{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T15:39:23Z","timestamp":1785425963647,"version":"3.56.0"},"reference-count":35,"publisher":"National Academy of Sciences","issue":"27","license":[{"start":{"date-parts":[[2026,7,1]],"date-time":"2026-07-01T00:00:00Z","timestamp":1782864000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"name":"Key Program of National Natural Science of China","award":["22438001"],"award-info":[{"award-number":["22438001"]}]},{"name":"Science and Technology Project of Southwest United Graduate School of Yunnan","award":["202302AP370002"],"award-info":[{"award-number":["202302AP370002"]}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"crossref","award":["42303003"],"award-info":[{"award-number":["42303003"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":["www.pnas.org"],"crossmark-restriction":true},"short-container-title":["Proc. Natl. Acad. Sci. U.S.A."],"published-print":{"date-parts":[[2026,7,7]]},"abstract":"<jats:p>\n                    Isotopic fractionation is a unique indicator of the mechanisms of mineral precipitation from aqueous solutions, but existing theory does not account for nucleation effects or nonclassical growth mechanisms. Here, using barite (BaSO\n                    <jats:sub>4<\/jats:sub>\n                    ) as a model crystal, we provide an experimental measurement of isotope fractionation associated with nucleation. We isolated nucleation effects by precipitating crystals on an organic film, where cation enrichment creates a highly supersaturated microenvironment so nucleation dominates over crystal growth. In a single batch experiment, we retrieved nanocrystals (~1.5 nm) from the organic substrate and large microcrystals in bulk solution where growth dominates. The\n                    <jats:sup>138<\/jats:sup>\n                    Ba\/\n                    <jats:sup>134<\/jats:sup>\n                    Ba isotopic fractionation of \u22120.6 to \u22120.8\u2030 for the microcrystals match those expected for classical ion-by-ion growth from a moderately supersaturated solution, whereas the fractionation for the nucleation-dominated nanocrystals is about \u22120.1\u2030, falling within the reported equilibrium fractionation range between barite and aqueous Ba\n                    <jats:sup>2+<\/jats:sup>\n                    . These results demonstrate that cation isotopic fractionation in sparingly soluble salts like barite and calcite is not a single-valued function of saturation indices (SI) and precipitation rate as predicted with current theory, with the fractionation factor (\u2206\n                    <jats:sup>138\/134<\/jats:sup>\n                    Ba\n                    <jats:sub>barite-soln<\/jats:sub>\n                    = \u03b4\n                    <jats:sup>138\/134<\/jats:sup>\n                    Ba\n                    <jats:sub>barite<\/jats:sub>\n                    \u2212 \u03b4\n                    <jats:sup>138\/134<\/jats:sup>\n                    Ba\n                    <jats:sub>solution<\/jats:sub>\n                    ) increasing in magnitude with increasing SI. Instead, the shifting precipitation mechanism(s) at high SI cause the fractionation factor to return to near-equilibrium values. This finding may be critical for understanding isotopic fractionation in localized extreme environments in nature, including for Ba isotopes during biomineralization.\n                  <\/jats:p>","DOI":"10.1073\/pnas.2609659123","type":"journal-article","created":{"date-parts":[[2026,7,1]],"date-time":"2026-07-01T17:41:20Z","timestamp":1782927680000},"update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":0,"title":["Measurement of isotope fractionation associated with crystal nucleation: Implications for biocrystallization studies"],"prefix":"10.1073","volume":"123","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2980-5331","authenticated-orcid":false,"given":"Chuan","family":"Liu","sequence":"first","affiliation":[{"id":[{"id":"https:\/\/ror.org\/02v51f717","id-type":"ROR","asserted-by":"publisher"}],"name":"Key Laboratory of Water and Sediment Sciences, Ministry of Education; College of Environmental Sciences and Engineering, Peking University","place":["Beijing, People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas L.","family":"Go\u00fbt","sequence":"additional","affiliation":[{"id":[{"id":"https:\/\/ror.org\/02v51f717","id-type":"ROR","asserted-by":"publisher"}],"name":"Key Laboratory of Water and Sediment Sciences, Ministry of Education; College of Environmental Sciences and Engineering, Peking University","place":["Beijing, People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8506-9335","authenticated-orcid":false,"given":"Yandi","family":"Hu","sequence":"additional","affiliation":[{"id":[{"id":"https:\/\/ror.org\/02v51f717","id-type":"ROR","asserted-by":"publisher"}],"name":"Key Laboratory of Water and Sediment Sciences, Ministry of Education; College of Environmental Sciences and Engineering, Peking University","place":["Beijing, People\u2019s Republic of 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