Biotic Transformation of Abiotically Stable Nanoscale UiO-66 Metal–Organic Framework by Daphnia magna Results in Chronic Reproductive Toxicity

作者
Swaroop Chakraborty,Pankti Dhumal,Iuliia Mikulska,Sang T. Pham,Laura‐Jayne A. Ellis,Dhruv Menon,Superb K. Misra,Iseult Lynch
出处
期刊:ACS Nano [American Chemical Society]
卷期号:19 (49): 41874-41887
标识
DOI:10.1021/acsnano.5c16532
摘要

Metal-organic frameworks (MOFs) are entering water technologies on the premise that abiotic stability predicts ecological safety. We overturn this assumption by showing that UiO-66 - often regarded as chemically and structurally robust - remains intact after 7-day aging in natural borehole water yet undergoes rapid in vivo transformation in Daphnia magna. Synchrotron Microfocus X-ray absorption spectroscopy (XAS) revealed collapse of the ordered Zr-carboxylate coordination into disordered Zr-O environments within the gut; Extended X-ray Absorption Fine Structure (EXAFS) showed loss of second-shell features, and Transmission Electron Microscopy (TEM) confirmed loss of crystallinity with nanoscale aggregates appearing within 24 h of ingestion. Although acute immobilization was limited (48 h EC50 ≈ 26.5 μg mL-1), a sublethal, environmentally relevant exposure (10 μg mL-1) caused pronounced chronic effects: brood initiation was delayed by 3-5 days and cumulative reproduction decreased by ∼74% without mortality. We attribute these outcomes to gut-level transformation and associated energetic/physiological burdens, not captured by standard acute tests. These results show that abiotic stability does not necessarily imply biological inertness and highlight the need to integrate in vivo transformation pathways with chronic end points in environmental risk assessment for water-sector materials. This perspective provides a mechanistic basis to inform Safe-and-Sustainable-by-Design (SSbD) MOFs before widespread deployment in water treatment.
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