基于微流控技术的重质非水相液体氧化修复机理

王泽君; 杨志兵; 胡冉; 陈益峰

PDF(4622 KB)

中国环境科学 ›› 2024, Vol. 44 ›› Issue (8) : 4530-4538.

环境生态

基于微流控技术的重质非水相液体氧化修复机理

王泽君, 杨志兵, 胡冉, 陈益峰

作者信息 +

Pore-scale mechanisms of DNAPL oxidative remediation in a microfluidic device

WANG Ze-jun, YANG Zhi-bing, HU Ran, CHEN Yi-Feng

Author information +

文章历史 +

摘要

为揭示重非水相污染物(DNAPL)氧化修复中多相渗流-化学反应-相演变耦合过程的物理化学机理,利用新兴的微流控技术开展了高锰酸钾(KMnO₄)氧化修复三氯乙烯(TCE)的实验.结果表明:当浓度3g/L以上的KMnO₄氧化TCE时,二氧化锰(MnO₂)固相产物会在流道深度方向上产生“固体墙”,后续MnO₄^-只能缓慢渗入墙内对TCE进行氧化,此时MnO₄^-成为限制性因素并转化为Mn²⁺,而Mn²⁺扩散出墙外后再次被氧化为MnO₂固相,形成一个负反馈系统并造成修复效率急剧降低.当3g/L以下的KMnO₄氧化TCE时,MnO₂固相产物附着在流道壁面上,后续MnO₄^-可以和TCE持续反应并生成MnO₂,KMnO₄溶液-DNAPL界面不断后退且修复效率较高.当加入磷酸氢盐后,MnO₂固相产物被显著抑制从而提高了修复效率,且1~2g/L是孔隙尺度TCE修复的理想KMnO₄浓度.

Abstract

To elucidate pore-scale mechanisms governing the coupled process of multiphase flow, chemical reactions, and phase transformations during the oxidation remediation of dense non-aqueous phase liquids (DNAPLs), we conducted 48microfluidic experiments to investigate the trichloroethylene (TCE) oxidation by potassium permanganate (KMnO₄). The results show that when KMnO₄ concentration exceeded 3g/L, the manganese dioxide (MnO₂) solid products during TCE oxidation formed a "solid wall", which hindered the contact between MnO₄^- and TCE. Under such conditions, the residual TCE oxidation proceeded only via the slow penetration of KMnO₄ solution through the MnO₂ wall, where limited MnO₄^- was converted to Mn²⁺. As Mn²⁺ diffused out of the MnO₂ wall, it was re-oxidized to MnO₂ solid phase, creating a negative feedback loop and significantly reducing remediation efficiency. At KMnO₄ concentrations below 3g/L, the MnO₂ solid products were able to attach to the channel surfaces, permitting continuous reaction between MnO₄^- and TCE, thereby resulting in a higher remediation efficiency. The introduction of phosphate significantly suppressed the formation of MnO₂ solid products and improved remediation efficiency, with an optimal KMnO₄ concentration for TCE remediation determined to be 1~2g/L.

导出引用

王泽君, 杨志兵, 胡冉, 陈益峰. 基于微流控技术的重质非水相液体氧化修复机理[J]. 中国环境科学. 2024, 44(8): 4530-4538

WANG Ze-jun, YANG Zhi-bing, HU Ran, CHEN Yi-Feng. Pore-scale mechanisms of DNAPL oxidative remediation in a microfluidic device[J]. China Environmental Science. 2024, 44(8): 4530-4538

中图分类号： X13 X523

参考文献

[1] 郑德凤,赵勇胜,王本德.轻非水相液体在地下环境中的运移特征与模拟预测研究[J]. 水科学进展, 2002,13(3):321-325. Zheng D F, Zhao Y S, Wang B D. Research on the moving behaviors and modeling of light nonaqueous phase liquid in subsurface [J]. Advances in Water Science, 2002,13(3):321-325.
[2] 施小清,姜蓓蕾,吴吉春,等.非均质介质中重非水相污染物运移受泄漏速率影响数值分析[J]. 水科学进展, 2012,23(3):376-382. Shi X Q, Jiang B L, Wu J C, et al. Numerical analysis of the effect of leakage rate on dense non-aqueous phase liquid transport in heterogonous porous media [J]. Advances in Water Science, 2012, 23(3):376-382.
[3] 李胜,窦智,陈永强,等.基于低场核磁共振的二元结构含水层LNAPL迁移及分布规律研究[J]. 中南大学学报(自然科学版), 2023,54(5):1970-1977. Li S, Dou Z, Chen Y Q, et al. Migration and distribution of LNAPL in binary structure stratum based on low field nuclear magnetic resonance [J]. Journal of Central South University (Science and Technology), 2023,54(5):1970-1977.
[4] 潘明浩,时健,左锐,等.水位波动下包气带透镜体影响LNAPL迁移的数值模拟研究[J]. 水文地质工程地质, 2022,49(1):154-163. Pan M H, Shi J, Zuo R, et al. A numerical simulation study of the effect of the vadose zone with lenses on LNAPL migration under the fluctuating water table [J]. Hydrogeology & Engineering Geology, 2022,49(1):154-163.
[5] 杨宾,李慧颖,伍斌,等.4种NAPLs污染物在二维砂箱中的指进锋面形态特征研究[J]. 环境科学, 2013,34(4):1545-1552. Yang B, Li H Y, Wu B, et al. Sand box study on fingering front morphology for NAPLs infiltrated in homogeneous porous media [J]. Environmental Science, 2013,34(4):1545-1552.
[6] Siegrist R L, Crimi M, Simpkin T J. In situ chemical oxidation for groundwater remediation [M]. New York: Springer Science & Business Media, 2011.
[7] Yang Z, Niemi A, Fagerlund F, et al. Effects of single-fracture aperture statistics on entrapment, dissolution and source depletion behavior of dense non-aqueous phase liquids [J]. Journal of Contaminant Hydrology, 2012,133:1-16.
[8] 王宁,彭胜,陈家军.蒸汽-空气混合注射修复TCE污染的二维土箱实验研究[J]. 环境科学, 2014,35(7):2785-2790. Wang N, Peng S, Chen J J. Steam and air co-injection in removing TCE in 2D-sand box [J]. Environmental Science, 2014,35(7):2785-2790.
[9] 严芳敏,郭明帅,王菲.炭铁材料修复三氯乙烯污染地下水的性能[J]. 中国环境科学, 2024,44(2):825-831. Yan F M, Guo M S, Wang F. The performance of biochar/nZVI composite in remediating trichloroethylene contaminated groundwater [J]. China Environmental Science, 2024,44(2):825-831.
[10] 邢志林,石云椿,苏夏,等.微氧环境氯代烃生物降解的研究现状与展望[J]. 中国环境科学, 2023,43(9):4837-4848. Xing Z L, Shi Y C, Su X, et al. The current status and prospects of biodegradation of chlorinated hydrocarbons under micro-aerobic conditions [J]. China Environmental Science, 2023,43(9):4837-4848.
[11] 康学远,施小清,史良胜,等.基于集合卡尔曼滤波的多相流模型参数估计——以室内二维砂箱中重质非水相污染物入渗为例[J]. 吉林大学学报(地球科学版), 2017,47(3):848-859. Kang X Y, Shi X Q, Shi L S, et al. Inverse multiphase flow simulation using ensemble kalman filter: application to a 2D sandbox experiment of DNAPL migration [J]. Journal of jilin University (Earth Science Edition), 2017,47(3):848-859.
[12] 邓亚平,张烨,施小清,等.非均质裂隙介质中重非水相流体运移[J]. 水科学进展, 2015,26(5):722-730. Deng Y P, Zhang Y, Shi X Q, et al. Study on the migration of dense non-aqueous phase liquids in heterogeneous fractured media [J]. Advances in Water Science, 2015,26(5):722-730.
[13] 束善治,梁宏伟,袁勇.轻非水相液体在非均质地层包气带中运移和分布特征数值分析[J]. 水利学报, 2002,11:31-37. Shu S Z, Liang H W, Yuan Y. Numerical analysis of transportation and distribution of light non-aqueous phase liquids in partially saturated heterogeneous soils [J]. Journal of Hydraulic Engineering, 2002,11:31-37.
[14] 胡黎明,邢巍巍,吴照群.多孔介质中非水相流体运移的数值模拟[J]. 岩土力学, 2007,5:951-955. Hu L M, Xing W W, Wu Z Q. Numerical simulation of non-aqueous phase liquids migration in porous media [J]. Rock and Soil Mechanics, 2007,5:951-955.
[15] Wang Z, Yang Z, Chen Y F. Pore-scale investigation of surfactant-enhanced DNAPL mobilization and solubilization [J]. Chemosphere, 2023,341:140071.
[16] 王慧婷,徐红霞,郭琼泽,等.饱和多孔介质中DNAPL污染源区结构及质量溶出[J]. 中国环境科学, 2019,39(8):3474-3483. Wang H T, Xu H X, Guo Q Z, et al. Dense non-aqueous phase liquid source zone architecture and dissolution in saturated porous media [J]. China Environmental Science, 2019,39(8):3474-3483.
[17] 黄菀,耿竹凝,李广贺,等.热修复过程中重质非水相液体(DNAPL)共沸实验[J]. 中国环境科学, 2020,40(9):3903-3910. Huang W, Geng Z N, Li G H, et al. Laboratory study on dense non-aqueous phase liquid co-boiling during thermal remediation [J]. China Environmental Science, 2020,40(9):3903-3910.
[18] 肖鹏,刘汉乐.饱和砂土中DNAPL污染物迁移过程及数值模拟[J]. 中国环境科学, 2024,44(1):386-395. Xiao P, Liu H L. Transport processes and numerical simulation of DNAPL contaminants in saturated sandy soils. [J]. China Environmental Science, 2024,44(1):386-395.
[19] Yuan S, Liao P, Alshawabken A N. Electrolytic manipulation of persulfate reactivity by iron electrodes for trichloroethylene degradation in groundwater [J]. Environmental science & technology, 2014,48(1):656-663.
[20] Cheng Z, Gao B, Xu H, et al. Effects of surface active agents on DNAPL migration and distribution in saturated porous media [J]. Science of the Total Environment, 2016,571:1147-1154.
[21] Pak T, Luz J R L F L, Tosco T, et al. Pore-scale investigation of the use of reactive nanoparticles for in situ remediation of contaminated groundwater source [J]. Proceedings of the National Academy of Sciences, 2020,117(24):13366-13373.
[22] 卢文喜,罗建男,辛欣,等.表面活性剂强化的DNAPLs污染含水层修复过程的数值模拟[J]. 地球科学(中国地质大学学报), 2012, 37(5):1075-1081. Lu W X, Luo J N, Xin X, et al. Numerical simulation of surfactant enhanced aquifer remediation processes at DNAPLs contaminated aquifer [J]. Earth Science (Journal of China University of Geosciences), 2012,37(5):1075-1081.
[23] Wang Z, Yang Z, Hu R, et al. Mass transfer during surfactant- enhanced DNAPL remediation: Pore-scale experiments and new correlation [J]. Journal of Hydrology, 2023,621:129586.
[24] Wang Z, Yang Z, Fagerlund F, et al. Pore-scale mechanisms of solid phase emergence during DNAPL remediation by chemical oxidation [J]. Environmental Science & Technology, 2022,56(16):11343-11353.
[25] Li X D, Schwartz F W. DNAPL mass transfer and permeability reduction during in situ chemical oxidation with permanganate [J]. Geophysical Research Letters, 2004,31(6):1-5.
[26] West M R, Grant G P, Gerhard J I, et al. The influence of precipitate formation on the chemical oxidation of TCE DNAPL with potassium permanganate [J]. Advances in Water Resources, 2008,31(2):324-338.
[27] West M R, Kueper B H. Numerical simulation of DNAPL source zone remediation with in situ chemical oxidation (ISCO) [J]. Advances in Water Resources, 2012,44:126-139.
[28] Freeman F, Kappos J C. Permanganate ion oxidations. 15. Additional evidence for formation of soluble (colloidal) manganese dioxide during the permanganate ion oxidation of carbon-carbon double bonds in phosphate-buffered solutions [J]. Journal of the American Chemical Society, 1985,107(23):6628-6633.
[29] Li X D, Schwartz F W. Using phosphate to control the Mn oxide precipitation during in situ chemical oxidation of chlorinated ethylenes by permanganate [M]. Washington: American Chemical Society, 2005.
[30] Crimi M, Ko S. Control of manganese dioxide particles resulting from in situ chemical oxidation using permanganate [J]. Chemosphere, 2009,74(6):847-853.
[31] Kao C M, Huang K D, Wang J Y, et al. Application of potassium permanganate as an oxidant for in situ oxidation of trichloroethylene- contaminated groundwater: a laboratory and kinetics study [J]. Journal of Hazardous Materials, 2008,153(3):919-927.
[32] Loomer D B, Al T A, Banks V J, et al. Manganese valence in oxides formed from in situ chemical oxidation of TCE by KMnO₄ [J]. Environmental science & technology, 2010,44(15):5934-5939.
[33] 刘洋,谢雯静,郑云松,等.电化学循环井驱动模拟含水层化学氧化降解三氯乙烯[J]. 地学前缘, 2021,28(5):197-207. Liu Y, Xie W J, Zheng Y S, et al. Electrolytic circulation well drives chemical oxidation of TCE in a simulated aquifer. [J]. Earth Science Frontiers, 2021,28(5):197-207.
[34] Demiray Z, Akyol N H, Akyol G, et al. Surfactant-enhanced in-situ oxidation of DNAPL source zone: Experiments and numerical modeling [J]. Journal of Contaminant Hydrology, 2023,258:104233.
[35] Almpanis A, Gerhard J, Power C. Mapping and monitoring of DNAPL source zones with combined direct current resistivity and induced polarization: a field-scale numerical investigation [J]. Water Resources Research, 2021,57(11):e2021WR031366.
[36] Versteeg G F, Van Swaaij W P M. Solubility and diffusivity of acid gases (carbon dioxide, nitrous oxide) in aqueous alkanolamine solutions [J]. Journal of Chemical & Engineering Data, 1988,33(1):29-34.
[37] Seyedpour S M, Janmaleki M, Henning C, et al. Contaminant transport in soil: A comparison of the Theory of Porous Media approach with the microfluidic visualization [J]. Science of the total environment, 2019,686:1272-1281.
[38] Guo Y, Lou J, Cho J K, et al. Transport of colloidal particles in microscopic porous medium analogues with surface charge heterogeneity: experiments and the fundamental role of single-bead deposition [J]. Environmental Science & Technology, 2020,54(21):13651-13660.
[39] Yang J Q, Zhang X, Bourg I C, et al. 4D imaging reveals mechanisms of clay-carbon protection and release [J]. Nature communications, 2021,12(1):622.
[40] Zhu X, Wang K, Yan H, et al. Microfluidics as an emerging platform for exploring soil environmental processes: a critical review [J]. Environmental Science & Technology, 2022,56(2):711-731.
[41] Kurz D L, Secchi E, Carrillo F J, et al. Competition between growth and shear stress drives intermittency in preferential flow paths in porous medium biofilms [J]. Proceedings of the National Academy of Sciences, 2022,119(30):e2122202119.
[42] Huang X, Li Y, Guggenberger G, et al. Direct evidence for thickening nanoscale organic films at soil biogeochemical interfaces and its relevance to organic matter preservation [J]. Environmental Science: Nano, 2020,7(9):2747-2758.
[43] 臧潇倩,李哲煜,张笑颜,等.基于微流控芯片的细菌趋化性检测研究进展[J]. 分析化学, 2017,45(11):1734-1744. Zang X Q, Li Z Y, Zhang X Y, et al. Advance in Bacteria Chemotaxis on Microfluidic Devices [J]. Chinese Journal of Analytical Chemistry, 2017,45(11):1734-1744.