Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

doi:10.1007/s11783-020-1252-y

Front. Environ. Sci. Eng.

2020, Vol. 14

Issue (4) : 73 https://doi.org/10.1007/s11783-020-1252-y

RESEARCH ARTICLE

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

Hanzhong Jia^1,², Yafang Shi¹, Xiaofeng Nie¹, Song Zhao¹, Tiecheng Wang¹(

), Virender K. Sharma³(

)

¹. College of Resources and Environment, Northwest A&F University, Yangling 712100, China
². State Key Laboratory of Soil Erosion and Dryland Farming on Loess Plateau, Institute of Soil and Water Conservation, Northwest A&F University, Yangling 712100, China
³. Program for the Environment and Sustainability, Department of Occupational and Environmental Health, School of Public Health, Texas A&M University, College Station, TX 77843, USA

Download: PDF(1297 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

• Regulation of redox conditions promotes the generation of free radicals on HM.

• HM-PFRs can be fractionated into active and inactive types depending on stability.

• The newly produced PFRs readily release electrons to oxygen and generate ROS.

• PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM.

The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.

Keywords Humic substance Polycyclic aromatic hydrocarbons (PAHs) Persistent free radicals (PFRs) Redox Reactive oxygen species (ROS)

Corresponding Author(s): Tiecheng Wang,Virender K. Sharma

Issue Date: 19 June 2020

Cite this article:

Hanzhong Jia,Yafang Shi,Xiaofeng Nie, et al. Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons[J]. Front. Environ. Sci. Eng., 2020, 14(4): 73.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-020-1252-y
https://academic.hep.com.cn/fese/EN/Y2020/V14/I4/73

Fig.1 (a) EPR spectra of the isolated peat humins (HM) (or original HM), and H₂O₂ and L-ascorbic acid (VC) treated HM samples, assigned as H₂O₂-HM and VC-HM samples, respectively; (b) Variation of peak area and g-Factor for the treated HM by H₂O₂ and L-ascorbic acid (VC) at varied concentrations ranging from 0.0 to 0.10 mol/L.

Fig.2 X-ray photoelectron spectra (XPS) of the original and treated peat HM, including (a) original HM (or untreated samples), (b) HM treated with 0.04 mol/L H₂O₂, (c) HM treated with 0.10 mol/L H₂O₂, (d) HM treated with 0.04 mol/L L-ascorbic acid, and (e) HM treated with 0.10 mol/L L-ascorbic acid.

Fig.3 Evolution of spin densities as a function of aging time for the originally isolated HM, H₂O₂- and L-ascorbic acid-treated HM samples under different conditions, such as (a) Air, RH= 60%, (b) air, RH= 7%, (c) Air, ~100%, and (d) no Air, RH= 0%.

Fig.4 Variation of concentrations of hydroxyl radials and ROS with concentration of EPFRs of HM samples treated by H₂O₂ and L-ascorbic acid.

Fig.5 (a) Evolution of PAHs, including benzo[a]pyrene (B[a]P), anthracene (ANT), phenanthrene (PHE), and naphthalene (NAP), as a function of reaction time during the transformation process by 0.10 mol/L L-ascorbic acid-HM sample; Evolution of ANT as a function of reaction time in the reaction systems involving in HM samples treated by different amounts of (b) H₂O₂ and (c) L-ascorbic acid. (d) Transformation of ANT by 0.10 mol/L L-ascorbic acid-HM in the presence of coumarin and benzoquinone.

1	J M Campos-Martin, G Blanco-Brieva, J L G Fierro (2006). Hydrogen peroxide synthesis: An outlook beyond the anthraquinone process. Angewandte Chemie International Edition, 45(42): 6962–6984 https://doi.org/10.1002/anie.200503779
2	I Cwielag-Piasecka, M Witwicki, M Jerzykiewicz, J Jezierska (2017). Can carbamates undergo radical oxidation in the soil environment? A case study on carbaryl and carbofuran. Environmental Science & Technology, 51(24): 14124–14134 https://doi.org/10.1021/acs.est.7b03386
3	G Fang, C Zhu, D D Dionysiou, J Gao, D Zhou (2015). Mechanism of hydroxyl radical generation from biochar suspensions: implications to diethyl phthalate degradation. Bioresource Technology, 176: 210–217 https://doi.org/10.1016/j.biortech.2014.11.032
4	K Gohre, R Scholl, G C Miller (1986). Singlet oxygen reactions on irradiated soil surfaces. Environmental Science & Technology, 20(9): 934–938 https://doi.org/10.1021/es00151a013
5	H Z Jia, L Li, H X Chen, Y Zhao, X Y Li, C Y Wang (2015). Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light. Journal of Hazardous Materials, 287: 16–23 https://doi.org/10.1016/j.jhazmat.2015.01.040
6	H Z Jia, G Nulaji, H W Gao, F Wang, Y Q Zhu, C Wang (2016). Formation and stabilization of environmentally persistent free radicals induced by the interaction of anthracene with Fe(III)-modified clays. Environmental Science & Technology, 50(12): 6310–6319 https://doi.org/10.1021/acs.est.6b00527
7	H Z Jia, J C Zhao, X Y Fan, K Dilimulati, C Y Wang (2012). Photodegradation of phenanthrene on cation-modified clays under visible light. Applied Catalysis B: Environmental, 123-124: 43–51 https://doi.org/10.1016/j.apcatb.2012.04.017
8	H Z Jia, S Zhao, Y F Shi, L Y Zhu, C Y Wang, V K Sharma (2018). Transformation of polycyclic aromatic hydrocarbons and formation of environmentally persistent free radicals on modified montmorillonite: The role of surface metal ions and polycyclic aromatic hydrocarbon molecular properties. Environmental Science & Technology, 52(10): 5725–5733 https://doi.org/10.1021/acs.est.8b00425
9	X Jin, F O Kengara, X Yue, F Wang, R Schroll, J C Munch, C Gu, X Jiang (2019). Shorter interval and multiple flooding-drying cycling enhanced the mineralization of 14C-DDT in a paddy soil. Science of the Total Environment, 676: 420–428 https://doi.org/10.1016/j.scitotenv.2019.04.284
10	L Khachatryan, J Adounkpe, Z Maskos, B Dellinger (2006). Formation of cyclopentadienyl radical from the gas-phase pyrolysis of hydroquinone, catechol, and phenol. Environmental Science & Technology, 40(16): 5071–5076 https://doi.org/10.1021/es051878z
11	L Khachatryan, B Dellinger (2011). Environmentally persistent free radicals (EPFRs)-2. Are free hydroxyl radicals generated in aqueous solutions? Environmental Science & Technology, 45(21): 9232– 9239 https://doi.org/10.1021/es201702q
12	L Khachatryan, C A McFerrin, R W Hall, B Dellinger (2014). Environmentally persistent free radicals (EPFRs). 3. Free versus bound hydroxyl radicals in EPFR aqueous solutions. Environmental Science & Technology, 48(16): 9220–9226 https://doi.org/10.1021/es501158r
13	Y Li, J Niu, E Shang, J C Crittenden (2016). Influence of dissolved organic matter on photogenerated reactive oxygen species and metal-oxide nanoparticle toxicity. Water Research, 98: 9–18 https://doi.org/10.1016/j.watres.2016.03.050
14	Z Maskos, B Dellinger (2008). Formation of the secondary radicals from the aging of tobacco smoke. Energy & Fuels, 22(1): 382–388 https://doi.org/10.1021/ef700446v
15	Z Maskos, L Khachatryan, B Dellinger (2005). Precursors of radicals in tobacco smoke and the role of particulate matter in forming and stabilizing radicals. Energy & Fuels, 19(6): 2466–2473 https://doi.org/10.1021/ef058018o
16	L Munk, A K Sitarz, D C Kalyani, J D Mikkelsen, A S Meyer (2015). Can laccases catalyze bond cleavage in lignin? Biotechnology Advances, 33(1): 13–24 https://doi.org/10.1016/j.biotechadv.2014.12.008
17	T Oniki, U Takahama (1994). Effects of reaction time, chemical reduction, and oxidation on ESR in aqueous solutions of humic acids. Soil Science, 158(3): 204–210 https://doi.org/10.1097/00010694-199409000-00006
18	S E Page, M Sander, W A Arnold, K McNeill (2012). Hydroxyl radical formation upon oxidation of reduced humic acids by oxygen in the dark. Environmental Science & Technology, 46(3): 1590–1597 https://doi.org/10.1021/es203836f
19	A Paul, R Stosser, A Zehl, E Zwirnmann, R D Vogt, C E W Steinberg (2006). Nature and abundance of organic radicals in natural organic matter: Effect of pH and irradiation. Environmental Science & Technology, 40(19): 5897–5903 https://doi.org/10.1021/es060742d
20	A Piccolo, P Conte, I Scheunert, M Paci (1998). Atrazine interactions with soil humic substances of different molecular structure. Journal of Environmental Quality, 27(6): 1324–1333 https://doi.org/10.2134/jeq1998.00472425002700060009x
21	L R Radovic (2009). Active sites in graphene and the mechanism of CO2 formation in carbon oxidation. Journal of the American Chemical Society, 131(47): 17166–17175 https://doi.org/10.1021/ja904731q
22	M Rechcigl, C R Co (1977). CRC Handbook Series in Nutrition and Food- Sect. D: Nutritional Requirements. v. 1: Comparative and Qualitative Requirements. Boca Raton: CRC Press
23	R W Rex (1960). Electron paramagnetic resonance studies of stable free radicals in lignins and humic acids. Nature, 188(4757): 1185–1186 https://doi.org/10.1038/1881185a0
24	E E Roden, A Kappler, I Bauer, J Jiang, A Paul, R Stoesser, H Konishi, H F Xu (2010). Extracellular electron transfer through microbial reduction of solid-phase humic substances. Nature Geoscience, 3(6): 417–421 https://doi.org/10.1038/ngeo870
25	S C Saab, L Martin-Neto (2004). Studies of semiquinone free radicals by ESR in the whole soil, HA, FA and humin substances. Journal of the Brazilian Chemical Society, 15(1): 34–37 https://doi.org/10.1590/S0103-50532004000100007
26	N Senesi, Y Chen, M Schnitzer (1977). The role of free radicals in the oxidation and reduction of fulvic acid. Soil Biology & Biochemistry, 9(6): 397–403 https://doi.org/10.1016/0038-0717(77)90018-9
27	V K Sharma, X Yu, T J McDonald, Jinadatha C, D D Dionysiou, Feng M (2019). Elimination of antibiotic resistance genes and control of horizontal transfer risk by UV-based treatment of drinking water: A mini review. Frontiers of Environmental Science & Engineering, 13(3): 2–10 https://doi.org/10.1007/s11783-019-1122-7
28	A J Simpson (2002). Determining the molecular weight, aggregation, structures and interactions of natural organic matter using diffusion ordered spectroscopy. Magnetic Resonance in Chemistry, 40(13): S72–S82 https://doi.org/10.1002/mrc.1106
29	Y J Tian, J R Zou, L Feng, L Q Zhang, Y Z Liu (2019). Chlorella vulgaris enhance the photodegradation of chlortetracycline in aqueous solution via extracellular organic matters (EOMs): Role of triplet state EOMs. Water Research, 149: 35–41 https://doi.org/10.1016/j.watres.2018.10.076
30	E P Vejerano, G Y Rao, L Khachatryan, S A Cormier, S Lomnicki (2018). Environmentally persistent free radicals: insights on a new class of pollutants. Environmental Science & Technology, 52(5): 2468–2481 https://doi.org/10.1021/acs.est.7b04439
31	C Wang, Y Z Li, H Tan, A K Zhang, Y L Xie, B Wu, H Xu (2019). A novel microbe consortium, nano-visible light photocatalyst and microcapsule system to degrade PAHs. Chemical Engineering Journal, 359: 1065–1074 https://doi.org/10.1016/j.cej.2018.11.077
32	T C Wang, Y Cao, G Z Qu, Q H Sun, T J Xia, X T Guo, H Z Jia, L Y Zhu (2018). Novel Cu(II)EDTA decomplexation by discharge plasma oxidation and coupled Cu removal by alkaline precipitation: Underneath mechanisms. Environmental Science & Technology, 52(14): 7884–7891 https://doi.org/10.1021/acs.est.8b02039
33	K K Zhang , P Sun , Y R Zhang (2019). Decontamination of Cr(VI) facilitated formation of persistent free radicals on rice husk derived biochar. Frontiers of Environmental Science & Engineering, 13(2): 85–93 https://doi.org/10.1007/s11783-019-1169-5
34	K C Zhu, H Z Jia, S Zhao, T J Xia, X T Guo, T C Wang, L Y Zhu (2019). Formation of environmentally persistent free radicals on microplastics under light irradiation. Environmental Science & Technology, 53(14): 8177–8186 https://doi.org/10.1021/acs.est.9b01474
35	K Zhu, H Jia, F Wang, Y Zhu, C Wang, C Ma(2017). Efficient removal of Pb(II) from aqueous solution by modified montmorillonite/carbon composite: Equilibrium, Kinetics and Thermodynamics. Journal of Chemical & Engineering Data, 62(1): 333–340 https://doi.org/10.1021/acs.jced.6b00676

[1]

FSE-20057-OF-JHZ_suppl_1

Download

[1]	Jianmei Zou, Jianzhi Huang, Huichun Zhang, Dongbei Yue. Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization[J]. Front. Environ. Sci. Eng., 2021, 15(1): 5-.
[2]	Yafang Shi, Yunchao Dai, Ziwen Liu, Xiaofeng Nie, Song Zhao, Chi Zhang, Hanzhong Jia. Light-induced variation in environmentally persistent free radicals and the generation of reactive radical species in humic substances[J]. Front. Environ. Sci. Eng., 2020, 14(6): 106-.
[3]	Lingchen Kong, Xitong Liu. Emerging electrochemical processes for materials recovery from wastewater: Mechanisms and prospects[J]. Front. Environ. Sci. Eng., 2020, 14(5): 90-.
[4]	Chao Pan, Daniel Giammar. Interplay of transport processes and interfacial chemistry affecting chromium reduction and reoxidation with iron and manganese[J]. Front. Environ. Sci. Eng., 2020, 14(5): 81-.
[5]	Yuning YANG,Huan LI. Recovering humic substances from the dewatering effluent of thermally treated sludge and its performance as an organic fertilizer[J]. Front. Environ. Sci. Eng., 2016, 10(3): 578-584.
[6]	Qiuying CHEN,Jingling LIU,Feng LIU,Binbin WANG,Zhiguo CAO. Biologic risk and source diagnose of 16 PAHs from Haihe River Basin, China[J]. Front. Environ. Sci. Eng., 2016, 10(1): 46-52.
[7]	XIA Tianxiang,JIANG Lin,JIA Xiaoyang,ZHONG Maosheng,LIANG Jing. Application of probabilistic risk assessment at a coking plant site contaminated by Polycyclic Aromatic Hydrocarbons[J]. Front.Environ.Sci.Eng., 2014, 8(3): 441-450.
[8]	Kai LIU, Fengkui DUAN, Kebin HE, Yongliang MA, Yuan CHENG. Investigation on sampling artifacts of particle associated PAHs using ozone denuder systems[J]. Front Envir Sci Eng, 2014, 8(2): 284-292.
[9]	Guangxia QI, Dongbei YUE, Yongfeng NIE. Characterization of humic substances in bio-treated municipal solid waste landfill leachate[J]. Front Envir Sci Eng, 2012, 6(5): 711-716.
[10]	Chunhua ZHANG, Ying GE, Huan YAO, Xiao CHEN, Minkun HU. Iron oxidation-reduction and its impacts on cadmium bioavailability in paddy soils: a review[J]. Front Envir Sci Eng, 2012, 6(4): 509-517.
[11]	Osamu SHITAMICHI, Taiki MATSUI, Yamei HUI, Weiwei CHEN, Totaro IMASAKA. Determination of persistent organic pollutants by gas chromatography/laser multiphoton ionization/time-of-flight mass spectrometry[J]. Front Envir Sci Eng, 2012, 6(1): 26-31.
[12]	Rongchang WANG, Xinmin ZHAN, Yalei ZHANG, Jianfu ZHAO. Nitrifying population dynamics in a redox stratified membrane biofilm reactor (RSMBR) for treating ammonium-rich wastewater[J]. Front Envir Sci Eng Chin, 2011, 5(1): 48-56.
[13]	Jinbao WU, Zongqiang GONG, Liyan ZHENG, Yanli YI, Jinghua JIN, Xiaojun LI, Peijun LI. Removal of high concentrations of polycyclic aromatic hydrocarbons from contaminated soil by biodiesel[J]. Front Envir Sci Eng Chin, 2010, 4(4): 387-394.
[14]	Zhenyi ZHANG, Chihiro INOUE, Guanghe LI, . Impact of solids on biphasic biodegradation of phenanthrene in the presence of hydroxypropyl- β -cyclodextrin (HPCD)[J]. Front.Environ.Sci.Eng., 2010, 4(3): 329-333.
[15]	XIA Xinghui, HU Lijuan, MENG Lihong. Adsorption and partition of benzo(a)pyrene on sediments with different particle sizes from the Yellow River[J]. Front.Environ.Sci.Eng., 2007, 1(2): 172-178.

Viewed

Full text

Abstract

Cited

Shared

Discussed