{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/124682"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/124682","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Isotopic fractionations associated with hexavalent chromium cycling in the natural subsurface","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01","abstract_has_math":false,"creators":["Gholizadeh Ansari, Mahta"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Geology","degree_department":null,"school":null,"contributors":["Johnson, Thomas Martin","Lundstrom, Craig","Sanford, Robert","McClain, Cynthia"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2024,"date_issued":"2024-04-26","date_published":"2024-04-26","updated_at":"2026-07-22T22:25:02Z","subjects":["Chromium","Isotopes","Redox"],"languages":["en","eng"],"rights":["Copyright 2024 Mahta Gholizadeh Ansari"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/124682","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Johnson, Thomas Martin","Lundstrom, Craig","Sanford, Robert","McClain, Cynthia"]},{"key":"dc:creator","label":"Author","values":["Gholizadeh Ansari, Mahta"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2024-04-26","2024-05"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Geology"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chromium","Isotopes","Redox"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2024 Mahta Gholizadeh Ansari"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/124682"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01","The student, Mahta Gholizadeh Ansari, accepted the attached license on 2024-04-22 at 12:16.","The student, Mahta Gholizadeh Ansari, submitted this Dissertation for approval on 2024-04-22 at 12:25.","This Dissertation was approved for publication on 2024-04-26 at 10:26.","DSpace SAF Submission Ingestion Package generated from Vireo submission #20538 on 2024-09-16 at 00:49:54","Hexavalent chromium, Cr(VI), is a common groundwater contaminant worldwide that can have adverse health effects and impact our groundwater quality. In conjunction with changes in concentration, the variation in isotopic ratios of dissolved Cr(VI) is used to more accurately quantify reactions in the subsurface and underlying hydrogeochemical processes. However, the complexities associated with Cr mobilization through weathering processes and their unknown isotopic signatures significantly challenge the interpretation of field data and limit the use of Cr stable isotope methods. The work presented here seeks to improve our understanding of Cr cycling in the subsurface and identify the processes that can impact the Cr(VI) isotopic ratios. To quantify the isotopic signatures associated with Cr cycling in the natural subsurface, I conducted reduction, adsorption and oxidation experiments and measured the isotopic fractionation associated with each one. While reduction of Cr(VI) and its isotopic fractionation is well studied, reduction with sulfur-bearing species had not been explored. I conducted reduction experiments with hydrogen sulfide at circumneutral pH. The result indicated that the isotopic fractionation induced by this reaction is pH dependent and will lead to isotopically heavy Cr(VI) remaining in the solution with ε reaching up to - 3.0 ±0.1‰ (ε ≈ δproduct flux - δreactant). A major pathway for mobilization of Cr and generation of naturally occurring Cr(VI) contamination is oxidation of Cr(III) bearing solids by manganese oxides. However, the Cr isotopic shifts induced by this reaction are poorly understood. Oxidation experiments conducted with three different Cr(III)-bearing solids (Cr(OH)3, CrFe(OH)3 and chromite) revealed a lack of persistent isotopic offset between the oxidized Cr(VI) and the Cr-bearing solids. Although I have observed ephemeral, significant isotopic fractionation, this fractionation is not sustained through time and its magnitude is too small to explain the range of δ53Cr values reported for geogenic Cr(VI). Another reaction involved in Cr cycle in the subsurface is adsorption of Cr(VI) on manganese oxides. Cr isotopic fractionation during Cr(VI) adsorption has been assumed to be negligible and, therefore, has not been considered during the interpretation of isotopic data in environmental studies. I conducted Cr(VI) adsorption experiments with pyrolusite at varying pH conditions. The results indicate that adsorption of Cr(VI) on manganese oxide surfaces can lead to isotopically heavy Cr(VI) in the aqueous phase. These experiments suggest that both outer-sphere and inner-sphere mechanisms are involved during adsorption of Cr(VI) on pyrolusite. However, isotopic fractionation is related only to the inner-sphere complexes, which form much more slowly. My findings challenge the existing belief that reduction is the only possible pathway for decreasing the concentration of Cr(VI) that is accompanied by large isotopic fractionations. In summary, the results of these studies advance our understanding of fundamental processes that impact Cr isotope ratios. Filling these knowledge gaps improves our ability to detect Cr(VI) reduction and to fingerprint naturally produced Cr(VI) using Cr isotopes."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Isotopic fractionations associated with hexavalent chromium cycling in the natural subsurface"]}]}],"canonical_facts":{"dc:contributor":["Johnson, Thomas Martin","Lundstrom, Craig","Sanford, Robert","McClain, Cynthia"],"dc:creator":["Gholizadeh Ansari, Mahta"],"dc:date":["2024-04-26","2024-05"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01","The student, Mahta Gholizadeh Ansari, accepted the attached license on 2024-04-22 at 12:16.","The student, Mahta Gholizadeh Ansari, submitted this Dissertation for approval on 2024-04-22 at 12:25.","This Dissertation was approved for publication on 2024-04-26 at 10:26.","DSpace SAF Submission Ingestion Package generated from Vireo submission #20538 on 2024-09-16 at 00:49:54","Hexavalent chromium, Cr(VI), is a common groundwater contaminant worldwide that can have adverse health effects and impact our groundwater quality. In conjunction with changes in concentration, the variation in isotopic ratios of dissolved Cr(VI) is used to more accurately quantify reactions in the subsurface and underlying hydrogeochemical processes. However, the complexities associated with Cr mobilization through weathering processes and their unknown isotopic signatures significantly challenge the interpretation of field data and limit the use of Cr stable isotope methods. The work presented here seeks to improve our understanding of Cr cycling in the subsurface and identify the processes that can impact the Cr(VI) isotopic ratios. To quantify the isotopic signatures associated with Cr cycling in the natural subsurface, I conducted reduction, adsorption and oxidation experiments and measured the isotopic fractionation associated with each one. While reduction of Cr(VI) and its isotopic fractionation is well studied, reduction with sulfur-bearing species had not been explored. I conducted reduction experiments with hydrogen sulfide at circumneutral pH. The result indicated that the isotopic fractionation induced by this reaction is pH dependent and will lead to isotopically heavy Cr(VI) remaining in the solution with ε reaching up to - 3.0 ±0.1‰ (ε ≈ δproduct flux - δreactant). A major pathway for mobilization of Cr and generation of naturally occurring Cr(VI) contamination is oxidation of Cr(III) bearing solids by manganese oxides. However, the Cr isotopic shifts induced by this reaction are poorly understood. Oxidation experiments conducted with three different Cr(III)-bearing solids (Cr(OH)3, CrFe(OH)3 and chromite) revealed a lack of persistent isotopic offset between the oxidized Cr(VI) and the Cr-bearing solids. Although I have observed ephemeral, significant isotopic fractionation, this fractionation is not sustained through time and its magnitude is too small to explain the range of δ53Cr values reported for geogenic Cr(VI). Another reaction involved in Cr cycle in the subsurface is adsorption of Cr(VI) on manganese oxides. Cr isotopic fractionation during Cr(VI) adsorption has been assumed to be negligible and, therefore, has not been considered during the interpretation of isotopic data in environmental studies. I conducted Cr(VI) adsorption experiments with pyrolusite at varying pH conditions. The results indicate that adsorption of Cr(VI) on manganese oxide surfaces can lead to isotopically heavy Cr(VI) in the aqueous phase. These experiments suggest that both outer-sphere and inner-sphere mechanisms are involved during adsorption of Cr(VI) on pyrolusite. However, isotopic fractionation is related only to the inner-sphere complexes, which form much more slowly. My findings challenge the existing belief that reduction is the only possible pathway for decreasing the concentration of Cr(VI) that is accompanied by large isotopic fractionations. In summary, the results of these studies advance our understanding of fundamental processes that impact Cr isotope ratios. Filling these knowledge gaps improves our ability to detect Cr(VI) reduction and to fingerprint naturally produced Cr(VI) using Cr isotopes."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/124682"],"dc:language":["en","eng"],"dc:rights":["Copyright 2024 Mahta Gholizadeh Ansari"],"dc:subject":["Chromium","Isotopes","Redox"],"dc:title":["Isotopic fractionations associated with hexavalent chromium cycling in the natural subsurface"],"dc:type":["text"],"thesis:degree_discipline":["Geology"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:02Z"}