J]. Chinese Journal of Analytical Chemistry, 2019, 47(6): 846−854. doi: 10.19756/i.issn.0253-3820.191084
[26]	张文文. 碳基材料对典型 PPCPs在水环境中的吸附行为研究[D]. 北京: 北京建筑大学, 2017. Zhang W W. Study on the sorption behavior of typical PPCPs to carbonaceous materials[D]. Beijing: Beijing University of Civil Engineering and Architecture, 2017.
[27]	张威, 孔祥科, 韩占涛, 等. 7-ACA发酵药渣生物炭对水体中Pb(Ⅱ)和Cd(Ⅱ)的吸附特性[J]. 安全与环境工程, 2022, 29(4): 1−9. doi: 10.13578/j.cnki.issn.1671-1556.20210694 Zhang W, Kong X K, Han Z T, et al. Adsorption characteristics of Pb(Ⅱ) and Cd(Ⅱ) in water bodies onto biochars derived from 7-ACA fermented residue[J]. Safety and Environmental Engineering, 2022, 29(4): 1−9. doi: 10.13578/j.cnki.issn.1671-1556.20210694
[28]	Wang P, Kong X K, Ma L S, et al. Metal(loid)s removal by zeolite-supported iron particles from mine contaminated groundwater: Performance and mechanistic insights[J]. Environmental Pollution, 2022, 313: 120155. doi: 10.1016/j.envpol.2022.120155
[29]	Shi G W, Li Y S, Liu Y C, et al. Predicting the speciation of ionizable antibiotic ciprofloxacin by biochars with varying carbonization degrees[J]. RSC Advances, 2023, 13: 9892−9902. doi: 10.1039/d3ra00122a
[30]	Manjunath S V, Singh B 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
[31]	Rajapaksha A, Ok Y, Vithanage M, et al. Steam activation of biochars facilitates kinetics and pH-resilience of sulfamethazine sorption[J]. Journal of Soils and Sediments, 2016, 16(3): 889−895. doi: 10.1007/s11368-015-1325-x
[32]	时雯雯, 魏兴, 周金龙, 等. 新疆不同质地土壤对石油类污染物的吸附作用[J]. 环境工程, 2022, 40(4): 127−133. doi: 10.13205/j.hjgc.202204018 Shi W W, Wei X, Zhou J L, et al. Adsorption of petroleum pollutants on different texture soils in Xinjiang China[J]. Environmental Engineering, 2022, 40(4): 127−133. doi: 10.13205/j.hjgc.202204018
[33]	汤家喜, 向彪, 李玉, 等. 硅藻土对水中氟化物的吸附特性研究[J]. 生态环境学报, 2022, 31(2): 335−343. doi: 10.16258/j.cnki.1674-5906.2022.02.014 Tang J X, Xiang B, Li Y, et al. Study on adsorption characteristics of fluoride in water by diatomite[J]. Ecology and Environmental Sciences, 2022, 31(2): 335−343. doi: 10.16258/j.cnki.1674-5906.2022.02.014
[34]	Jiang Y, Ma X L, Sun F Y, et al. A comparative study on the adsorption properties of heavy metal Cr in lake sediment and soil[J]. Applied Ecology and Environmental Research, 2021, 19(2): 901−914. doi: 10.15666/AEER/1902_901914
[35]	何红珠, 王欣怡, 卫潇, 等. 牡丹果荚基多孔碳材料对水中四环素的吸附[J]. 农业环境科学学报, 2024, 43(6): 1389−1399. doi: 10.11654/jaes.2023-1106 He H Z, Wang X Y, Wei X, et al. Adsorption of tetracycline in water by peony pod–based porous carbon material[J]. Journal of Agro-Environment Science, 2024, 43(6): 1389−1399. doi: 10.11654/jaes.2023-1106
[36]	钱子妍, 曾娟, 张立刚, 等. 南海深海沉积物对Cu(Ⅱ)的吸附特性研究[J]. 环境科学学报, 2023, 43(9): 152−163. doi: 10.13671/j.hjkxxb.2023.0006 Qian Z Y, Zeng J, Zhang L G, et al. Cu(Ⅱ) adsorption characteristics by deep-sea sediment from the South China Sea[J]. Acta Scientiae Circumstantiae, 2023, 43(9): 152−163. doi: 10.13671/j.hjkxxb.2023.0006
[37]	Chauhan M, Saini V K, Suthar S, et al. Removal of pharmaceuticals and personal care products (PPCPs) from water by adsorption on aluminum pillared clay[J]. Journal of Porous Materials, 2020, 27: 383−393. doi: 10.1007/s10934-019-00817-8
[38]	俞伟, 赵思钰, 王宇航, 等. 苜蓿生物炭对磺胺甲恶唑的吸附机理研究[J]. 西北大学学报(自然科学版), 2022, 52(1): 116−127. doi: 10.16152/j.cnki.xdxbzr.2022-01-014 Yu W, Zhao S Y, Wang Y H, et al. Mechanism of adsorption of sulfamethoxazole by alfalfa biochar at different pyrolysis temperatures[J]. Journal of Northwest University (Natural Science Edition), 2022, 52(1): 116−127. doi: 10.16152/j.cnki.xdxbzr.2022-01-014
[39]	李仁杰. 有机质和团聚物对PPCPs在土壤中吸附和迁移的影响[D]. 北京: 中国科学院大学, 2020. Li R J. Effects of organic matter and aggregate on adsorption and transport of PPCPs in soil[D]. Beijing: University of Chinese Academy of Sciences, 2020.
[40]	Wu Q L, Xian Y, He Z L, et al. Adsorption characteristics of Pb(Ⅱ) using biochar derived from spent mushroom substrate[J]. Scientific Reports, 2019, 9: 15999. doi: 10.1038/s41598-019-52554-2
[41]	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. doi: 10.13227/j.hjkx.202103284 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. doi: 10.13227/j.hjkx.202103284
[42]	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
[43]	Rizzuto S, Baho D L, Jones K C, et al. Binding of waterborne pharmaceutical and personal care products to natural dissolved organic matter[J]. Science of the Total Environment, 2021, 784(36): 147208. doi: 10.1016/j.scitotenv.2021.147208
[44]	汪玉瑛, 尤凌聪, 刘玉学, 等. 蒙脱石对恩诺沙星吸附性能研究[J]. 安全与环境学报, 2019, 19(4): 1349−1358. doi: 10.13637/j.issn.1009-6094.2019.04.034 Wang Y Y, You L C, Liu Y X, et al. Investigation of adsorptive properties of enrofloxacin by using montmorillonite[J]. Journal of Safety and Environment, 2019, 19(4): 1349−1358. doi: 10.13637/j.issn.1009-6094.2019.04.034
[45]	Zhi D, Yang D, Zheng Y, et al. Current progress in the adsorption, transport and biodegradation of antibiotics in soil[J]. Journal of Environmental Management, 2019, 251: 109598. doi: 10.1016/j.jenvman.2019.109598