Distribution of Minerals in Typical Sediment Cores and Their Indicative Role in Nitrobenzene Abiotic Reduction
-
摘要:
为了探究沉积物中矿物分布、还原能力以及非生物还原有机污染物速率之间的关系，选取了两组典型柱状沉积物样品，系统开展了沉积物常量元素与粒径组成、矿物分布及铁赋存状态等地球化学特征分析，定量表征了不同粒径沉积物的供电子能力（electron-donating capacity，EDC），探究了沉积物非生物还原硝基苯的动力学过程.结果表明：不同粒径沉积物中主要矿物不同，伊利石等活性黏土矿物主要富集在黏粒中；黏粒的EDC高于粉粒，且黏粒对硝基苯的非生物还原速率高于粉粒；EDC不仅可以定量表征沉积物的还原能力，而且可作为评估沉积物非生物还原硝基苯能力的指示参数，为预测含水层中硝基苯发生非生物还原的潜力提供理论依据.
Abstract:To explore the relationships among mineral distribution in sediments, their reducing capacity, and the abiotic reduction rate of organic pollutants in groundwater, this study utilized two sets of typical columnar sediment cores. A systematic investigation of sediments was conducted, including particle size composition, mineral distribution, iron speciation, electron-donating capacity (EDC), and abiotic reduction rate of nitrobenzene induced by sediment. Results show that the predominant minerals in sediments varied with sediment particle size, with clay minerals such as illite primarily concentrated in the clay fractions. Clay fractions exhibited a higher EDC than silt fractions, and presented a faster abiotic reduction rate for nitrobenzene. Moreover, EDC not only can serve as a quantitative measure of sediment reducing capacity, but also can act as a valuable indicator for assessing the potential for abiotic reduction of nitrobenzene by sediments. These findings provide a new perspective for predicting the abiotic natural reduction capacity of sediments and groundwater organic contaminant remediation.
-
图 2 柱状沉积物常量地球化学元素含量(以化合物形式表示)统计图与UCC归一化折线
a，b.剖面A；c，d.剖面B
Fig. 2. Statistical graphs and UCC normalized line graph of geochemical element contents in columnar sediments
图 3 剖面A(a)和剖面B(b)柱状沉积物组分含量与平均粒径的垂向特征
Fig. 3. Vertical characteristics of component content and average particle size of columnar sediments in profile A (a) and profile B (b)
图 4 剖面A与剖面B中砂粒(a、d)和粉粒(b、e)中主要矿物箱体图以及剖面A与剖面B中黏粒(c、f)中主要矿物和黏土矿物箱体图
Fig. 4. Box plots of the main minerals in the sand (a, d) and silt (b, e) in profile A and profile B, box plots of the main minerals and clay minerals in clay in profile A (c) and profile B (f)
图 8 剖面A(a~c)、剖面B(d~f)中粉粒和剖面B中黏粒(g~i)的硝基苯还原动力学、拟一级动力学拟合结果及硝基苯还原速率
Fig. 8. NB degradation kinetics, first-order kinetic fitting and nitrobenzene reduction rates of silt from Profile A (a-c), profile B (d-f) and clay from profile B (g-i)
图 9 沉积物样品硝基苯还原率(k)与电子给体容量(EDC)的线性拟合关系
Fig. 9. Linear fitting relationship between nitrobenzene reduction rates (k) and electron-donating capacity (EDC) of sediment samples
图 10 Fecarb/FeSi与EDC相关性分析(a、b)以及Fecarb/FeSi与硝基苯还原速率(k)相关性分析(c、d)
Fig. 10. Correlation analysis of Fecarb/FeSi with EDC of sediment samples (a, b); correlation analysis of Fecarb/FeSi with nitrobenzene reduction rates (k) of sediment samples (c, d)
表 1 柱状沉积物取样层位
Table 1. Sampling layers of columnar sediments
剖面A 剖面B 编号 深度(m) 编号 深度(m) A1 1.0~2.0 B1 1.0~2.0 A2 2.0~3.0 B2 2.0~3.0 A3 3.0~4.0 B3 3.0~4.0 A4 4.0~5.0 B4 4.0~5.0 A5 5.0~6.0 B5 5.0~6.0 A6 6.0~7.0 B6 6.0~7.0 B7 7.0~8.0 
下载: 导出CSV
表 2 柱状沉积物中TOC含量
Table 2. TOC content in columnar sediments
编号 TOC含量占比(%) 编号 TOC含量占比(%) A1 0.70 B1 0.008 3 A2 0.032 B2 0.006 5 A3 0.025 B3 0.005 2 A4 0.024 B4 0.003 1 A5 0.015 B5 0.002 2 A6 0.007 2 B6 0.002 7 B7 0.003 1
下载: 导出CSV
表 3 剖面A、剖面B粉粒和剖面B中黏粒的硝基苯还原速率拟合统计
Table 3. Fitting statistics of the nitrobenzene reduction rates of silt from profile A, profile B and clay from profile B
分组 编号 速率常数k(h-1) R2 剖面A-粉粒 A1 0.001 2 0.89 A2 0.002 2 0.91 A3 0.002 3 0.86 A4 0.001 8 0.85 A5 0.005 9 0.93 A6 0.002 4 0.98 剖面B-粉粒 B1 0.003 5 0.96 B2 0.005 3 0.99 B3 0.002 9 0.98 B4 0.002 5 0.99 B5 0.001 7 0.90 B6 0.002 5 0.97 B7 0.002 8 0.86 剖面B-黏粒 B1 0.002 4 0.99 B2 0.010 6 0.99 B3 0.006 2 0.99 B4 0.007 8 0.97 B5 0.002 8 0.89 B6 0.002 2 0.90 B7 0.002 2 0.88
下载: 导出CSV
-
Aeppli, M., Thompson, A., Dewey, C., et al., 2022. Redox Properties of Solid Phase Electron Acceptors Affect Anaerobic Microbial Respiration under Oxygen⁃Limited Conditions in Floodplain Soils. Environmental Science Technology, 56(23): 17462-17470. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.2c05797">https://doi.org/10.1021/acs.est.2c05797 Cárdenas⁃Hernández, P. A., Murillo⁃Gelvez, J., Rincón⁃Rodríguez, J. C., et al., 2025. Predicting Abiotic Reduction Rate Constants of Munition Compounds in Soils. Environmental Science Technology, 59(6): 3229-3238. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.4c12872">https://doi.org/10.1021/acs.est.4c12872 Chen, H. Y., Shen, R. J., Huang, H. B., et al., 2025. Adsorption Characteristics and Spatial Distribution Prediction of Antibiotics in Sediments of the Yangtze River Delta. Rock and Mineral Analysis, 44(5): 1051-1068 (in Chinese with English abstract). Dong, H. L., Zeng, Q., Sheng, Y. Z., et al., 2023. Coupled Iron Cycling and Organic Matter Transformation across Redox Interfaces. Nature Reviews Earth Environment, 4(9): 659-673. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1038/s43017⁃023⁃00470⁃5">https://doi.org/10.1038/s43017⁃023⁃00470⁃5 Entwistle, J., Latta, D. E., Scherer, M. M., et al., 2019. Abiotic Degradation of Chlorinated Solvents by Clay Minerals and Fe(Ⅱ): Evidence for Reactive Mineral Intermediates. Environmental Science Technology, 53(24): 14308-14318. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.9b04665">https://doi.org/10.1021/acs.est.9b04665 Fang, Q., Li, Y., Ding, H. R., et al., 2025. Formation and Transformation of Clay Minerals in Mars⁃Analog Rock Varnish. American Mineralogist, 110(9): 1343-1360. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.2138/am⁃2024⁃9585">https://doi.org/10.2138/am⁃2024⁃9585 Gorski, C. A., Scherer, M. M., 2009. Influence of Magnetite Stoichiometry on FeⅡ Uptake and Nitrobenzene Reduction. Environmental Science Technology, 43(10): 3675-3680. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/es803613a">https://doi.org/10.1021/es803613a He, Y. T., Wilson, J. T., Su, C., et al., 2015. Review of Abiotic Degradation of Chlorinated Solvents by Reactive Iron Minerals in Aquifers. Groundwater Monitoring Remediation, 35(3): 57-75. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1111/gwmr.12111">https://doi.org/10.1111/gwmr.12111 Hoving, A. L., Sander, M., Bruggeman, C., et al., 2017. Redox Properties of Clay⁃Rich Sediments as Assessed by Mediated Electrochemical Analysis: Separating Pyrite, Siderite and Structural Fe in Clay Minerals. Chemical Geology, 457: 149-161. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.chemgeo.2017.03.022">https://doi.org/10.1016/j.chemgeo.2017.03.022 Huang, J. Z., Jones, A., Waite, T. D., et al., 2021. Fe(Ⅱ) Redox Chemistry in the Environment. Chemical Reviews, 121(13): 8161-8233. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.chemrev.0c01286">https://doi.org/10.1021/acs.chemrev.0c01286 Huang, S. B., Even, E., Wang, Y. X., 2012. Mineralogical Characteristics of Sediments and Arsenic Mobilization in the Aquifer, Jianghan Plain. Journal of Mineralogy and Petrology, 32(4): 7-11 (in Chinese with English abstract). Institute of Soil Science, Chinese Academy of Sciences, 1978. Physical and Chemical Analysis of Soil. Shanghai Scientific and Technical Press, Shanghai (in Chinese). Kocur, C. M. D., Fan, D. M., Tratnyek, P. G., et al., 2020. Predicting Abiotic Reduction Rates Using Cryogenically Collected Soil Cores and Mediated Reduction Potential Measurements. Environmental Science Technology Letters, 7(1): 20-26. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.estlett.9b00665">https://doi.org/10.1021/acs.estlett.9b00665 Kong, F. X., Liu, X. T., Li, A. C., et al., 2024. Depositional Control on the Fate of Reactive Iron in Shelf Sediments since the Last Deglaciation: A Case Study of the East China Sea. Marine Geology, 475: 107358. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.margeo.2024.107358">https://doi.org/10.1016/j.margeo.2024.107358 Kurek, M. R., Garcia⁃Tigreros, F., Nichols, N. A., et al., 2023. High Voltage: The Molecular Properties of Redox⁃Active Dissolved Organic Matter in Northern High⁃Latitude Lakes. Environmental Science Technology, 57(23): 8617-8627. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.3c01782">https://doi.org/10.1021/acs.est.3c01782 Li, X. X., Yan, C., Zeng, Y. X., et al., 2024. Abiotic Transformation of Chlorinated Organics at the Active Surface of Iron⁃Bearing Minerals in Soils and Sediments. Science China Technological Sciences, 67(10): 2991-3008. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1007/s11431⁃024⁃2655⁃y">https://doi.org/10.1007/s11431⁃024⁃2655⁃y Li, X., Zhang, H. X., Yang, S. S., et al., 2025. Abiotic Attenuation of Nitrobenzene Controlled by Reduction Capacity Shifts during Fe(Ⅱ)aq-Catalyzed Ferrihydrite Transformation. Environmental Science Technology, 59(25): 12958-12966. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.5c01613">https://doi.org/10.1021/acs.est.5c01613 Liao, G. M., Ma, J., Gu, C. Y., et al., 2021. Research Progress on Abiotic Natural Attenuation of Halogenated Hydrocarbons at Contaminated Sites. Research of Environmental Sciences, 34(3): 742-754 (in Chinese with English abstract). Liao, W. J., Yuan, S. H., Liu, X. X., et al., 2019. Anoxic Storage Regenerates Reactive Fe(Ⅱ) in Reduced Nontronite with Short⁃Term Oxidation. Geochimica et Cosmochimica Acta, 257: 96-109. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.gca.2019.04.027">https://doi.org/10.1016/j.gca.2019.04.027 Liu, F., 2012. Brief Review on Achievements of Groundwater Contamination Monitoring and Remediation. Rock and Mineral Analysis, 31(4): 645-646 (in Chinese with English abstract). Liu, Y., Yang, Y. M., You, D., et al., 2025. Research Progress on Effects of Iron⁃Containing Minerals on the Natural Attenuation of Organic Pollutants at Sites. Research of Environmental Sciences, 38(5): 1098-1108 (in Chinese with English abstract). Liu, Z. K., Ni, F. J., Li, G. R., et al., 2026. Danxia Red Caused by Surface Iron Coating: Study on the Occurrence State of Iron in Typical Danxia Strata in Southern China. Earth Science, 51(2): 744-755 (in Chinese with English abstract). Lu, Y. X., Chen, R., Zhao, W. J., et al., 2025. Accurate and Simple Determination of Sediment Redox Capacity by a Modified Chemical Probe Method: Implications to Contaminant Remediation. Water Research, 284: 124014. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.watres.2025.124014">https://doi.org/10.1016/j.watres.2025.124014 Lu, Y. X., Zhao, W. J., Zhang, P., et al., 2024. Influence of Dam on the Distribution of Solid Iron Species in Riparian Sediment Particles at Different Sizes. Applied Geochemistry, 165: 105949. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.apgeochem.2024.105949">https://doi.org/10.1016/j.apgeochem.2024.105949 Na, S., Wei, Z. S., Pee, G. Y., et al., 2020. Effect of Sediment Particle Size on Polycyclic Aromatic Hydrocarbon Bioaccessibility and Degradation by Ultrasound. Ultrasonics Sonochemistry, 68: 105203. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.ultsonch.2020.105203">https://doi.org/10.1016/j.ultsonch.2020.105203 Qian, Y. T., Scheinost, A. C., Grangeon, S., et al., 2024. Influence of Structural Fe Content in Clay Minerals on Selenite Redox Reactions: Kinetics and Structural Transformations. Geochimica et Cosmochimica Acta, 377: 19-33. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.gca.2024.05.012">https://doi.org/10.1016/j.gca.2024.05.012 Rincón⁃Rodríguez, J. C., Cárdenas⁃Hernández, P. A., Murillo⁃Gelvez, J., et al., 2024. Comparative Evaluation of Mediated Electrochemical Reduction and Chemical Redox Titration for Quantifying the Electron Accepting Capacities of Soils and Redox⁃Active Soil Constituents. Environmental Science Technology, 58(40): 17674-17684. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.4c06514">https://doi.org/10.1021/acs.est.4c06514 Sander, M., Hofstetter, T. B., Gorski, C. A., 2015. Electrochemical Analyses of Redox⁃Active Iron Minerals: A Review of Nonmediated and Mediated Approaches. Environmental Science Technology, 49(10): 5862-5878. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.5b00006">https://doi.org/10.1021/acs.est.5b00006 Steffens, M., Rogge, D. M., Mueller, C. W., et al., 2017. Identification of Distinct Functional Microstructural Domains Controlling C Storage in Soil. Environmental Science Technology, 51(21): 12182-12189. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.7b03715">https://doi.org/10.1021/acs.est.7b03715 Takeuchi, M., Kawabe, Y., Watanabe, E., et al., 2011. Comparative Study of Microbial Dechlorination of Chlorinated Ethenes in an Aquifer and a Clayey Aquitard. Journal of Contaminant Hydrology, 124(1-4): 14-24. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.jconhyd.2011.01.003">https://doi.org/10.1016/j.jconhyd.2011.01.003 Wei, H. Y., Wei, S. S., Chen, Q. Z., et al., 2025. Nano⁃Scale Insights into Clay Minerals Regulating the Fe(Ⅱ)⁃Catalyzed Ferrihydrite Transformation under Anoxic Conditions. Environmental Science Technology, 59(8): 3982-3991. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.4c11232">https://doi.org/10.1021/acs.est.4c11232 Wu, K. N., Zhao, R., 2019. Soil Texture Classification and Its Application in China. Acta Pedologica Sinica, 56(1): 227-241 (in Chinese with English abstract). Yu, C. L., Qian, A., Lu, Y. X., et al., 2024. Electron Transfer Processes Associated with Structural Fe in Clay Minerals. Critical Reviews in Environmental Science and Technology, 54(1): 13-38. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1080/10643389.2023.2221154">https://doi.org/10.1080/10643389.2023.2221154 Yu, C. L., Zhang, Y. T., Lu, Y. X., et al., 2021. Mechanistic Insight into Humic Acid⁃Enhanced Hydroxyl Radical Production from Fe(Ⅱ)⁃Bearing Clay Mineral Oxygenation. Environmental Science Technology, 55(19): 13366-13375. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1021/acs.est.1c02461">https://doi.org/10.1021/acs.est.1c02461 Zhang, H. X., Li, X., Yang, S. S., et al., 2025. Disentangling the Fe Species⁃Dependent Electron Donating Capacity and Abiotic Reduction Capacity towards Nitrobenzene of the Sediment Cores. Environment International, 202: 109674. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1016/j.envint.2025.109674">https://doi.org/10.1016/j.envint.2025.109674 Zhou, Y., LaChance, A. M., Smith, A. T., et al., 2019. Strategic Design of Clay⁃Based Multifunctional Materials: From Natural Minerals to Nanostructured Membranes. Advanced Functional Materials, 29(16): 1807611. http://www.w3.org/1999/xlink" xlink:href="https://doi.org/10.1002/adfm.201807611">https://doi.org/10.1002/adfm.201807611 Zhu, H., Ye, S. J., Wu, J. C., et al., 2021. Characteristics of Soil Lithology and Pollutants in Typical Contamination Sites in China. Earth Science Frontiers, 28(5): 26-34 (in Chinese with English abstract). 陈海英, 申汝佳, 黄海波, 等, 2025. 长江三角洲沉积物中抗生素的吸附特征及空间分布预测. 岩矿测试, 44(5): 1051-1068. 黄爽兵, Emilie Even, 王焰新, 2012. 高砷含水层沉积物矿物学特征及砷的活化. 矿物岩石, 32(4): 7-11. 廖高明, 马杰, 谷春云, 等, 2021. 污染场地卤代烃非生物自然衰减研究进展. 环境科学研究, 34(3): 742-754. 刘菲, 2012. "地下水污染监测与修复"专栏成果简评. 岩矿测试, 31(4): 645-646. 刘瑶, 杨延梅, 尤迪, 等, 2025. 含铁矿物对场地有机污染物自然衰减影响研究进展. 环境科学研究, 38(5): 1098-1108. 刘振康, 倪凤娟, 黎广荣, 等, 2026. 表面铁膜主导的丹霞红: 我国南方典型丹霞地层铁的赋存状态研究. 地球科学, 51(2): 744-755. doi: 10.3799/dqkx.2025.222 吴克宁, 赵瑞, 2019. 土壤质地分类及其在我国应用探讨. 土壤学报, 56(1): 227-241. 中国科学院南京土壤研究所, 1978. 土壤理化分析. 上海: 上海科学技术出版社. 朱辉, 叶淑君, 吴吉春, 等, 2021. 中国典型有机污染场地土层岩性和污染物特征分析. 地学前缘, 28(5): 26-34. -
点击查看大图
计量
- 文章访问数: 224
- HTML全文浏览量: 17
- PDF下载量: 48
- 被引次数: 0
