Mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to Chlorella vulgaris in the presence of NOM eco-corona

Widespread applications and release of photoactive nanoparticles (NPs) such as titanium dioxide (TiO2) into environmental matrices warrant mechanistic investigations addressing toxicity of NPs under environmentally relevant conditions. Accordingly, we investigated the effects of surface adsorbed nat...

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Main Authors: Ziruo Liu, Subhasis Ghoshal, Audrey Moores, Saji George
Format: Article
Language:English
Published: Elsevier 2023-09-01
Series:Ecotoxicology and Environmental Safety
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S0147651323006681
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author Ziruo Liu
Subhasis Ghoshal
Audrey Moores
Saji George
author_facet Ziruo Liu
Subhasis Ghoshal
Audrey Moores
Saji George
author_sort Ziruo Liu
collection DOAJ
description Widespread applications and release of photoactive nanoparticles (NPs) such as titanium dioxide (TiO2) into environmental matrices warrant mechanistic investigations addressing toxicity of NPs under environmentally relevant conditions. Accordingly, we investigated the effects of surface adsorbed natural organic matters (NOMs) such as humic acid, tannic acid and lignin on the band gap energy, abiotic reactive oxygen species (ROS) generation, surface chemistry and phototoxicity of TiO2 NPs. Initially, a liquid assisted grinding method was optimized to produce TiO2 NPs with a NOM layer of defined thickness for further analysis. Generally, adsorption of NOM reduced the band-gap energy of TiO2 NPs from 3.08 eV to 0.56 eV with humic acid, 1.92 eV with tannic acid and 2.48 eV with lignin. Light activated ROS generation by TiO2 NPs such as hydroxyl radicals, however, was reduced by 4, 2, 9 times in those coated with humic acid, tannic acid and lignin, respectively. This reduction in ROS despite decrease in band gap energy corroborated with the decreased surface oxygen vacancy (as revealed by X-ray Photoelectron Spectroscopy (XPS)) and quenching of ROS by surface adsorbed NOM. Despite the reduced ROS generation, the NOM-modified TiO2 NPs exhibited an increased phototoxicity to Chlorella vulgaris in comparison to pristine TiO2 NPs. Further analysis suggested that photoactivation of NOM modified TiO2 NPs releases toxic degradation products. Findings from our studies thus provide mechanistic insight into the ecotoxic potential of NOM-modified TiO2 NPs when exposed to light in the environment.
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spelling doaj.art-40d200c44cf647b5bf0c73b85fce812d2023-08-13T04:51:49ZengElsevierEcotoxicology and Environmental Safety0147-65132023-09-01262115164Mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to Chlorella vulgaris in the presence of NOM eco-coronaZiruo Liu0Subhasis Ghoshal1Audrey Moores2Saji George3Department of Food Science and Agricultural Chemistry, Macdonald Campus, McGill University, 21,111 Lakeshore, Ste Anne de Bellevue, Quebec H9X 3V9, Canada; Department of Materials Engineering, McGill University, 3610 University Street, Montreal, Quebec H3A 0C5, Canada; Centre in Green Chemistry and Catalysis, Department of Chemistry, McGill University, 801 Sherbrooke St. West, Montreal, QC, H3A 0B8, CanadaDepartment of Civil Engineering, McGill University, Montreal, Quebec H3A 0C3, CanadaDepartment of Materials Engineering, McGill University, 3610 University Street, Montreal, Quebec H3A 0C5, Canada; Centre in Green Chemistry and Catalysis, Department of Chemistry, McGill University, 801 Sherbrooke St. West, Montreal, QC, H3A 0B8, Canada; Corresponding author at: Department of Materials Engineering, McGill University, 3610 University Street, Montreal, Quebec H3A 0C5, Canada.Department of Food Science and Agricultural Chemistry, Macdonald Campus, McGill University, 21,111 Lakeshore, Ste Anne de Bellevue, Quebec H9X 3V9, Canada; Correspondence to: Department of Food Science and Agricultural Chemistry, Macdonald-Stewart Building, Macdonald Campus, McGill University, Room-1039, 21,111 Lakeshore, Ste Anne de Bellevue, Québec H9X 3V9, Canada.Widespread applications and release of photoactive nanoparticles (NPs) such as titanium dioxide (TiO2) into environmental matrices warrant mechanistic investigations addressing toxicity of NPs under environmentally relevant conditions. Accordingly, we investigated the effects of surface adsorbed natural organic matters (NOMs) such as humic acid, tannic acid and lignin on the band gap energy, abiotic reactive oxygen species (ROS) generation, surface chemistry and phototoxicity of TiO2 NPs. Initially, a liquid assisted grinding method was optimized to produce TiO2 NPs with a NOM layer of defined thickness for further analysis. Generally, adsorption of NOM reduced the band-gap energy of TiO2 NPs from 3.08 eV to 0.56 eV with humic acid, 1.92 eV with tannic acid and 2.48 eV with lignin. Light activated ROS generation by TiO2 NPs such as hydroxyl radicals, however, was reduced by 4, 2, 9 times in those coated with humic acid, tannic acid and lignin, respectively. This reduction in ROS despite decrease in band gap energy corroborated with the decreased surface oxygen vacancy (as revealed by X-ray Photoelectron Spectroscopy (XPS)) and quenching of ROS by surface adsorbed NOM. Despite the reduced ROS generation, the NOM-modified TiO2 NPs exhibited an increased phototoxicity to Chlorella vulgaris in comparison to pristine TiO2 NPs. Further analysis suggested that photoactivation of NOM modified TiO2 NPs releases toxic degradation products. Findings from our studies thus provide mechanistic insight into the ecotoxic potential of NOM-modified TiO2 NPs when exposed to light in the environment.http://www.sciencedirect.com/science/article/pii/S0147651323006681Titanium dioxideEco-coronaPhototoxicityNatural organic mattersSurface oxygen vacancyBand gap energy
spellingShingle Ziruo Liu
Subhasis Ghoshal
Audrey Moores
Saji George
Mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to Chlorella vulgaris in the presence of NOM eco-corona
Ecotoxicology and Environmental Safety
Titanium dioxide
Eco-corona
Phototoxicity
Natural organic matters
Surface oxygen vacancy
Band gap energy
title Mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to Chlorella vulgaris in the presence of NOM eco-corona
title_full Mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to Chlorella vulgaris in the presence of NOM eco-corona
title_fullStr Mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to Chlorella vulgaris in the presence of NOM eco-corona
title_full_unstemmed Mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to Chlorella vulgaris in the presence of NOM eco-corona
title_short Mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to Chlorella vulgaris in the presence of NOM eco-corona
title_sort mechanistic study of the increased phototoxicity of titanium dioxide nanoparticles to chlorella vulgaris in the presence of nom eco corona
topic Titanium dioxide
Eco-corona
Phototoxicity
Natural organic matters
Surface oxygen vacancy
Band gap energy
url http://www.sciencedirect.com/science/article/pii/S0147651323006681
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