Progress on Redox Characteristics of an Iron Oxide-Ferrous System in the Hyporheic Zone
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摘要:
潜流带是河流与地下水交互的关键带，具有非均质性，其中低渗透区富含的铁氧化物，在污染物的非生物自然衰减过程中发挥着重要作用。本文从铁氧化物和溶解性二价铁Fe(Ⅱ)aq的共存体系出发，评述了该体系的氧化还原能力及影响因素，并以地下水中常见的污染物氯代烃为例阐述了铁氧化物-Fe(Ⅱ)aq体系在氯代烃非生物自然衰减中的作用。指出铁氧化物-Fe(Ⅱ)aq体系的还原能力可用氧化还原电位（Eh）表示，Eh的大小受pH值、温度、溶解氧（DO）、溶解性二价铁浓度、无机和有机配体等因素的影响，可用来定量描述氯代烃等污染物被还原的速率常数。目前铁氧化物-Fe(Ⅱ)aq体系Eh的快速测定、含水层中铁氧化物种类和含量、不同铁氧化物共存和复杂水化学条件下Eh与氯代烃等污染物还原速率常数之间的关系，是准确评估污染物非生物自然衰减能力和程度的重要内容。
Abstract:The hyporheic zone is a critical zone for the interaction between groundwater and surface water. The heterogeneous system composed of iron oxides and ferrous in the low-permeability zone of the hyporheic zone is vital for the abiotic natural attenuation of pollutants. This review summarized the universality, reduction ability, and influencing factors of the iron oxides and ferrous in groundwater. Chlorinated hydrocarbons are taken as typical pollutants to indicate the role of iron oxide and ferrous system in their abiotic natural attenuation process. The review indicates that the reducing ability of the iron oxide and ferrous system can be expressed by Eh which is influenced by pH, ferrous concentration, and natural organic matter. Whereas the rate constant of abiotic natural attenuation of pollutants can be quantitatively described by Eh. So far, the rapid and accurate determination of Eh and the establishment of quantitative relationships between various pollutants and Eh under complex hydrochemical conditions will be the key to evaluating the abiotic natural attenuation of pollutants in aquifers. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202309090150 .-
Key words:
- hyporheic zone /
- iron oxides /
- heterogeneity /
- abiotic natural attenuation
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表 1 常见铁氧化物的类型
Table 1. Types of common iron oxides.
氧化铁 水合羟基氧化铁 化学式 铁氧化物 化学式 铁氧化物 β-Fe2O3 β-Fe2O3 Fe5HO8·4H2O 水铁矿 ε-Fe2O3 ε-Fe2O3 α-FeOOH 针铁矿 FeO 方铁矿 γ-FeOOH 纤铁矿 Fe3O4 磁铁矿 β-FeOOH 四方纤铁矿 γ-Fe3O4 磁赤铁矿 δ’-FeOOH(结晶度低) 六方纤铁矿 α-Fe2O3 赤铁矿 δ-FeOOH(结晶度高) 六方纤铁矿 Fe16O16(OH)y(SO4)x·nH2O 施氏矿物 Fe(OH)3 纳伯尔矿 FexⅢFeyⅡ(OH)3x+2y−z(A−)z (A=Cl−；1/2CO32−；1/2SO42−) 绿锈 注：修改自杨忠兰等(2021)［7］。 
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[1] He Y T, Wilson J T, Su C, et al. Review of abiotic degradation of chlorinated solvents by reactive iron minerals in aquifers[J]. Ground Water Monitoring and Remediation, 2015, 35(3): 57−75. doi: 10.1111/gwmr.12111
[2] Huang J Z, Wang Q H, Wang Z M, et al. Interactions and reductive reactivity in ternary mixtures of Fe(Ⅱ), goethite, and phthalic acid based on a combined experimental and modeling approach[J]. Langmuir, 2019, 35(25): 8220−8227.
[3] Stewart S M, Hofstetter T B, Joshi P, et al. Linking thermodynamics to pollutant reduction kinetics by Fe(Ⅱ) bound to iron oxides[J]. Environmental Science & Technology, 2018, 52(10): 5600−5609.
[4] Chen Y L, Dong H, Zhang H C. Reduction of isoxazoles including sulfamethoxazole by aqueous Fe-Ⅱ-iron complex: Impact of structures[J]. Chemical Engineering Journal, 2018, 352: 501−509. doi: 10.1016/j.cej.2018.07.052
[5] Li X, Chen Y L, Zhang H C. Reduction of nitrogen-oxygen containing compounds (NOCs) by surface-associated Fe(Ⅱ) and comparison with soluble Fe(Ⅱ) complexes[J]. Chemical Engineering Journal, 2019, 370: 782−791. doi: 10.1016/j.cej.2019.03.203
[6] 李响, 蔡元峰. 沉积物中铁氧化物的定量方法及其在白垩纪大洋红层中的应用[J]. 高校地质学报, 2014, 20(3): 433−444.
Li X, Cai Y F. The quantitative analysis methods for iron oxides in sediment and their application in Cretaceous oceanic red beds[J]. Geological Jounal of China Universities, 2014, 20(3): 433−444.
[7] 杨忠兰, 曾希柏, 孙本华, 等. 铁氧化物固定土壤重金属的研究进展[J]. 土壤通报, 2021, 52(3): 728−735.
Yang Z L, Zeng X B, Sun B H, et al. Research advances on the fixation of soil heavy metals by iron oxide[J]. Chinese Journal of Soil Science, 2021, 52(3): 728−735.
[8] Zhang D N, Cao R, Wang S F, et al. Fate of arsenic during up to 4.5 years of aging of Fe-Ⅲ-As-V coprecipitates at acidic pH: Effect of reaction media (nitrate vs. sulfate), Fe/As molar ratio, and pH[J]. Chemical Engineering Journal, 2020, 388: 124239. doi: 10.1016/j.cej.2020.124239
[9] 董有进, 杨立辉, 张硕. 风化壳中主要铁氧化物矿物的研究进展[J]. 安庆师范大学学报(自然科学版), 2018, 24(2): 85−89, 99.
Dong Y J, Yang L H, Zhang S. Research advances of main iron oxide minerals in weathering crust[J]. Journal of Anqing Normal University (Natual Science Edition), 2018, 24(2): 85−89, 99.
[10] Stumm W, Sulzberger B. The cycling of iron in natural environments-considerations based on laboratory studies of heterogeneous redox processes[J]. Geochimica et Cosmochimica Acta, 1992, 56(8): 3233−3257. doi: 10.1016/0016-7037(92)90301-X
[11] Melton E D, Swanner E D, Behrens S, et al. The interplay of microbially mediated and abiotic reactions in the biogeochemical Fe cycle[J]. Nature Reviews Microbiology, 2014, 12(12): 797−808. doi: 10.1038/nrmicro3347
[12] 何晗晗, 于扬, 刘新星, 等. 赣南小流域水体中溶解态稀土含量及pH和Eh值变化特征[J]. 岩矿测试, 2015, 34(4): 487−493.
He H H, Yu Y, Liu X X, et al. pH and Eh variations and the drees contens of a small watershed in South Jiangxi Province[J]. Rock and Mineral Analysis, 2015, 34(4): 487−493.
[13] 周国华. 富硒土地资源研究进展与评价方法[J]. 岩矿测试, 2020, 39(3): 319−336.
Zhou G H. Research progress of selenium-enriched land resources and evaluation methods[J]. Rock and Mineral Analysis, 2020, 39(3): 319−336.
[14] 王妍妍, 曹文庚, 潘登, 等. 豫北平原地下水高砷和高氟分布规律与成因[J]. 岩矿测试, 2022, 41(6): 1095−1109. doi: 10.3969/j.issn.0254-5357.2022.6.ykcs202206020
Wang Y Y, Cao W G, Pan D, et al. Distribution and origin of high arsenic and fluoride in groundwater of the North Henan Plain[J]. Rock and Mineral Analysis, 2022, 41(6): 1095−1109. doi: 10.3969/j.issn.0254-5357.2022.6.ykcs202206020
[15] Amonette J E, Workman D J, Kennedy D W, et al. Dechlorination of carbon tetrachloride by Fe(Ⅱ) associated with goethite[J]. Environmental Science and Technology, 2000, 34(21): 4606−4613. doi: 10.1021/es9913582
[16] Strathmann T J, Stone A T. Mineral surface catalysis of reactions between Fe-Ⅱ and oxime carbamate pesticides[J]. Geochimica et Cosmochimica Acta, 2003, 67(15): 2775−2791. doi: 10.1016/S0016-7037(03)00088-7
[17] Fan D M, Bradley M J, Hinkle A W, et al. Chemical reactivity probes for assessing abiotic natural attenuation by reducing iron minerals[J]. Environmental Science & Technology, 2016, 50(4): 1868−1876.
[18] Chun C L, Penn R L, Arnold W A. Kinetic and microscopic studies of reductive transformations of organic contaminants on goethite[J]. Environmental Science & Technology, 2006, 40(10): 3299−3304.
[19] Jones A M, Kinsela A S, Collins R N, et al. The reduction of 4-chloronitrobenzene by Fe(Ⅱ)-Fe(Ⅲ) oxide systems-correlations with reduction potential and inhibition by silicate[J]. Journal of Hazardous Materials, 2016, 320: 143−149. doi: 10.1016/j.jhazmat.2016.08.031
[20] Cardenas-Hernandez P A, Anderson K A, Murillo-Gelvez J, et al. Reduction of 3-nitro-1, 2, 4-triazol-5-one (NTO) by the hematite-aqueous Fe(Ⅱ) redox couple[J]. Environmental Science & Technology, 2020, 54(19): 12191−12201.
[21] Colon D, Weber E J, Anderson J L. QSAR study of the reduction of nitroaromatics by Fe(Ⅱ) species[J]. Environmental Science & Technology, 2006, 40(16): 4976−4982.
[22] 叶力, 周红刚, 成捷凤. Fe(Ⅱ)及键合(Fe(Ⅱ)铁对环境污染物治理的作用研究[J]. 广州化工, 2015, 43(20): 48−49, 67.
Ye L, Zhou H G, Cheng J F. Study on the effect of Fe(Ⅱ) and bonding Fe(Ⅱ) iron on the environment pollutant control[J]. Guangzhou Chemical Industry, 2015, 43(20): 48−49, 67.
[23] Stumm W. Chemistry of the solid-water interface: Processes at the mineral-water and particle-water interface in natural systems [M]. Canada: John Wiley & Sons, 1992: 448.
[24] Orsetti S, Laskov C, Haderlein S B. Electron transfer between iron minerals and quinones: Estimating the reduction potential of the Fe(Ⅱ)-goethite surface from AQDS speciation[J]. Environmental Science & Technology, 2013, 47(24): 14161−14168.
[25] Aeppli M, Voegelin A, Gorski C A, et al. Mediated electrochemical reduction of iron (oxyhydr-)oxides under defined thermodynamic boundary conditions[J]. Environmental Science & Technology, 2018, 52(2): 560−570.
[26] Zarzycki P, Kerisit S, Rosso K M. Molecular dynamics study of Fe(Ⅱ) adsorption, electron exchange, and mobility at goethite (alpha-FeOOH) surfaces[J]. Journal of Physical Chemistry C, 2015, 119(6): 3111−3123. doi: 10.1021/jp511086r
[27] Gorski C A, Edwards R, Sander M, et al. Thermodynamic characterization of iron oxide-aqueous Fe(Ⅱ) redox couples[J]. Environmental Science & Technology, 2016, 50(16): 8538−8547.
[28] Krumina L, Lyngsie G, Tunlid A, et al. Oxidation of a dimethoxyhydroquinone by ferrihydrite and goethite nanoparticles: Iron reduction versus surface catalysis[J]. Environmental Science & Technology, 2017, 51(16): 9053−9061.
[29] Jones A M, Griffin P J, Collins R N, et al. Ferrous iron oxidation under acidic conditions—The effect of ferric oxide surfaces[J]. Geochimica et Cosmochimica Acta, 2015, 156: 241. doi: 10.1016/j.gca.2015.03.001
[30] Sander M, Hofstetter T B, Gorski C A. Electrochemical analyses of redox-active iron minerals: A review of nonmediated and mediated approaches[J]. Environment-al Science & Technology, 2015, 49(10): 5862−5878.
[31] Schwarzenbach R P, Gschwend P M, Imboden D M. Environmental Organic Chemistry (The third edition)[J]. International Journal of Environmental Analytical Chemistry, 2017, 97(4): 398−399. doi: 10.1080/03067319.2017.1318869
[32] Larese-Casanova P, Kappler A, Haderlein S B. Heterogeneous oxidation of Fe(Ⅱ) on iron oxides in aqueous systems: Identification and controls of Fe(Ⅲ) product formation[J]. Geochimica et Cosmochimica Acta, 2012, 91: 171−186. doi: 10.1016/j.gca.2012.05.031
[33] Klupinski T P, Chin Y P, Traina S J. Abiotic degradation of pentachloronitrobenzene by Fe(Ⅱ): Reactions on goethite and iron oxide nanoparticles[J]. Environmental Science & Technology, 2004, 38(16): 4353−4360.
[34] Silvester E, Charlet L, Tournassat C, et al. Redox potential measurements and Mossbauer spectrometry of Fe(Ⅱ) adsorbed onto Fe(Ⅲ) (oxyhydr)oxides[J]. Geochimica et Cosmochimica Acta, 2005, 69(20): 4801−4815. doi: 10.1016/j.gca.2005.06.013
[35] Amirbahman A, Kent D B, Curtis G P, et al. Kinetics of homogeneous and surface-catalyzed mercury(Ⅱ) reduction by iron(Ⅱ)[J]. Environmental Science & Technology, 2013, 47(13): 7204−7213.
[36] Elsner M, Schwarzenbach R P, Haderlein S B. Reactivity of Fe(Ⅱ)-bearing minerals toward reductive transformation of organic contaminants[J]. Environmental Science & Technology, 2004, 38(3): 799−807.
[37] Wang Z M, Schenkeveld W D C, Kraemer S M, et al. Synergistic effect of reductive and ligand-promoted dissolution of goethite[J]. Environmental Science & Technology, 2015, 49(12): 7236−7244.
[38] Chen G D, Hofstetter T B, Gorski C A. The role of carbonate in thermodynamic relationships describing pollutant reduction kinetics by iron oxide-bound Fe[J]. Environmental Science & Technology, 2020, 54(16): 10109−10117.
[39] Jones A M, Collins R N, Rose J, et al. The effect of silica and natural organic matter on the Fe(Ⅱ)-catalysed transformation and reactivity of Fe(Ⅲ) minerals[J]. Geochimica et Cosmochimica Acta, 2009, 73(15): 4409−4422. doi: 10.1016/j.gca.2009.04.025
[40] Hinkle M A G, Wang Z M, Giammar D E, et al. Interaction of Fe(Ⅱ) with phosphate and sulfate on iron oxide surfaces[J]. Geochimica et Cosmochimica Acta, 2015, 158: 130−146. doi: 10.1016/j.gca.2015.02.030
[41] Vindedahl A M, Stemig M S, Arnold W A, et al. Character of humic substances as a predictor for goethite nanoparticle reactivity and aggregation[J]. Environmental Science & Technology, 2016, 50(3): 1200−1208.
[42] Taujale S, Baratta L R, Huang J Z, et al. Interactions in ternary mixtures of MnO2, Al2O3, and natural organic matter (NOM) and the impact on MnO2 oxidative reactivity[J]. Environmental Science & Technology, 2016, 50(5): 2345−2353.
[43] Strobel B W. Influence of vegetation on low-molecular-weight carboxylic acids in soil solution—A review[J]. Geoderma, 2001, 99(3-4): 169−198. doi: 10.1016/S0016-7061(00)00102-6
[44] Zhang H C, Taujale S, Huang J Z, et al. Effects of NOM on oxidative reactivity of manganese dioxide in binary oxide mixtures with goethite or hematite[J]. Langmuir, 2015, 31(9): 2790−2799. doi: 10.1021/acs.langmuir.5b00101
[45] Hwang Y S, Liu J, Lenhart J J, et al. Surface complexes of phthalic acid at the hematite/water interface[J]. Journal of Colloid and Interface Science, 2007, 307(1): 124−134. doi: 10.1016/j.jcis.2006.11.020
[46] Leeson A, Lebron C, Stroo H, et al. Summary report: SERDP and ESTCP workshop on research and development needs for chlorinated solvents in groundwater[R]. 2018.
[47] Xiao Z, Jiang W, Chen D, et al. Bioremediation of typical chlorinated hydrocarbons by microbial reductive dechlorination and its key players: A review[J]. Ecotoxicology and Environmental Safety, 2020, 202: 110925. doi: 10.1016/j.ecoenv.2020.110925
[48] Weatherill J J, Atashgahi S, Schneidewind U, et al. Natural attenuation of chlorinated ethenes in hyporheic zones: A review of key biogeochemical processes and in-situ transformation potential[J]. Water Research, 2018, 128: 362−382. doi: 10.1016/j.watres.2017.10.059
[49] Estuesta P. Evaluation of the protocol for natural attenuation of chlorinated solvents: Case study at the twin cities army ammunition plant [R]. 2001.
[50] Murray A M, Ottosen C B, Maillard J, et al. Chlorinated ethene plume evolution after source thermal remediation: Determination of degradation rates and mechanisms[J]. Journal of Contaminant Hydrology, 2019, 227: 103551. doi: 10.1016/j.jconhyd.2019.103551
[51] Yu R, Andrachek R G, Lehmicke L G, et al. Remediation of chlorinated ethenes in fractured sandstone by natural and enhanced biotic and abiotic processes: A crushed rock microcosm study[J]. Science of the Total Environment, 2018, 626: 497−506. doi: 10.1016/j.scitotenv.2018.01.064
[52] Wiedemeier T H, Wilson B H, Ferrey M L, et al. Efficacy of an in-well sonde todetermine magnetic susceptibility of aquifer sediment[J]. Ground Water Monitoring and Remediation, 2017, 37(2): 25−34. doi: 10.1111/gwmr.12197
[53] Entwistle J, Latta D E, Scherer M M, et al. Abiotic degradation of chlorinated solvents by clay minerals and Fe(Ⅱ): Evidence for reactive mineral intermediates[J]. Environmental Science & Technology, 2019, 53(24): 14308−14318.
[54] He Y T, Wilson J T, Wilkin R T. Impact of iron sulfide transformation on trichloroethylene degradation[J]. Geochimica et Cosmochimica Acta, 2010, 74(7): 2025−2039. doi: 10.1016/j.gca.2010.01.013
[55] Kocur C M D, Fan D M, Tratnyek P G, et al. Predicting abiotic reduction rates using cryogenically collected soil cores and mediated reduction potential measurements[J]. Environmental Science & Technology Letters, 2020, 7(1): 20−26.
[56] Ferrey M L, Wilkin R T, Ford R G, et al. Nonbiological removal of cis-dichloroethylene and 1,1-dichloro-ethylene in aquifer sediment containing magnetite[J]. Environmental Science & Technology, 2004, 38(6): 1746−1752.
[57] Ottosen C B, Murray A M, Broholm M M, et al. In situ quantification of degradation is needed for reliable risk assessments and site-specific monitored natural attenuation[J]. Environmental Science & Technology, 2019, 53(1): 1−3.
[58] Brown R A, Wilson J T, Ferrey M. Monitored natural attenuation forum: The case for abiotic MNA[J]. Remediation Journal, 2007, 17(2): 127-137.
[59] Noubactep C. Relevant reducing agents in remediation FeO/H2O systems[J]. Clean-Soil Air Water, 2013, 41(5): 493−502. doi: 10.1002/clen.201200406
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