Hierarchical Environmental Exposure Transforms Zeolitic Imidazolate Framework-8 and Increases Toxicity in Daphnia magna
9 affiliations
- 1School of Geography, Earth & Environmental Sciences
- 2University of Birmingham
- 3Diamond Light Source
- 4Harwell Science and Innovation Campus
- 5Facility of Electron Microscopy
- 6Materials Engineering, Indian Institute of Technology
- 7School of Life and Environmental Sciences, Bournemouth University (Talbot Campus), Fern Barrow, Poole BH125BB, U.K
- 8School of Science, Engineering and Environment
- 9University of Salford
Abstract
High Resolution Image Download MS PowerPoint Slide Metal–organic frameworks (MOFs) are increasingly deployed in environmental technologies, yet their fate and hazard under realistic multistep exposure scenarios remain poorly constrained. Here, we track hierarchical transformations of nanoscale ZIF-8 (Zeolitic Imidazolate Framework-8) across an exposure cascade spanning atmospheric aging (air and reactive gases O 3 /NO 2 ), aqueous aging in environmentally and biologically relevant media, and ingestion by the freshwater crustacean Daphnia magna . Synchrotron Zn K-edge X-ray absorption spectroscopy (XAS), micro-X-ray fluorescence (μ-XRF), X-ray photoelectron spectroscopy (XPS), and electron microscopy show that gas-phase exposure produces only minor surface perturbations, whereas aqueous contact drives pronounced medium-dependent restructuring, including nitrogen depletion and oxygen enrichment at the surface and time-resolved dissolved Zn release with chemistry-imposed plateaus. In vivo, Zn speciation diverges from the pristine Zn–N fingerprint; an unexposed endogenous Zn baseline and linear combination fitting (LCF) indicate a mixture of endogenous Zn with transformed Zn pools dominated by O/P/S-type coordination environments. Acute ecotoxicity assay demonstrates strong concentration dependence (48 h immobilization EC 50 ≈0.5 μg mL –1 ), and chronic exposure at 0.10 μg mL –1 reduces cumulative brood production with increased adult mortality over 24 days. Mechanistically, fractionated toxicity assays show that washed aged particles/precipitates and whole aged suspensions are more potent than particle-free filtrates, indicating that particle-associated transformed Zn pools contribute substantially beyond dissolved Zn alone. Together, these results show that ZIF-8 risk emerges from its sequential transformation trajectory rather than its pristine state, motivating tiered aging protocols coupled to in vivo speciation and fractionated hazard testing for MOF safety assessment.
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BibTeX
@article{chakraborty2026hierarchical,
title = {{Hierarchical Environmental Exposure Transforms Zeolitic Imidazolate Framework-8 and Increases Toxicity in Daphnia magna}},
author = {Swaroop Chakraborty and Iuliia Mikulska and Rhiannon E. Boseley and Sang T. Pham and Prathmesh Bhadane and Pankti Dhumal and Santanu Majumder and Jajati Mandal and Tina Geraki and Superb K. Misra and Christian Pfrang and Iseult Lynch},
journal = {ACS Nano},
year = {2026},
month = may,
doi = {10.1021/acsnano.6c01107},
url = {https://doi.org/10.1021/acsnano.6c01107},
note = {CC BY},
}
RIS
TY - JOUR
TI - Hierarchical Environmental Exposure Transforms Zeolitic Imidazolate Framework-8 and Increases Toxicity in Daphnia magna
AU - Swaroop Chakraborty
AU - Iuliia Mikulska
AU - Rhiannon E. Boseley
AU - Sang T. Pham
AU - Prathmesh Bhadane
AU - Pankti Dhumal
AU - Santanu Majumder
AU - Jajati Mandal
AU - Tina Geraki
AU - Superb K. Misra
AU - Christian Pfrang
AU - Iseult Lynch
PY - 2026
DA - 2026/05/26
JO - ACS Nano
DO - 10.1021/acsnano.6c01107
UR - https://doi.org/10.1021/acsnano.6c01107
AB - High Resolution Image Download MS PowerPoint Slide Metal–organic frameworks (MOFs) are increasingly deployed in environmental technologies, yet their fate and hazard under realistic multistep exposure scenarios remain poorly constrained. Here, we track hierarchical transformations of nanoscale ZIF-8 (Zeolitic Imidazolate Framework-8) across an exposure cascade spanning atmospheric aging (air and reactive gases O 3 /NO 2 ), aqueous aging in environmentally and biologically relevant media, and ingestion by the freshwater crustacean Daphnia magna . Synchrotron Zn K-edge X-ray absorption spectroscopy (XAS), micro-X-ray fluorescence (μ-XRF), X-ray photoelectron spectroscopy (XPS), and electron microscopy show that gas-phase exposure produces only minor surface perturbations, whereas aqueous contact drives pronounced medium-dependent restructuring, including nitrogen depletion and oxygen enrichment at the surface and time-resolved dissolved Zn release with chemistry-imposed plateaus. In vivo, Zn speciation diverges from the pristine Zn–N fingerprint; an unexposed endogenous Zn baseline and linear combination fitting (LCF) indicate a mixture of endogenous Zn with transformed Zn pools dominated by O/P/S-type coordination environments. Acute ecotoxicity assay demonstrates strong concentration dependence (48 h immobilization EC 50 ≈0.5 μg mL –1 ), and chronic exposure at 0.10 μg mL –1 reduces cumulative brood production with increased adult mortality over 24 days. Mechanistically, fractionated toxicity assays show that washed aged particles/precipitates and whole aged suspensions are more potent than particle-free filtrates, indicating that particle-associated transformed Zn pools contribute substantially beyond dissolved Zn alone. Together, these results show that ZIF-8 risk emerges from its sequential transformation trajectory rather than its pristine state, motivating tiered aging protocols coupled to in vivo speciation and fractionated hazard testing for MOF safety assessment.
SN - 1936-0851
SN - 1936-086X
ER -