{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,23]],"date-time":"2026-10-23T19:43:01Z","timestamp":1792784581576,"version":"4.5.0"},"reference-count":68,"publisher":"American Chemical Society (ACS)","issue":"36","license":[{"start":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T00:00:00Z","timestamp":1787788800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T00:00:00Z","timestamp":1787788800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T00:00:00Z","timestamp":1787788800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"name":"National Natural Science Foundation of China (NSFC)","award":["22176150"],"award-info":[{"award-number":["22176150"]}],"id":[{"id":"https:\/\/ror.org\/01h0zpd94","id-type":"ROR","asserted-by":"crossref"}]},{"name":"National Natural Science Foundation of China (NSFC)","award":["22576159"],"award-info":[{"award-number":["22576159"]}],"id":[{"id":"https:\/\/ror.org\/01h0zpd94","id-type":"ROR","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,15]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Copper-based particulates, from nanomaterials to commercial pesticides, are widely used in agriculture. Runoff from high-dose applications leads to accumulation in aquatic systems, where they interact with sulfide-rich environments. Although sulfidation is considered as a detoxification pathway for metal-based nanomaterials, its effects on the developmental toxicity of copper-based pesticides with different oxidation states remains unclear. Herein, we investigated the sulfidation of copper nanoparticles (Cu NPs), Cu2O, and Cu(OH)2 pesticides to link physicochemical transformations with zebrafish developmental toxicity. Transformation pathways were valence-dependent, i.e., Cu NPs formed Cu2S via a core\u2013shell mechanism, whereas Cu2O and Cu(OH)2 transformed via dissolution\u2013precipitation. After sulfidation, Cu NPs and Cu2O exhibited reduced copper ion release and alleviated hatching inhibition. In contrast, sulfidation of Cu(OH)2 aggravated hatching inhibition. Sulfidation also led to organic additives removal, improving survival despite persistent hatching inhibition in the Cu(OH)2 group. Histological and cellular analyses confirmed cardiac injury and apoptosis after exposure to copper-based particles and their sulfidation products. Transcriptional profiling showed that sulfidation partially normalized cardiac development genes in Cu NPs and Cu2O groups but not in the Cu(OH)2 group. These findings demonstrate that sulfidation does not universally mitigate copper toxicity, highlighting the importance of copper oxidation states in environmental risk assessment.<\/jats:p>","DOI":"10.1021\/acs.est.6c04746","type":"journal-article","created":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T16:04:45Z","timestamp":1788278685000},"page":"25268-25278","source":"Crossref","is-referenced-by-count":0,"title":["Valence-Dependent\nTransformation of Copper-Based Pesticides:\nDivergent Sulfidation Pathways and Differential Toxicity of Cu, Cu2O, and Cu(OH)2 in Zebrafish"],"prefix":"10.1021","volume":"60","author":[{"given":"Xiaoying","family":"Lin","sequence":"first","affiliation":[{"name":"Tongji University , , ,","place":["Shanghai, China, 200092"]},{"name":"Shanghai Institute of Pollution Control and Ecological Security , , ,","place":["Shanghai, China, 200092"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stephanie Ling Jie","family":"Lee","sequence":"additional","affiliation":[{"name":"Tongji University , , ,","place":["Shanghai, China, 200092"]},{"name":"Shanghai Institute of Pollution Control and Ecological Security , , ,","place":["Shanghai, China, 200092"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fei","family":"He","sequence":"additional","affiliation":[{"name":"Tongji University , , ,","place":["Shanghai, China, 200092"]},{"name":"Shanghai Institute of Pollution Control and Ecological Security , , ,","place":["Shanghai, China, 200092"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xueran","family":"Xu","sequence":"additional","affiliation":[{"name":"Tongji University , , ,","place":["Shanghai, China, 200092"]},{"name":"Shanghai Institute of Pollution Control and Ecological Security , , ,","place":["Shanghai, China, 200092"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5712-2824","authenticated-orcid":true,"given":"Suman","family":"Pokhrel","sequence":"additional","affiliation":[{"name":"University of Bremen , , ,","place":["Bremen, Germany, 28359"]},{"name":"Leibniz Institute for Materials Engineering IWT , ,","place":["Bremen, Germany, 28359"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9390-4222","authenticated-orcid":true,"given":"Yiannis","family":"Deligiannakis","sequence":"additional","affiliation":[{"name":"University of Ioannina , , ,","place":["Ioannina, Greece, 45110"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6970-8221","authenticated-orcid":true,"given":"Sijie","family":"Lin","sequence":"additional","affiliation":[{"name":"Tongji University , , ,","place":["Shanghai, China, 200092"]},{"name":"Shanghai Institute of Pollution Control and Ecological Security , , ,","place":["Shanghai, China, 200092"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,27]]},"reference":[{"issue":"1","key":"2026091511114889300_cit1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-025-57650-8","article-title":"Learning lessons from\nnano-medicine to improve the design and performances of nano-agrochemicals","volume":"16","author":"Vu Thanh","year":"2025","journal-title":"Nat. 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Pollut."},{"issue":"4","key":"2026091511114889300_cit5","doi-asserted-by":"publisher","first-page":"303","DOI":"10.1515\/ntrev-2018-0031","article-title":"Copper\nand copper nanoparticles: role in management of insect-pests and pathogenic\nmicrobes","volume":"7","author":"Rai","year":"2018","journal-title":"Nanotechnol. Rev."},{"key":"2026091511114889300_cit6","unstructured":"https:\/\/www.marketgrowthreports.com (accessed on June 30, 2026)."},{"issue":"1","key":"2026091511114889300_cit7","article-title":"Peer review\nof the pesticide risk assessment of the active substance copper compounds\ncopper(I), copper(II) variants namely copper hydroxide, copper oxychloride,\ntribasic copper sulfate, copper(I) oxide, Bordeaux mixture","volume":"16","author":"Arena","year":"2018","journal-title":"EFSA J."},{"key":"2026091511114889300_cit8","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemosphere.2021.130940","article-title":"Copper-based nanoparticles in the soil-plant environment: Assessing\ntheir applications, interactions, fate and toxicity","volume":"281","author":"Bakshi","year":"2021","journal-title":"Chemosphere"},{"issue":"4","key":"2026091511114889300_cit9","doi-asserted-by":"publisher","DOI":"10.1016\/j.emcon.2024.100352","article-title":"Copper nanoparticles\nas a potential emerging pollutant:\nDivergent effects in the agriculture, risk-benefit balance and integrated\nstrategies for its use","volume":"10","author":"Tortella","year":"2024","journal-title":"Emerging Contam."},{"issue":"48","key":"2026091511114889300_cit10","doi-asserted-by":"publisher","first-page":"19407","DOI":"10.1021\/acs.est.3c06284","article-title":"Neurotoxicity of the\nCu(OH)2 Nanopesticide through Perturbing Multiple Neurotransmitter\nPathways in Developing Zebrafish","volume":"57","author":"Chen","year":"2023","journal-title":"Environ. Sci.\nTechnol."},{"issue":"1","key":"2026091511114889300_cit11","doi-asserted-by":"publisher","DOI":"10.1038\/s41598-023-31471-5","article-title":"Spatial and temporal\ndistribution characteristics of antibiotics and heavy metals in the\nYitong River basin and ecological risk assessment","volume":"13","author":"Zhao","year":"2023","journal-title":"Sci. Rep."},{"key":"2026091511114889300_cit12","doi-asserted-by":"publisher","first-page":"374","DOI":"10.1016\/j.watres.2016.06.056","article-title":"Release and detection\nof nanosized copper from a commercial antifouling paint","volume":"102","author":"Adeleye","year":"2016","journal-title":"Water Res."},{"key":"2026091511114889300_cit13","doi-asserted-by":"publisher","DOI":"10.1016\/j.envint.2020.105646","article-title":"Transformation pathways\nand fate\nof engineered nanoparticles (ENPs) in distinct interactive environmental\ncompartments: A review","volume":"138","author":"Abbas","year":"2020","journal-title":"Environ. Int."},{"issue":"1","key":"2026091511114889300_cit14","doi-asserted-by":"publisher","first-page":"97","DOI":"10.1007\/s10311-019-00920-x","article-title":"Fate and risk of metal\nsulfide nanoparticles in the environment","volume":"18","author":"Ubaid","year":"2020","journal-title":"Environ.\nChem. Lett."},{"issue":"4\u20135","key":"2026091511114889300_cit15","doi-asserted-by":"publisher","first-page":"389","DOI":"10.1007\/s11051-005-4272-4","article-title":"Metal sulfide cluster complexes and\ntheir biogeochemical\nimportance in the environment","volume":"7","author":"Luther","year":"2005","journal-title":"J. Nanopart.\nRes."},{"issue":"17","key":"2026091511114889300_cit16","doi-asserted-by":"publisher","first-page":"3021","DOI":"10.1021\/es981206r","article-title":"Measuring metal\nsulfide complexes\nin oxic river waters with square wave voltammetry","volume":"33","author":"Rozan","year":"1999","journal-title":"Environ. Sci. 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Technol."},{"issue":"5\u20136","key":"2026091511114889300_cit22","doi-asserted-by":"publisher","first-page":"577","DOI":"10.1023\/b:nano.0000006100.25744.fa","article-title":"Studies on\nthe evolution of silver nanoparticles in micelle by UV-photoactivation","volume":"5","author":"Ghosh","year":"2003","journal-title":"J. Nanopart. Res."},{"issue":"10","key":"2026091511114889300_cit23","doi-asserted-by":"publisher","first-page":"8715","DOI":"10.1021\/nn403080y","article-title":"Biological\nand Environmental Transformations of Copper-Based Nanomaterials","volume":"7","author":"Wang","year":"2013","journal-title":"ACS Nano"},{"issue":"4","key":"2026091511114889300_cit24","doi-asserted-by":"publisher","first-page":"2486","DOI":"10.1021\/es505878f","article-title":"Sulfidation\nas a natural antidote to metallic nanoparticles is overestimated:\nCuO sulfidation yields CuS nanoparticles with increased toxicity in\nMedaka (Oryzias latipes) embryos","volume":"49","author":"Li","year":"2015","journal-title":"Environ. Sci. Technol."},{"issue":"6","key":"2026091511114889300_cit25","doi-asserted-by":"publisher","first-page":"2527","DOI":"10.1021\/es3035347","article-title":"Sulfidation\nMechanism for Zinc Oxide Nanoparticles and the Effect of Sulfidation\non Their Solubility","volume":"47","author":"Ma","year":"2013","journal-title":"Environ. Sci. Technol."},{"issue":"6","key":"2026091511114889300_cit26","doi-asserted-by":"publisher","DOI":"10.1016\/j.jece.2025.119488","article-title":"Multivalent copper-carbon-catalyzed\npersulfate\/O2 system: The relation between copper valence\nand the species of reactive oxygen","volume":"13","author":"Fan","year":"2025","journal-title":"J. Environ.\nChem. Eng."},{"issue":"13","key":"2026091511114889300_cit27","doi-asserted-by":"publisher","first-page":"6772","DOI":"10.1021\/acs.est.5b04719","article-title":"Dissolution\nand Persistence of Copper-Based Nanomaterials\nin Undersaturated Solutions with Respect to Cupric Solid Phases","volume":"50","author":"Kent","year":"2016","journal-title":"Environ. Sci. Technol."},{"issue":"2","key":"2026091511114889300_cit28","doi-asserted-by":"publisher","first-page":"2038","DOI":"10.1021\/nn507216f","article-title":"Understanding the\nTransformation, Speciation, and Hazard Potential of Copper Particles\nin a Model Septic Tank System Using Zebrafish to Monitor the Effluent","volume":"9","author":"Lin","year":"2015","journal-title":"ACS Nano"},{"issue":"4","key":"2026091511114889300_cit29","doi-asserted-by":"publisher","first-page":"4166","DOI":"10.1021\/acsnano.9b08938","article-title":"Redox Activity and\nNano-Bio Interactions Determine the Skin Injury Potential of Co3O4-Based Metal Oxide Nanoparticles toward Zebrafish","volume":"14","author":"Peng","year":"2020","journal-title":"ACS Nano"},{"issue":"19","key":"2026091511114889300_cit30","doi-asserted-by":"publisher","first-page":"13033","DOI":"10.1021\/acs.est.1c04431","article-title":"Comprehensive\nInterrogation of Metabolic and Bioenergetic Responses of Early-Staged\nZebrafish (Danio rerio) to a Commercial\nCopper Hydroxide Nanopesticide","volume":"55","author":"Wang","year":"2021","journal-title":"Environ. Sci.\nTechnol."},{"key":"2026091511114889300_cit31","doi-asserted-by":"publisher","DOI":"10.1016\/j.jhazmat.2025.140294","article-title":"Commercial\nformulations of copper-based conventional and nano-formulated pesticides\naffect chironomid-associated microbiota and hosts traits","volume":"499","author":"Moura","year":"2025","journal-title":"J. Hazard. Mater."},{"issue":"12","key":"2026091511114889300_cit32","doi-asserted-by":"publisher","first-page":"8438","DOI":"10.1021\/acs.est.1c08875","article-title":"Perfluorooctane\nSulfonamide (PFOSA) Induces Cardiotoxicity via Aryl Hydrocarbon Receptor\nActivation in Zebrafish","volume":"56","author":"Chen","year":"2022","journal-title":"Environ. Sci. Technol."},{"issue":"20","key":"2026091511114889300_cit33","doi-asserted-by":"publisher","first-page":"23652","DOI":"10.1021\/acsanm.4c03938","article-title":"Cu2S Nanosheets for the\nCatalytic Decomposition of Ozone","volume":"7","author":"Ma","year":"2024","journal-title":"ACS Appl.\nNano Mater."},{"issue":"11","key":"2026091511114889300_cit34","doi-asserted-by":"publisher","first-page":"4783","DOI":"10.1021\/acs.chemmater.7b00579","article-title":"Reversible Crystal Phase Interconversion between Covellite\nCuS and High Chalcocite Cu2S Nanocrystals","volume":"29","author":"Liu","year":"2017","journal-title":"Chem. Mater."},{"key":"2026091511114889300_cit35","doi-asserted-by":"publisher","DOI":"10.1016\/j.watres.2022.119030","article-title":"Effects of zinc oxide\nnanoparticles transformation in sulfur-containing water on its toxicity\nto microalgae: Physicochemical analysis, photosynthetic efficiency\nand potential mechanisms","volume":"223","author":"Zhang","year":"2022","journal-title":"Water Res."},{"issue":"12","key":"2026091511114889300_cit36","doi-asserted-by":"publisher","first-page":"6168","DOI":"10.1039\/D3TA00213F","article-title":"Uncovering\nthe untapped potential of copper(I) sulphide toward lithium-ion storage\nunder ultra-low temperatures","volume":"11","author":"Chen","year":"2023","journal-title":"J. Mater. Chem.\nA"},{"key":"2026091511114889300_cit37","doi-asserted-by":"publisher","DOI":"10.1016\/j.colsurfa.2020.124984","article-title":"Effect of\ntemperature and reaction time on the morphology of L-cysteine surface\ncapped chalcocite (Cu2S) snowflakes dendrites nanoleaves\nand photodegradation study of methyl orange dye under visible light","volume":"601","author":"Iqbal","year":"2020","journal-title":"Colloids Surf., A"},{"issue":"8","key":"2026091511114889300_cit38","doi-asserted-by":"publisher","DOI":"10.1016\/j.cclet.2025.111181","article-title":"MgWO4 microflowers\nassembled by ultrathin nanosheets with highly-exposed (001) facet:\nDensity functional theory and novel energy storage in Mg-ion batteries","volume":"37","author":"Zhang","year":"2026","journal-title":"Chin. Chem. Lett."},{"issue":"5","key":"2026091511114889300_cit39","doi-asserted-by":"publisher","first-page":"1737","DOI":"10.1007\/s10311-020-01035-4","article-title":"Cu(OH)2 nanorods undergo\nsulfidation in water: In situ\nformation of CuO nanorods as intermediates and enhanced toxicity to Escherichia coli","volume":"18","author":"Su","year":"2020","journal-title":"Environ.\nChem. Lett."},{"key":"2026091511114889300_cit40","doi-asserted-by":"publisher","first-page":"576","DOI":"10.1016\/j.jallcom.2018.02.283","article-title":"Mechanochemistry\nof copper sulfides: Characterization, surface oxidation and photocatalytic\nactivity","volume":"746","author":"Bala\u0301z\u030c","year":"2018","journal-title":"J. Alloys Compd."},{"issue":"2","key":"2026091511114889300_cit41","doi-asserted-by":"publisher","first-page":"1949","DOI":"10.1016\/j.ceramint.2024.11.169","article-title":"Aerosol-assisted chemical\nvapor deposited Cu2S structured films with photo activated\nNO2 sensing properties","volume":"51","author":"Trabelsi","year":"2025","journal-title":"Ceram. Int."},{"issue":"3","key":"2026091511114889300_cit42","doi-asserted-by":"publisher","DOI":"10.1002\/bte2.20230060","article-title":"Preparation of Cu(OH)2\/Cu2S arrays\nfor enhanced hydrogen evolution reaction","volume":"3","author":"Xu","year":"2024","journal-title":"Battery\nEnergy"},{"issue":"2","key":"2026091511114889300_cit43","doi-asserted-by":"publisher","DOI":"10.3390\/catal12020147","article-title":"In Situ Partial Sulfidation\nfor Preparing Cu\/Cu2-xS Core\/Shell Nanorods with\nEnhanced Photocatalytic Degradation","volume":"12","author":"Cheng","year":"2022","journal-title":"Catalysts"},{"issue":"9","key":"2026091511114889300_cit44","doi-asserted-by":"publisher","first-page":"5076","DOI":"10.1021\/es405612f","article-title":"Occurrence of Surface\nPolysulfides during the Interaction\nbetween Ferric (Hydr)Oxides and Aqueous Sulfide","volume":"48","author":"Wan","year":"2014","journal-title":"Environ. Sci. Technol."},{"issue":"13","key":"2026091511114889300_cit45","doi-asserted-by":"publisher","first-page":"2448","DOI":"10.1039\/c3tc00639e","article-title":"Quantitative X-ray absorption and\nemission spectroscopies: electronic structure elucidation of Cu2S and CuS","volume":"1","author":"Kumar","year":"2013","journal-title":"J. Mater. Chem. C"},{"issue":"2","key":"2026091511114889300_cit46","doi-asserted-by":"publisher","first-page":"642","DOI":"10.1021\/jacsau.3c00703","article-title":"Surface Structure\nto Tailor the Electrochemical Behavior\nof Mixed-Valence Copper Sulfides during Water Electrolysis","volume":"4","author":"Kundu","year":"2024","journal-title":"JACS Au"},{"issue":"19","key":"2026091511114889300_cit47","doi-asserted-by":"publisher","first-page":"13664","DOI":"10.1021\/acs.est.2c04859","article-title":"Controllable\nDisordered Copper Sulfide with a Sulfur-Rich Interface for High-Performance\nGaseous Elemental Mercury Capture","volume":"56","author":"Liu","year":"2022","journal-title":"Environ.\nSci. Technol."},{"issue":"4\u20136","key":"2026091511114889300_cit48","doi-asserted-by":"publisher","first-page":"327","DOI":"10.1089\/ars.2021.0170","article-title":"Chemical Biology of Reactive Sulfur Species: Hydrolysis-Driven\nEquilibrium of Polysulfides as a Determinant of Physiological Functions","volume":"36","author":"Sawa","year":"2022","journal-title":"Antioxid. Redox Signal."},{"issue":"5","key":"2026091511114889300_cit49","doi-asserted-by":"publisher","first-page":"1200","DOI":"10.1039\/C8EN00190A","article-title":"Differential\neffects of metal oxide nanoparticles on zebrafish embryos and developing\nlarvae","volume":"5","author":"Peng","year":"2018","journal-title":"Environ. Sci. Nano"},{"issue":"4","key":"2026091511114889300_cit50","doi-asserted-by":"publisher","first-page":"347","DOI":"10.1039\/C4EN00018H","article-title":"Sulfidation of copper\noxide nanoparticles and properties of resulting copper sulfide","volume":"1","author":"Ma","year":"2014","journal-title":"Environ. Sci. Nano"},{"issue":"37","key":"2026091511114889300_cit51","doi-asserted-by":"publisher","first-page":"19350","DOI":"10.1039\/D0NR05934J","article-title":"CuS nanoparticles\nin humid environments: adsorbed water enhances the transformation\nof CuS to CuSO4","volume":"12","author":"Wu","year":"2020","journal-title":"Nanoscale"},{"issue":"38","key":"2026091511114889300_cit52","doi-asserted-by":"publisher","first-page":"30248","DOI":"10.1039\/C4RA17322H","article-title":"Sulfidation modulates the toxicity of biogenic copper\nnanoparticles","volume":"5","author":"Dharsana","year":"2015","journal-title":"RSC Adv."},{"issue":"6","key":"2026091511114889300_cit53","doi-asserted-by":"publisher","first-page":"1690","DOI":"10.1039\/D1EN00305D","article-title":"Mechanisms\nand effects of zinc oxide nanoparticle transformations\non toxicity to zebrafish embryos","volume":"8","author":"Lee","year":"2021","journal-title":"Environ. 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