Progress on Redox Characteristics of an Iron Oxide-Ferrous System in the Hyporheic Zone

LUO Weijia; FENG Chen; HOU Guohua; CHEN Jiawei

doi:10.15898/j.ykcs.202309090150

Rock and Mineral Analysis > 2024 > 43(2): 397-406. > DOI: 10.15898/j.ykcs.202309090150

LUO Weijia，FENG Chen，HOU Guohua，et al. Progress on Redox Characteristics of an Iron Oxide-Ferrous System in the Hyporheic Zone[J]. Rock and Mineral Analysis，2024，43（2）：397−406. DOI: 10.15898/j.ykcs.202309090150

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Progress on Redox Characteristics of an Iron Oxide-Ferrous System in the Hyporheic Zone

1.
China Aero Geophysical Survey and Remote Sensing Center for Natural Resources, China Geological Survey, Beijing 100083, China
2.
School of Water Resource and Environment, China University of Geoscience (Beijing), Beijing 100083, China
3.
Qingdao Institute of Marine Geology, China Geological Survey, Qingdao 266237, China
4.
School of Earth Sciences and Resources, China University of Geoscience (Beijing), Beijing 100083, China

More Information

Received Date: September 08, 2023
Revised Date: November 21, 2023
Accepted Date: November 25, 2023
Available Online: April 28, 2024

Abstract

HIGHLIGHTS
(1) The hyporheic zone where rivers interact with groundwater exists in the low permeability zone rich in iron oxide, which is the place where pollutants occur and transform.

(2) The reduction capacity of iron oxide-Fe(Ⅱ)_aq in the low-permeability zone is stronger than the individual systems of oxide or aqueous phase ferrous.

(3) The abiotic natural attenuation rate of chlorohydrocarbon can be quantitatively described by Eh of iron oxide-Fe(Ⅱ)_aq system.

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.
- hyporheic zone,
- iron oxides,
- heterogeneity,
- abiotic natural attenuation
BRIEF REPORT
The hyporheic zone is a crucial area for the interaction between rivers and groundwater. The low-permeability zone of the hyporheic zone is composed of fine particles which are rich in iron minerals. Surface water and groundwater interact to varying degrees with changes in water level and spatial location. The equilibrium between soluble iron and mineral-bearing iron is disrupted and affects iron biogeochemical processes. Under natural conditions, soluble iron mainly exists in different forms of divalent iron in the subsurface environment, expressed as Fe(Ⅱ)_aq. Research shows that iron oxides in aquifers can significantly enhance the reducibility of Fe(Ⅱ)_aq, which is expressed by the increase of the rate constant of pollutant reduction and degradation^[1-2]. Stewart et al.^[3] and Li et al.^[5] obtained a relationship between the reduction rate constant of nitrobenzene and the Eh and pH of the iron oxide-Fe(Ⅱ)_aq. However, these insights were obtained through batch experiments under very simple hydrochemical conditions and a single iron mineral, which differ significantly from the actual composition of the aquifer medium, hydrochemical composition, and hydrodynamic conditions. Especially in the hyporheic zone with significant changes in dissolved oxygen (DO), the mechanism of the reduction and degradation of pollutants by iron oxide and Fe(Ⅱ)_aq is still unclear. The conditions and influencing factors for their occurrence need to be studied further. The results of these studies can provide theoretical support for the quantitative evaluation of the possibility and degree of abiotic natural attenuation (ANA) of pollutants in the field. This review starts with the low-permeability part with iron oxides in the hyporheic zone, summarizes the reduction ability (Eh) of the coexistence system of iron oxides and soluble divalent iron, and sorts out the influencing factors of its reduction ability. At the same time, taking chlorinated hydrocarbons as an example, the role of the iron oxide-Fe(Ⅱ)_aq in the ANA of pollutants is analyzed.

　　Usually, both iron oxides and hydroxides are collectively known as iron oxides. Iron oxides are widely present in water environments and participate in numerous reduction reactions^[10-11]. The Fe(Ⅱ)_aq can also reduce pollutants. Therefore, these reduction reactions are crucial for the abiotic attenuation and remediation of pollutants in groundwater. The rate and degree of pollutant reduction depend on the concentration and form of Fe(Ⅱ)_aq^[17]. Fe(Ⅱ) in the bound state on the surface of iron oxides has a faster reduction rate of pollutants than Fe(Ⅱ) alone in solution^[18]. This system is called the iron oxide-Fe(Ⅱ)_aq system. The Eh of the iron oxide-Fe(Ⅱ)_aq can be used to estimate the rate constant (K_obs) of pollutant removal^[31], which has been validated in the reaction of removing nitrobenzene and other pollutants^[32]. However, during the reduction process of TCE and other pollutants, due to multi-step electron transfer, the quantitative relationship between Eh and the reduced K_obs of pollutants still needs further examination. The pH of the solution, the concentration of soluble Fe(Ⅱ), and the morphology of Fe(Ⅱ) on the surface of iron oxides are the main factors affecting the reduction of pollutants by iron oxide-Fe(Ⅱ)_aq^[37]. Moreover, small-molecule carboxylates also affect the dissolution, weathering, and other geochemical processes of iron oxides, as well as the fate of pollutants in the environment^[45].

　　The abiotic natural degradation of chlorinated hydrocarbons caused by the reduction of iron minerals is an important part of the natural attenuation of such pollutants^[46-47]. Although the abiotic natural degradation reaction is rather slow, it still has significant implications for the time scale of groundwater remediation (usually over a decade or several decades)^[48]. Laboratory studies have demonstrated the possibility of ANA of chlorinated organic solvents^[50-51], which is more complex than expected^[52]. The mineral is a crucial factor in this process, especially the new mineral phase related to Fe(Ⅱ)_aq concentration^[19,53]. This new mineral phase is defined as reactive mineral intermediates (RMIs), which are continuously generated and consumed during the ANA process. Field investigations have found that 0.5% active mineral content is sufficient to cause abiotic decay of chlorinated hydrocarbons. Under specific conditions, the contribution of abiotic reactions to natural attenuation cannot be ignored, especially when the mineral content that can cause reduction of chlorinated hydrocarbons in aquifers is relatively high, the contribution of abiotic attenuation is particularly important. The possibility and degree of ANA of pollutants under specific conditions such as hyporheic zone depend on the Eh of iron oxide-Fe(Ⅱ)_aq, which is related to the type and content of iron oxides, pH, DO, concentration of soluble divalent iron, and other hydrochemical parameters.

　　Due to the complexity of the types of iron oxides and hydrochemical conditions in aquifers, there is still an urgent need for probe research in the following areas: (1) Rapid and accurate determination of the redox potential (Eh) of iron oxide-Fe(Ⅱ)_aq heterogeneous systems; (2) The kinetic mechanism of iron oxide-Fe(Ⅱ)_aq in reducing pollutants; (3) Quantitative evaluation of ANA of pollutants.

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References (59)

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