| Professional Committee of Rock and Mineral Testing Technology of the Geological Society of China, National Geological Experiment and Testing Center | Host |
| Citation: |
REN Yu, TAN Jun, WANG Jihua, CAO Wengeng, WU Lin, LI Xiangzhi, LUO Silang. The Influence of Small Molecule Organic Acids on the Adsorption of Carbamazepine by Straw Biochar/Montmorillonite Complex and the Threshold Effect[J]. Rock and Mineral Analysis, 2025, 44(4): 628-644. doi: 10.15898/j.ykcs.202505160124
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The Influence of Small Molecule Organic Acids on the Adsorption of Carbamazepine by Straw Biochar/Montmorillonite Complex and the Threshold Effect
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Abstract
Crop straw biochar, as a green and efficient pollution remediation material, demonstrates significant environmental benefits and economic advantages in removing pharmaceutical active compounds (PhACs) from soil. Carbamazepine (CBZ), a persistent environmental risk pollutant within PhACs, represents a crucial target substance for removal from soil. However, the impact of low molecular weight organic acids (LMWOAs) produced by plant root exudates and organic matter degradation on the CBZ adsorption capacity of straw biochar remains poorly understood. This study investigates the adsorption capacity of biochar derived from corn, wheat, and rice straws on CBZ in montmorillonite through laboratory batch experiments and chromatographic analysis, as well as the influence of two LMWOAs (citric acid and oxalic acid) on the adsorption process. The results indicate that the adsorption capacity of montmorillonite for CBZ progressively increases with higher CBZ concentrations. Significant correlations between O/C, H/C, and (O+N)/C ratios with the adsorption affinity coefficient KF suggest that CBZ adsorption by straw biochar results from the combined effects of physical and chemical adsorption mechanisms, including pore filling, hydrophobic interactions, and π–π interactions. Notably, rice straw biochar exhibits the highest maximum adsorption capacity for CBZ at 115.6mg/g, significantly surpassing corn straw biochar (13.1mg/g) and wheat straw biochar (19.5mg/g), attributed to its stronger surface aromaticity and non-polarity. Although the addition of citric acid and oxalic acid reduces the adsorption coefficient (Kd) of CBZ on montmorillonite by 99%, it has minimal impact on the CBZ adsorption capacity of straw biochar. The threshold effect of LMWOAs in the montmorillonite-biochar composite system, characterized by “low concentration promotion and high concentration inhibition” in CBZ adsorption, indicates their influence on mineral-biochar interface interactions. These findings demonstrate that the incorporation of straw biochar into soil significantly enhances CBZ adsorption capacity, suggesting its potential as a soil remediation agent with robust resistance to environmental interference and promising application prospects. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202505160124 . -
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References
[1] Ban M J, Lee D H, Lee B T, et al. Assessing the environmental determinants of micropollutant contamination in streams using explainable machine learning and network analysis[J]. Chemosphere, 2025, 370: 144041. doi: 10.1016/j.chemosphere.2024.144041 [2] Wilkinson J L, Boxall A B A, Kolpin D W, et al. Pharmaceutical pollution of the world’s rivers[J]. Proceedings of the National Academy of Sciences of the United States of America, 2022, 119(8): 1−10. doi: 10.1073/pnas.2113947119 [3] Bunting S Y, Lapworth D J, Crane E J, et al. Emerging organic compounds in European groundwater[J]. Environmental Pollution, 2021, 269: 115945. doi: 10.1016/j.envpol.2020.115945 [4] Tapia I V, Martínez T S, Castro M A, et al. Occurrence of emerging organic contaminants and endocrine disruptors in different water compartments in Mexico—A review[J]. Chemosphere, 2022, 308(1): 136285. doi: 10.1016/j.Chemosphere.2022.136285 [5] K’oreje K O, Okoth M, van Langenhove H, et al. Occurrence and treatment of contaminants of emerging concern in the African aquatic environment: Literature review and a look ahead(Review)[J]. Journal of Environmental Management, 2020, 254: 109752. doi: 10.1016/j.jenvman.2019.109752 [6] Muambo K E, Kim M G, Kim D H, et al. Pharmaceuticals in raw and treated water from drinking water treatment plants nationwide: Insights into their sources and exposure risk assessment[J]. Water Research X, 2024, 24: 100256. doi: 10.1016/j.wroa.2024.100256 [7] 梁贝竹, 陈建耀, 杨再智, 等. 华南滨海小流域地下水中PPCPs的分布、来源及影响因素[J]. 生态环境学报, 2024, 33(2): 249−260. doi: 10.16258/j.cnki.1674-5906.2024.02.009 Liang B Z, Chen J Y, Yang Z Z, et al. Spatial pattern and sources of PPCPs in groundwater and relevant influencing factors in a coastal watershed in South China: A case study in Tangjiawan Town of Zhuhai, Guangdong Province[J]. Ecology and Environmental Sciences, 2024, 33(2): 249−260. doi: 10.16258/j.cnki.1674-5906.2024.02.009 [8] Trognon J, Albasi C, Choubert J M. A critical review on the pathways of carbamazepine transformation products in oxidative wastewater treatment processes[J]. Science of the Total Environment, 2024, 912: 169040. doi: 10.1016/j.scitotenv.2023.169040 [9] Lu Z Y, Liu C Y, Hu Y Y, et al. Unmasking spatial heterogeneity in phytotoxicology mechanisms induced by carbamazepine by mass spectrometry imaging and multiomics analyses[J]. Environmental Science & Technology, 2024, 58(31): 13986−13994. doi: 10.1021/acs.est.4c04628 [10] Liu Q Z, Wang L, Xu X, et al. Antiepileptic drugs in aquatic environments: Occurrence, toxicity, transformation mechanisms and fate[J]. Critical Reviews in Environmental Science and Technology, 2023, 53(23): 2030−2054. doi: 10.1080/10643389.2023.2209010 [11] 阎晓静, 王金花, 朱鲁生, 等. 卡马西平对小球藻生长的影响和氧化损伤[J]. 农业环境科学学报, 2017, 36(4): 643−650. doi: 10.11654/jaes.2016-1259 Yan X J, Wang J H, Zhu L S, et al. Effects of carbamazepine on the growth and the oxidative damage of Chlorella[J]. Journal of Agro-Environment Science, 2017, 36(4): 643−650. doi: 10.11654/jaes.2016-1259 [12] Schapira M, Manor O, Golan N, et al. Involuntary human exposure to carbamazepine: A cross-sectional study of correlates across the lifespan and dietary spectrum[J]. Environment International, 2020, 143: 105951. doi: 10.1016/j.envint.2020.105951 [13] 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]. 中国地质, 2024, 51(6): 1895−1916. doi: 10.12029/gc20231028001 Cao W G, Wang Y Y, Zhang Y N, et al. Pollution status, environmental risk and development trend of groundwater containing microplastics[J]. Geology in China, 2024, 51(6): 1895−1916. doi: 10.12029/gc20231028001 [14] 任宇, 曹文庚, 肖舜禹, 等. 重金属在土壤中的分布、危害与治理技术研究进展[J]. 中国地质, 2024, 51(1): 118−142. doi: 10.12029/gc20230320001 Ren Y, Cao W G, Xiao S Y, et al. Research progress on distribution, harm and control technology of heavy metals in soil[J]. Geology in China, 2024, 51(1): 118−142. doi: 10.12029/gc20230320001 [15] 杨梦楠, 孙晗, 曹海龙, 等. 生物炭-壳聚糖磁性复合吸附剂的制备及去除地下水中铅和铜[J]. 岩矿测试, 2023, 42(3): 563−575. doi: 10.15898/j.ykcs.202208230155 Yang M N, Sun H, Cao H L, et al. Preparation and application of biochar-chitosan magnetic composite adsorbent for removal of lead and copper from groundwater[J]. Rock and Mineral Analysis, 2023, 42(3): 563−575. doi: 10.15898/j.ykcs.202208230155 [16] Liu S W, Cen B T, Yu Z N, et al. The key role of biochar in amending acidic soil: Reducing soil acidity and improving soil acid buffering capacity[J]. Biochar, 2025, 7(1): 1−20. doi: 10.1007/s42773-025-00432-8 [17] 周松, 杨健豪, 晏士玮, 等. 根际有机酸对土壤中重金属化学行为和生物有效性的影响研究进展[J]. 生物学杂志, 2022, 39(3): 103−106, 124. doi: 10.3969/j.issn.2095-1736.2022.03.103 Zhou S, Yang J H, Yan S W, et al. Research progress on the effects of rhizosphere organic acids on the chemical behavior and bioavailability of heavy metals in soil[J]. Journal of Biology, 2022, 39(3): 103−106, 124. doi: 10.3969/j.issn.2095-1736.2022.03.103 [18] Jia M Y, Wang F, Bian Y R, et al. Sorption of sulfamethazine to biochars as affected by dissolved organic matters of different origin[J]. Bioresource Technology, 2018, 248: 36−43. doi: 10.1016/j.biortech.2017.08.082 [19] Zhou X, Zhong Y, He L, et al. Surface modification of wood activated carbon by CVD of NH3 to improve its micropore volume and adsorption to carbamazepine[J]. International Journal of Nanomedicine, 2025, 20: 3251−3267. doi: 10.2147/IJN.S495746 [20] Aylin A, Ramin A , Ajay K D, et al. Effective adsorption of carbamazepine from water by adsorbents developed from flax shives and oat hulls: Key factors and characterization[J]. Industrial Crops and Products, 2021, 170: 113721. doi: 10.1016/j.indcrop.2021.113721 [21] Bakkaloglu S, Ersan M, Karanfil T, et al. Effect of superfine pulverization of powdered activated carbon on adsorption of carbamazepine in natural source waters[J]. Science of the Total Environment, 2021, 793: 148473. doi: 10.1016/j.scitotenv.2021.148473 [22] Baghdadi M, Ghaffari E, Aminzadeh B. Removal of carbamazepine from municipal wastewater effluent using optimally synthesized magnetic activated carbon: Adsorption and sedimentation kinetic studies[J]. Journal of Environmental Chemical Engineering, 2016, 4(3): 3309−3321. doi: 10.1016/j.jece.2016.06.034 [23] Xue Y T, Guo Y T, Zhang X, et al. Efficient adsorptive removal of ciprofloxacin and carbamazepine using modified pinewood biochar—A kinetic, mechanistic study[J]. Chemical Engineering Journal, 2022, 450: 137896. doi: 10.1016/j.cej.2022.137896 [24] Chu G, Zhao J, Liu Y, et al. The relative importance of different carbon structures in biochars to carbamazepine and bisphenol A sorption[J]. Journal of Hazardous Materials, 2019, 373: 106−114. doi: 10.1016/j.jhazmat.2019.03.078 [25] He Q, Liang J J, Chen L X, et al. Removal of the environmental pollutant carbamazepine using molecular imprinted adsorbents: Molecular simulation, adsorption properties, and mechanisms[J]. Water Research, 2020, 168: 115164. doi: 10.1016/j.watres.2019.115164 [26] Zhong H, Zhu G J, Wang Z Z, et al. Efficient adsorption removal of carbamazepine from water by dual-activator modified hydrochar[J]. Separation and Purification Technology, 2025, 353(Part B): 128287. doi: 10.1016/j.seppur.2024.128287 [27] 刘忠珍. 丁草胺与土壤及土壤组分作用机理的研究[D]. 杭州: 浙江大学, 2007. Liu Z Z. The mechanism of butachlor adsorption on soils and soil components[D]. Hangzhou: Zhejiang University, 2007. [28] 薛英文, 赵曼妤, 胡张怡. 蒙脱土吸附去除盐酸四环素(TCH)实验研究[J]. 中国农村水利水电, 2024(2): 147−152, 159. doi: 10.12396/znsd.231178 Xue Y W, Zhao M Y, Hu Z Y. Research on the removal of tetracycline hydrochloride (TCH) by adsorption on montmorillonite[J]. China Rural Water and Hydropower, 2024(2): 147−152, 159. doi: 10.12396/znsd.231178 [29] 吴林. 蒙脱土和高岭土对吉非罗齐的吸附特征及影响因素研究[D]. 北京: 中国地质大学(北京), 2015. Wu L. Study on the sorption of gemfibrozil to montmorillonite and kaolinite and its influencing factors[D]. Beijing: China University of Geosciences (Beijing), 2015. [30] Yu Y W, Chen D Z, Xie S S, et al. Adsorption behavior of carbamazepine on Zn-MOFs derived nanoporous carbons: Defect enhancement, role of N doping and adsorption mechanism[J]. Journal of Environmental Chemical Engineering, 2022, 10(3): 107660. doi: 10.1016/j.jece.2022.107660 [31] 张威 张书缘, 孔祥科, 等. 磺胺甲恶唑和卡马西平在孔隙介质中的吸附行为与影响因素研究[J/OL]. 岩矿测试(2024-10-21) [2025-08-04]. https://doi.org/10.15898/j.ykcs.202407110154. Zhang W, Zhang S Y, Kong X K, et al. Adsorption behavior and influencing factors of sulfamethoxazole and carbamazepine on porous media [J/OL]. Rock and Mineral Analysis (2024-10-21) [2025-08-04]. https://doi.org/10.15898/j.ykcs.202407110154. [32] Nezhadali A, Koushali S E, Divsar F. Synthesis of polypyrrole-chitosan magnetic nanocomposite for the removal of carbamazepine from wastewater: Adsorption isotherm and kinetic study[J]. Journal of Environmental Chemical Engineering, 2021, 9(4): 105648. doi: 10.1016/j.jece.2021.105648 [33] Ashiq A, Sarkar B, Adassooriya N, et al. Sorption process of municipal solid waste biochar-montmorillonite composite for ciprofloxacin removal in aqueous media[J]. Chemosphere, 2019, 236: 124384. doi: 10.1016/j.chemosphere.2019.124384 [34] Zhang H Y, Li Q Y, Zhang X, et al. Insight into the mechanism of low molecular weight organic acids-mediated release of phosphorus and potassium from biochars[J]. Science of the Total Environment, 2020, 742: 140416. doi: 10.1016/j.scitotenv.2020.140416 [35] Rayanne M A V, Marlon L M, Luciano C B L, et al. Carbamazepine adsorption with a series of organoclays: Removal and toxicity analyses[J]. Applied Water Science, 2024, 14(6): 133. doi: 10.1007/s13201-024-02198-z [36] 石林. 土壤矿物对小分子有机酸的吸附保护机制[D]. 昆明: 昆明理工大学, 2021. Shi L. Mechanisms of soil mineral adsorption and protection on low molecular weight organic acids [D]. Kunming: Kunming University of Science and Technology, 2021. [37] Sun B B, Lian F, Bao Q L, et al. Impact of low molecular weight organic acids (LMWOAs) on biochar micropores and sorption properties for sulfamethoxazole[J]. Environmental Pollution, 2016, 214(16): 142−148. doi: 10.1016/j.envpol.2016.04.017 [38] Liu X L, Ji R, Shi Y, et al. Release of polycyclic aromatic hydrocarbons from biochar fine particles in simulated lung fluids: Implications for bioavailability and risks of airborne aromatics[J]. Science of the Total Environment, 2019, 655: 1159−1168. doi: 10.1016/j.scitotenv.2018.11.294 [39] Jiang Y F, Wu J L, Liu Z W, et al. Unveiling the impact of low-molecular-weight organic acids on enrofloxacin sorption in North China agricultural soil: Insights and implications[J]. Journal of Environmental Management, 2024, 370: 123060. doi: 10.1016/j.jenvman.2024.123060 [40] Xu Z B, Xu X Y, Yao C B, et al. Interaction with low molecular weight organic acids affects the electron shuttling of biochar for Cr(Ⅵ) reduction[J]. Journal of Hazardous Materials, 2019, 378: 120705. doi: 10.1016/j.jhazmat.2019.05.098 [41] Alozie N, Heaney N, Lin C X. Biochar immobilizes soil-borne arsenic but not cationic metals in the presence of low-molecular-weight organic acids[J]. Science of the Total Environment, 2018, 630(1): 1188−1194. doi: 10.1016/j.scitotenv.2018.02.319 [42] Huang Q X, Chen W Z, Gao J Y, et al. Impact of low molecular weight organic acids on heavy metal(loid) desorption in biochar-amended paddy soil[J]. Environmental Geochemistry and Health, 2024, 46(8): 289. doi: 10.1007/s10653-024-02064-6 [43] 彭章, 龚香宜, 熊武芳, 等. 有机酸对芘在土壤中的吸附影响研究[J]. 农业环境科学学报, 2020, 39(7): 1540−1547. doi: 10.11654/jaes.2020-0217 Peng Z, Gong X Y, Xiong W F, et al. Effects of organic acids on the adsorption of pyrene in soil[J]. Journal of Agro-Environment Science, 2020, 39(7): 1540−1547. doi: 10.11654/jaes.2020-0217 [44] Szabó L, Vancsik A, Bauer L, et al. Effects of root-derived organic acids on sorption of pharmaceutically active compounds in sandy topsoil[J]. Chemosphere, 2024, 355: 141759. doi: 10.1016/j.chemosphere.2024.141759 [45] Wang Y, Wang C X, Xiong J Y, et al. Effects of low molecular weight organic acids on aggregation behavior of biochar colloids at acid and neutral conditions[J]. Biochar, 2022, 4(1): 20. doi: 10.1007/s42773-022-00142-5 [46] 周丹丹, 梁妮, 李浩, 等. 小分子有机酸对生物炭吸附Cu(Ⅱ)的影响[J]. 农业环境科学学报, 2016, 35(10): 1923−1930. doi: 10.11654/jaes.2016-0376 Zhou D D, Liang N, Li H, et al. Effect of low molecular weight organic acids on Cu(Ⅱ) adsorption by biochars[J]. Journal of Agro-Environment Science, 2016, 35(10): 1923−1930. doi: 10.11654/jaes.2016-0376 -
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REN Yu, TAN Jun, WANG Jihua, CAO Wengeng, WU Lin, LI Xiangzhi, LUO Silang. The Influence of Small Molecule Organic Acids on the Adsorption of Carbamazepine by Straw Biochar/Montmorillonite Complex and the Threshold Effect[J]. Rock and Mineral Analysis, 2025, 44(4): 628-644. doi: 10.15898/j.ykcs.202505160124
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Figure 1.
Scanning electron microscope (SEM) images and Fourier transform infrared spectroscopy (FTIR) spectra of three types of straw biochar: (a) Rice; (b) Wheat; (c) Corn; (d) FTIR
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Figure 2.
Isothermal adsorption results of CBZ on straw biochar, the change of Gibbs free energy, and the relationship between physicochemical properties and adsorption performance. (a) Isothermal adsorption; (b) Gibbs free energy change; (c) Relationship between specific surface area, average pore diameter and micropore volume and KF in Freundlich equation; (d) Relationship between (O+N)/C and H/C of biochar and KF in Freundlich equation. Initial pH=7.0±0.25, background solution was 0.01mol/L NaCl solution
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Figure 3.
Experimental results of the adsorption kinetics (a) and isothermal adsorption (b) experiments of montmorillonite. (a) Initial CBZ concentration was 18.47mg/L, pH=7.0±0.3; (b) Initial pH=7.0±0.25, background solution was 0.01mol/L NaCl solution
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Figure 4.
The isothermal adsorption results of carbamazepine (CBZ) on montmorillonite after adding different proportions of straw biochar. Initial pH=7.0±0.25, background solution was 0.01mol/L NaCl solution
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Figure 5.
Theoretical and actual adsorption capacities of straw biochar at different liquid phase concentrations. (a) Wheat straw biochar; (b) Corn straw biochar; (c) Rice straw biochar
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Figure 6.
Adsorption coefficients (Kd) of carbamazepine by montmorillonite and biochar in the presence of different concentrations of LMWOAs. (a) Montmorillonite; (b) Wheat straw biochar; (c) Corn straw biochar; (d) Rice straw biochar. Initial pH=7.0±0.25, background solution was 0.01mol/L NaCl solution, initial concentration of CBZ was 30.97mg/L
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Figure 7.
Adsorption coefficient (Kd) of carbamazepine in montmorillonite-biochar systems with different concentrations of LMWOAs. (a) Addition of 5% wheat straw biochar; (b) Addition of 5% corn straw biochar; (c) Addition of 1% rice straw biochar. Initial pH=7.0±0.25, background solution was 0.01mol/L NaCl, initial CBZ concentration was 30.97mg/L.