Effects of Humic Acids on the Ecotoxicity of Fe3O4 Nanoparticles and Fe-Ions: Impact of Oxidation and Aging
Abstract
:1. Introduction
2. Materials and Methods
2.1. Synthesis and Modification of Fe3O4 Nanoparticles
2.1.1. Synthesis of Fe3O4 and Fe3O4/HA Nanoparticles
2.1.2. Simulation of Oxidation of Fe3O4/HA NPs in Mild and Harsh Conditions
2.1.3. Preparation of Complexes of HA with Fe2+ and/or Fe3+
2.2. Characterisation of the Microstructure of Magnetic NPs (MNPs)
2.3. Characterisation of the Magnetic Properties of Magnetite NPs (MNPs)
2.4. Analysis of the Surface Charge and Hydrodynamic Diameter of Magnetic NPs (MNPs)
2.5. Ecotoxicity Testing of Magnetic NPs (MNPs) and Fe-Ions
2.5.1. Paramecium caudatum Acute Toxicity Test
2.5.2. Sinapis alba L. Acute Toxicity Test
2.6. Statistical Analysis
3. Results and Discussion
3.1. Microstructure of Magnetite Nanoparticles (MNPs)
3.2. Evaluation of the Magnetic Properties of the Studied MNPs
3.3. The Ecotoxicity of Bare Fe3O4 NPs (MNPs) and Humic Acids-Modified MNPs Before and After Oxidation in Mild and Harsh Conditions
3.4. Structure–Bioactivity Relationship for MNPs
3.5. The Ecotoxicity of Fe-Ions before and after Addition of Humic Acids
3.5.1. Ecotoxicity of Fe2+/Fe3+
3.5.2. Effects of Humic Acids on the Ecotoxicity of Fe2+ and Fe3+
3.6. Acute Toxicity of Fe2+/Fe3+ with and without Addition of Humic Acids: Effect of Aging
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
Abbreviations
HA | Humic acids |
HS | Humic substances |
NPs | Nanoparticles |
MNPs | Magnetite nanoparticles |
SPIONs | Superparamagnet iron oxide nanoparticles |
XRD | X-ray diffraction analysis |
DOM | Dissolved organic matter |
nZVI | Nano zerovalent iron |
NOM | Natural organic matter |
DLS | Dynamic light scattering |
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Sample | Fe3O4 | Fe3O4/HA | Fe3O4/HA Harsh Oxidation | Fe3O4/HA Mild Oxidation | ||||
---|---|---|---|---|---|---|---|---|
hkl | 2θ, ° | d, Å | 2θ, ° | d, Å | 2θ, ° | d, Å | 2θ, ° | d, Å |
220 | 45.60 | 2.971 | 45.67 | 2.966 | 45.62 | 2.954861 | 49.33 | 2.74502038 |
311 | 53.98 | 2.535 | 54.01 | 2.535 | 53.92 | 2.526709 | 53.92 | 2.52670925 |
400 | 66.28 | 2.094 | 66.36 | 2.094 | 66.39 | 2.09233 | - | - |
422 | 84.25 | 1.714 | 84.25 | 1.714 | 84.38 | 1.705695 | 82.6 | 1.73564713 |
511 | 90.77 | 1.610 | 90.71 | 1.612 | 90.62 | 1.61133 | 92.69 | 1.58329633 |
440 | 101.52 | 1.476 | 101.4 | 1.476 | 101.68 | 1.477368 | 101.3 | 1.48137719 |
a, A | 8.383(2) | 8.382(6) | 8.365(5) | 8.250(8) | ||||
x | 0.387(7) | 0.382(1) | 0.232(7) | - | ||||
δ | 0.059(4) | 0.062(7) | 0.154(2) | - | ||||
Fe3-δO4 | Fe2.94O4 | Fe2.93O4 | Fe2.84O4 | - | ||||
% Fe3O4 | ~82.7 | ~79.2 | ~48.3 | 0 | ||||
D, nm | 6.9 ± 2.4 | 10.3 ± 1.3 | 7.8 ± 1.9 | 11.03 ± 5.1 | ||||
CV, % | 34 | 12.6 | 24.6 | 50.2 |
Sample | Saturation Magnetization Ms, emu/g | Remanent Magnetization Mr, emu/g | Coercive Force Hc, Oe |
---|---|---|---|
Fe3O4 (bare) | 68.2 | 6.88 | 74.1 |
Fe3O4/HA | 30.9 | 6.40 | 160 |
Fe3O4/HAox (harsh oxidation) | 15.7 | 4.11 | 159 |
Sample | %Fe3O4 | ξ, mV | Hydrodynamic Diameter, nm | 24 h EC50 for P. caudatum, mg/L | 96 h EC50 for S. alba, mg/L |
---|---|---|---|---|---|
Fe3O4 | 83 | −25.5 ± 6.03 | 400.8 | >33 ** | >3300 |
HA | - | - | - | >33 ** | 900.65 ± 106.2 |
Fe3O4/HA | 79 | −38.8 ± 7.1 | 153.2 | 32 ± 3.1 | 902.71 ± 211.5 |
Fe3O4/HA harsh oxidation | 48 | −16.19 ± 2.1 | 886.7 | 0.33 ± 0.01 | 330 ± 10.1 |
Fe3O4/HA mild oxidation | 0 * | −49.63 ± 2.2 | 586.1 | 1.40 ± 0.5 | 951.6 ± 80.2 |
Sample | EC50 ± SD (mg/L) |
---|---|
Toxicity to ciliates P. caudatum (24 h EC50) | |
Fe2+ a | 1.15 ± 1.4 |
Fe3+ a | 3.27 ± 0.8 |
Fe2+/Fe3+ c | 0.48 |
Fe3O4 | >33 |
HA | >33 |
Fe(II)HA | >33 |
Fe(III)HA | 24.6 ± 9.3 |
Fe(II,III)HA b,c | >15.1 |
Fe3O4/HA b | 32 ± 3.1 |
Toxicity to plants S. alba (96 h EC50) | |
Fe2+ | 35.92 ± 18.6 |
Fe3+ | 58.71 ± 21.2 |
Fe2+/Fe3+ | 75.21 ± 44.4 |
Fe3O4 c | >3300 |
HA | 900.65 ± 106.2 |
Fe(II)HA | 1402.3 ± 135.1 |
Fe(III)HA | 256.18 ± 50.4 |
Fe(II,III)HA | 910.43 ± 270.1 |
Fe3O4/HA | 902.71 ± 211.5 |
Sample | EC50 ± SD (mg Fe/L) |
---|---|
Toxicity to ciliates P. caudatum (24 h EC50) | |
HA * | >33 |
HA * (90 days) | 1.93 ± 0.55 |
Fe2+/Fe3+ | 0.48 ± 0.02 |
Fe2+/Fe3+ (90 days) | 0.67 ± 0.02 |
Fe(II,III)HA | >15.1 |
Fe(II,III)HA (90 days) | 1.4 ± 0.4 |
Toxicity to plants S. alba (96 h EC50) | |
HA * | 900.65 ± 106.2 |
HA * (90 days) | 880.1 ± 123.1 |
Fe2+/Fe3+ | 75.21 ± 44.4 |
Fe2+/Fe3+ (90 days) | 231.41 ± 97.46 |
Fe(II,III)HA | 910.43 ± 270.1 |
Fe(II,III)HA (90 days) | 915.23 ± 145.2 |
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Bondarenko, L.; Kahru, A.; Terekhova, V.; Dzhardimalieva, G.; Uchanov, P.; Kydralieva, K. Effects of Humic Acids on the Ecotoxicity of Fe3O4 Nanoparticles and Fe-Ions: Impact of Oxidation and Aging. Nanomaterials 2020, 10, 2011. https://doi.org/10.3390/nano10102011
Bondarenko L, Kahru A, Terekhova V, Dzhardimalieva G, Uchanov P, Kydralieva K. Effects of Humic Acids on the Ecotoxicity of Fe3O4 Nanoparticles and Fe-Ions: Impact of Oxidation and Aging. Nanomaterials. 2020; 10(10):2011. https://doi.org/10.3390/nano10102011
Chicago/Turabian StyleBondarenko, Lyubov, Anne Kahru, Vera Terekhova, Gulzhian Dzhardimalieva, Pavel Uchanov, and Kamila Kydralieva. 2020. "Effects of Humic Acids on the Ecotoxicity of Fe3O4 Nanoparticles and Fe-Ions: Impact of Oxidation and Aging" Nanomaterials 10, no. 10: 2011. https://doi.org/10.3390/nano10102011