All Issue

2025 Vol.30, Issue 6 Preview Page
Evaluation of Reaction Rates and Isotopic Fractionation during Denitrification in Organic-Based Permeable Reactive Barriers through Column Experiments

칼럼 실험을 통한 유기물 기반 투과성 반응벽의 탈질과정 반응 속도 및 동위원소 분별 작용 평가

Gyu Hyun Han1
,
Sung-Wook Jeen12*
한규현 1
,
진성욱 12*
1Department of Environment and Energy, Jeonbuk National University
2Department of Earth and Environmental Sciences & The Earth and Environmental Science System Research Center, Jeonbuk National University
1전북대학교 환경에너지융합학과, 전북대학교 지구환경과학과 & 지구환경시스템 연구소
2전북대학교 환경에너지융합학과, 전북대학교 지구환경과학과 & 지구환경시스템 연구소
*Corresponding Author
31 December 2025. pp. 42-54
PDF XML Citation
Abstract

This study conducted two column experiments simulating organic matter-based permeable reactive barriers (PRBs) for nitrate removal from groundwater. The columns used woodchips as the reactive material: one had been operated for approximately nine years (Old column), and the other was newly constructed for this study (New column). Nitrate removal performance was evaluated by comparing denitrification rates and assessing isotopic fractionation characteristics (δ15N-NO3⁻, δ18O-NO3⁻, δ2H-H2O, and δ18O-H2O). Changes in pH, alkalinity, Eh, dissolved oxygen (DO), and N2gas production suggested that geochemical conditions were favorable for denitrification. Calculation of denitrification rates (New: 1.3 mmol L⁻¹ day⁻¹; Old: 0.08 mmol L⁻¹ day⁻¹) indicated that reactivity was retained even after long-term operation, demonstrating the long-term feasibility of woodchips for PRBs. As nitrate concentrations decreased, δ15N-NO3⁻ and δ18O-NO3⁻ values increased from 8.27‰ to 27.13‰ and 19.81‰ to 39.08‰, respectively, with a 1:1 enrichment factor ratio typical of denitrification. On the other hand, no significant δ¹⁸O-H2O changes were observed. The findings from this study may support future research on isotopic fractionation during nitrogen transformations and its linkage to hydrological processes. The results may also serve as a quantitative reference for field-scale PRB design and performance assessment.

Keywords
Nitrate
Column test
Permeable reactive barrier
Denitrification rate
Isotopic fractionation
References

References

1

Amoako-Nimako, G.K., Yang, X., and Chen, F., 2021, Denitrification using permeable reactive barriers with organic substrate or zero-valent iron fillers: controlling mechanisms, challenges, and future perspectives, Environ. Sci. Pollut. Res., 28(17), 21045-21064.

10.1007/s11356-021-13260-7
2

Amos, R.T. and Mayer, K.U., 2006, Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling, J. Contam. Hydrol., 87(1), 123-154.

10.1016/j.jconhyd.2006.04.008
3

Betlach, M.R. and Tiedje, J.M., 1981, Kinetic explanation for accumulation of nitrite, nitric oxide, and nitrous oxide during bacterial denitrification, Appl. Environ. Microbiol., 42(6), 1074-1084.

10.1128/aem.42.6.1074-1084.1981
4

Bilardi, S., Calabrò, P.S., and Moraci, N., 2023, A review of the hydraulic performance of permeable reactive barriers based on granular zero valent iron, Water, 15(1), 200.

10.3390/w15010200
5

Böhlke, J.K., Mroczkowski, S.J., and Coplen, T.B., 2003, Oxygen isotopes in nitrate: New reference materials for 18O:17O:16O measurements and observations on nitrate‐water equilibration, Rapid Commun. Mass Spectrom., 17(16), 1835-1846.

10.1002/rcm.1123
6

Buyanjargal, A., Kang, J., Lee, J.H., and Jeen, S.-W., 2023, Nitrate removal rates, isotopic fractionation, and denitrifying bacteria in a woodchip-based permeable reactive barrier system: a long-term column experiment, Environ. Sci. Pollut. Res. Int., 30(13), 36364-36376.

10.1007/s11356-022-24826-4
7

Craswell, E., 2021, Fertilizers and nitrate pollution of surface and ground water: an increasingly pervasive global problem, SN. Appl. Sci., 3(4), 518.

10.1007/s42452-021-04521-8
8

Curt, M.D., Aguado, P., Sánchez, G., Bigeriego, M., and Fernández, J., 2004, Nitrogen isotope ratios of synthetic and organic sources of nitrate water contamination in Spain, Water Air Soil Pollut., 151(1), 135-142.

10.1023/b:wate.0000009889.36833.c0
9

Deb, S., Lewicka-Szczebak, D., and Rohe, L., 2024, Microbial nitrogen transformations tracked by natural abundance isotope studies and microbiological methods: A review, Sci. Total Environ., 926, 172073.

10.1016/j.scitotenv.2024.172073
10

Debernardi, L., De Luca, D.A., and Lasagna, M., 2008, Correlation between nitrate concentration in groundwater and parameters affecting aquifer intrinsic vulnerability, Environ. Geol., 55(3), 539-558.

10.1007/s00254-007-1006-1
11

Dincer, A.R. and Karg©¥, F., 2000, Kinetics of sequential nitrification and denitrification processes, Enzyme Microb. Technol., 27(1-2), 37-42.

10.1016/S0141-0229(00)00145-9
12

Foglar, L., Briški, F., Sipos, L., and Vuković, M., 2005, High nitrate removal from synthetic wastewater with the mixed bacterial culture, Bioresour. Technol., 96(8), 879-888.

10.1016/j.biortech.2004.09.001
13

Gavaskar, A.R., 1999, Design and construction techniques for permeable reactive barriers, J. Hazard. Mater., 68(1-2), 41-71.

10.1016/s0304-3894(99)00031-x
14

Gibert, O., Pomierny, S., Rowe, I., and Kalin, R.M., 2008, Selection of organic substrates as potential reactive materials for use in a denitrification permeable reactive barrier (PRB), Bioresour. Technol., 99(16), 7587-7596.

10.1016/j.biortech.2008.02.012
15

Gómez, M.A., Hontoria, E., and González-López, J., 2002, Effect of dissolved oxygen concentration on nitrate removal from groundwater using a denitrifying submerged filter, J. Hazard. Mater., 90(3), 267-278.

10.1016/s0304-3894(01)00353-3
16

Gonsalez, V.L., Dombrowski, P.M., Lee, M.D., and Ramsburg, C.A., 2023, The influence of pH on subsurface denitrification stimulated with emulsified vegetable oil, Water, 15(5), 883.

10.3390/w15050883
17

He, Q., Zhu, Y., Li, G., Fan, L., Ai, H., Huangfu, X., and Li, H., 2017, Impact of dissolved oxygen on the production of nitrous oxide in biological aerated filters, Front. Environ. Sci. Eng., 11(6), 16.

10.1007/s11783-017-0964-0
18

Huang, H., Liu, M., Wang, J., He, J., and Chen, H., 2018, Sources identification of nitrogen using major ions and isotopic tracers in Shenyang, China, Geofluids, 2018(1), 8683904.

10.1155/2018/8683904
19

Humphrey Jr., C.P., Iverson, G., and O¡¯Driscoll, M., 2025, Performance Assessment of a Permeable Reactive Barrier on Reducing Groundwater Transport of Nitrate from an Onsite Wastewater Treatment System, Hydrology, 12(1), 18.

10.3390/hydrology12010018
20

Jeen, S.-W., Amos, R.T., and Blowes, D.W., 2012, Modeling gas formation and mineral precipitation in a granular iron column, Environ. Sci. Technol., 46(12), 6742-6749.

10.1021/es300299r
21

Jung, H., Kim, Y.S., Yoo, J., Park, B., and Lee, J., 2021, Seasonal variations in stable nitrate isotopes combined with stable water isotopes in a wastewater treatment plant: Implications for nitrogen sources and transformation, J. Hydrol., 599, 126488.

10.1016/j.jhydrol.2021.126488
22

Jung, H., Koh, D.-C., Kim, Y.S., Jeen, S.-W., and Lee, J., 2020, Stable Isotopes of Water and Nitrate for the Identification of Groundwater Flowpaths: A Review, Water, 12(1), 138.

10.3390/w12010138
23

Kendall, C., 1998, Tracing nitrogen sources and cycling in catchments, In: Kendall, C., McDonnell, J.J., Isotope Tracers in Catchment Hydrology, Elsevier, Amsterdam, The Netherlands, p.519-576.

10.1016/b978-0-444-81546-0.50023-9
24

Kendall, C., Elliott, E.M., and Wankel, S.D., 2007, Tracing Anthropogenic Inputs of Nitrogen to Ecosystems, In: Michener, R. and Lajtha, K., Stable Isotopes in Ecology and Environmental Science, Wiley-Blackwell, Oxford, p. 375-449.

10.1002/9780470691854.ch12
25

Kim, I.S., Lee, K.-S., Bong, Y.-S., Ryu, J.-S., and Kim, K.J., 2012, Nitrogen and oxygen isotope analysis of nitrate using denitrification method, J. Geol. Soc. Korea., 48(4), 351-356.

26

Knöller, K., Vogt, C., Haupt, M., Feisthauer, S., and Richnow, H.H., 2011, Experimental investigation of nitrogen and oxygen isotope fractionation in nitrate and nitrite during denitrification, Biogeochemistry, 103(1), 371-384.

10.1007/s10533-010-9483-9
27

Ko, H.N., Kang, J., and Jeen, S.-W., 2021, Removal of Nitrate in Groundwater Using Passive Treatment Systems: Evaluation of Removal Efficiency Through a Long-Term Column Experiment, J. Soil Groundw. Environ., 26(2), 17-27.

28

Le, F., Li, R., Ruan, X., and Liu, C., 2023, Isotopic tracing of nitrogen source and interaction between surface water and groundwater of a small valley plain in the Zhangxi watershed, Appl. Geochem., 151, 105615.

10.1016/j.apgeochem.2023.105615
29

Li, H. and Liu, Q., 2022, Reaction medium for permeable reactive barrier remediation of groundwater polluted by heavy metals, Front. Environ. Sci., 10, 968546.

10.3389/fenvs.2022.968546
30

Liu, Y., Liu, Y., Ma, L., Gong, Y., and Qian, J., 2020, Corncob PRB for on-site nitrate removal in groundwater, Arabian J. Geosci., 13(20), 1084.

10.1007/s12517-020-06089-w
31

Moloantoa, K.M., Khetsha, Z.P., Van Heerden, E., Castillo, J.C., and Cason, E.D., 2022, Nitrate water contamination from industrial activities and complete denitrification as a remediation option, Water, 14(5), 799.

10.3390/w14050799
32

Mollamohammada, S., Aly Hassan, A., and Dahab, M., 2020, Nitrate removal from groundwater using immobilized heterotrophic algae, Water Air Soil Pollut., 231(1), 26.

10.1007/s11270-019-4334-3
33

Obiri-Nyarko, F., Grajales-Mesa, S.J., and Malina, G., 2014, An overview of permeable reactive barriers for in situ sustainable groundwater remediation, Chemosphere, 111, 243-259.

10.1016/j.chemosphere.2014.03.112
34

Ortmeyer, F., Begerow, D., Guerreiro, M.A., Wohnlich, S., and Banning, A., 2021, Comparison of denitrification induced by various organic substances—Reaction rates, microbiology, and temperature effect, Water Resour. Res., 57(11), e2021WR029793.

10.1029/2021wr029793
35

Osaka, K.I., Ohte, N., Koba, K., Yoshimizu, C., Katsuyama, M., Tani, M., Tayasu, I., and Nagata, T., 2010, Hydrological influences on spatiotemporal variations of ¥ä15N and ¥ä18O of nitrate in a forested headwater catchment in central Japan: Denitrification plays a critical role in groundwater, J. Geophys. Res., 115(G2).

10.1029/2009jg000977
36

Qin, Y., Zhang, D., and Wang, F., 2019, Using nitrogen and oxygen isotopes to access sources and transformations of nitrogen in the Qinhe Basin, North China, Environ. Sci. Pollut. Res., 26(1), 738-748.

10.1007/s11356-018-3660-0
37

Ren, C., Zhang, Q., Wang, H., and Wang, Y., 2021, Identification of sources and transformations of nitrate in the intense human activity region of North China using a multi-isotope and Bayesian model, Int. J. Environ. Res. Public Health., 18(16), 8642.

10.3390/ijerph18168642
38

Rust, C.M., Aelion, C.M., and Flora, J.R., 2000, Control of pH during denitrification in subsurface sediment microcosms using encapsulated phosphate buffer, Water Res., 34(5), 1447-1454.

10.1016/s0043-1354(99)00287-0
39

Sahoo, P.K., Kim, K., and Powell, M.A., 2016, Managing groundwater nitrate contamination from livestock farms: implication for nitrate management guidelines, Curr. Pollut. Rep., 2(3), 178-187.

10.1007/s40726-016-0033-5
40

Sánchez Hidalgo, G.C., Ábrego-Bonilla, J., Deago, E., and Ortega Del Rosario, M.D.L.A., 2025, Global Perspectives on Groundwater Decontamination: Advances and Challenges of the Role of Permeable Reactive Barriers, Hydrology, 12(4), 98.

10.3390/hydrology12040098
41

Skinner, S.J. and Schutte, C.F., 2006, The feasibility of a permeable reactive barrier to treat acidic sulphate-and nitrate-contaminated groundwater, Water SA, 32(2), 129-136.

10.4314/wsa.v32i2.5253
42

Šrajbek, M., Kranjčević, L., Kovač, I., and Biondić, R., 2022, Groundwater nitrate pollution sources assessment for contaminated wellfield, Water, 14(2), 255.

10.3390/w14020255
43

Stylianoudaki, C., Trichakis, I., and Karatzas, G.P., 2022, Modeling groundwater nitrate contamination using artificial neural networks, Water, 14(7), 1173.

10.3390/w14071173
44

Volokita, M., Belkin, S., Abeliovich, A., and Soares, M.I.M. (1996). Biological denitrification of drinking water using newspaper, Water Research, 30(4), 965-971.

10.1016/0043-1354(95)00242-1
45

Ward, M.H., Jones, R.R., Brender, J.D., De Kok, T.M., Weyer, P.J., Nolan, B.T., Villanueva, C.M., and Van Breda, S.G., 2018, Drinking Water Nitrate and Human Health: An Updated Review, Int. J. Environ. Res. Public Health., 15(7), 1557.

10.3390/ijerph15071557
46

Zhang, Y., Shi, P., Song, J., and Li, Q., 2018, Application of nitrogen and oxygen isotopes for source and fate identification of nitrate pollution in surface water: a review, Appl. Sci., 9(1), 18.

10.3390/app9010018
47

Zhang, Y., Li, F., Zhang, Q., Li, J., and Liu, Q., 2014, Tracing nitrate pollution sources and transformation in surface-and ground-waters using environmental isotopes, Sci. Total Environ., 490, 213-222.

10.1016/j.scitotenv.2014.05.004
Information
  • Publisher :The Korean Society of Soil and Groundwater Environment
  • Publisher(Ko) :한국지하수토양환경학회
  • Journal Title :Journal of Soil and Groundwater Environment
  • Journal Title(Ko) :지하수토양환경
  • Volume : 30
  • No :6
  • Pages :42-54
  • Received Date : 2025-10-02
  • Revised Date : 2025-10-17
  • Accepted Date : 2025-10-22
  • DOI :https://doi.org/10.7857/JSGE.2025.30.6.042
Journal Informaiton Journal of Soil and Groundwater Environment Journal of Soil and Groundwater Environment
Online Submission
  • KOFST
  • KISTI Current Status
  • KISTI Cited-by
  • orcid
  • open access
  • ccl
Journal Informaiton Journal Informaiton - close