A lab-on-a-chip approach integrating in-situ characterization and reactive transport modelling diagnostics to unravel (Ba,Sr)SO4 oscillatory zoning
Abstract The co-precipitation of sulphate minerals such as celestine and barite is widely studied because their formation is ubiquitous in natural and anthropogenic systems. Co-precipitation in porous media results in crystallization of solid solutions yielding characteristics such as oscillatory zo...
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| Format: | Article |
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Nature Portfolio
2021-12-01
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| Series: | Scientific Reports |
| Online Access: | https://doi.org/10.1038/s41598-021-02840-9 |
| _version_ | 1818723298498838528 |
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| author | Jenna Poonoosamy Mohamed Mahrous Enzo Curti Dirk Bosbach Guido Deissmann Sergey V. Churakov Thorsten Geisler Nikolaos Prasianakis |
| author_facet | Jenna Poonoosamy Mohamed Mahrous Enzo Curti Dirk Bosbach Guido Deissmann Sergey V. Churakov Thorsten Geisler Nikolaos Prasianakis |
| author_sort | Jenna Poonoosamy |
| collection | DOAJ |
| description | Abstract The co-precipitation of sulphate minerals such as celestine and barite is widely studied because their formation is ubiquitous in natural and anthropogenic systems. Co-precipitation in porous media results in crystallization of solid solutions yielding characteristics such as oscillatory zoning that are rarely observed in bulk solution or in batch experiments. In the past, the precipitation of compositionally-zoned (Ba,Sr)SO4 crystals was observed post-mortem in macroscopic silica gel counter-diffusion experiments. Their formation was originally explained by the difference in the solubility products of the end-members combined with diffusion-limited transport of solutes to the mineral-fluid interface, while a later study favored the idea of kinetically controlled reactions. With recent advances combining in-operando microfluidic experiments and reactive transport modelling, it is now possible to verify hypotheses on the driving forces of transport-coupled geochemical processes. We developed a “lab on a chip” experiment that enabled the systematic study of the nucleation and growth of oscillatory-zoned (Ba,Sr)SO4 crystals in a microfluidic reactor. The compositions of the solid solutions were determined by in-situ Raman spectroscopy. Our investigation shows (1) that the composition of the nucleating phases can be approximated using classical nucleation theory, (2) that the oscillatory zoning is not solely controlled by the limited diffusional transport of solutes, and (3) that nucleation kinetics plays a major role in the switch between different stoichiometric compositions. The zoning phenomena is governed by the complex interplay between the diffusion of reactants and the crystallization kinetics as well as other factors, e.g. surface tension and lattice mismatch. |
| first_indexed | 2024-12-17T21:08:18Z |
| format | Article |
| id | doaj.art-5a506f15d9b846fa997f7d79236e9952 |
| institution | Directory Open Access Journal |
| issn | 2045-2322 |
| language | English |
| last_indexed | 2024-12-17T21:08:18Z |
| publishDate | 2021-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj.art-5a506f15d9b846fa997f7d79236e99522022-12-21T21:32:31ZengNature PortfolioScientific Reports2045-23222021-12-0111111510.1038/s41598-021-02840-9A lab-on-a-chip approach integrating in-situ characterization and reactive transport modelling diagnostics to unravel (Ba,Sr)SO4 oscillatory zoningJenna Poonoosamy0Mohamed Mahrous1Enzo Curti2Dirk Bosbach3Guido Deissmann4Sergey V. Churakov5Thorsten Geisler6Nikolaos Prasianakis7Institute of Energy and Climate Research (IEK-6): Nuclear Waste Management and Reactor Safety, Forschungszentrum Jülich GmbHLaboratory for Waste Management, Paul Scherrer InstitutLaboratory for Waste Management, Paul Scherrer InstitutInstitute of Energy and Climate Research (IEK-6): Nuclear Waste Management and Reactor Safety, Forschungszentrum Jülich GmbHInstitute of Energy and Climate Research (IEK-6): Nuclear Waste Management and Reactor Safety, Forschungszentrum Jülich GmbHLaboratory for Waste Management, Paul Scherrer InstitutInstitut Für Geowissenschaften, Rheinische Friedrich-Wilhelms-Universität BonnLaboratory for Waste Management, Paul Scherrer InstitutAbstract The co-precipitation of sulphate minerals such as celestine and barite is widely studied because their formation is ubiquitous in natural and anthropogenic systems. Co-precipitation in porous media results in crystallization of solid solutions yielding characteristics such as oscillatory zoning that are rarely observed in bulk solution or in batch experiments. In the past, the precipitation of compositionally-zoned (Ba,Sr)SO4 crystals was observed post-mortem in macroscopic silica gel counter-diffusion experiments. Their formation was originally explained by the difference in the solubility products of the end-members combined with diffusion-limited transport of solutes to the mineral-fluid interface, while a later study favored the idea of kinetically controlled reactions. With recent advances combining in-operando microfluidic experiments and reactive transport modelling, it is now possible to verify hypotheses on the driving forces of transport-coupled geochemical processes. We developed a “lab on a chip” experiment that enabled the systematic study of the nucleation and growth of oscillatory-zoned (Ba,Sr)SO4 crystals in a microfluidic reactor. The compositions of the solid solutions were determined by in-situ Raman spectroscopy. Our investigation shows (1) that the composition of the nucleating phases can be approximated using classical nucleation theory, (2) that the oscillatory zoning is not solely controlled by the limited diffusional transport of solutes, and (3) that nucleation kinetics plays a major role in the switch between different stoichiometric compositions. The zoning phenomena is governed by the complex interplay between the diffusion of reactants and the crystallization kinetics as well as other factors, e.g. surface tension and lattice mismatch.https://doi.org/10.1038/s41598-021-02840-9 |
| spellingShingle | Jenna Poonoosamy Mohamed Mahrous Enzo Curti Dirk Bosbach Guido Deissmann Sergey V. Churakov Thorsten Geisler Nikolaos Prasianakis A lab-on-a-chip approach integrating in-situ characterization and reactive transport modelling diagnostics to unravel (Ba,Sr)SO4 oscillatory zoning Scientific Reports |
| title | A lab-on-a-chip approach integrating in-situ characterization and reactive transport modelling diagnostics to unravel (Ba,Sr)SO4 oscillatory zoning |
| title_full | A lab-on-a-chip approach integrating in-situ characterization and reactive transport modelling diagnostics to unravel (Ba,Sr)SO4 oscillatory zoning |
| title_fullStr | A lab-on-a-chip approach integrating in-situ characterization and reactive transport modelling diagnostics to unravel (Ba,Sr)SO4 oscillatory zoning |
| title_full_unstemmed | A lab-on-a-chip approach integrating in-situ characterization and reactive transport modelling diagnostics to unravel (Ba,Sr)SO4 oscillatory zoning |
| title_short | A lab-on-a-chip approach integrating in-situ characterization and reactive transport modelling diagnostics to unravel (Ba,Sr)SO4 oscillatory zoning |
| title_sort | lab on a chip approach integrating in situ characterization and reactive transport modelling diagnostics to unravel ba sr so4 oscillatory zoning |
| url | https://doi.org/10.1038/s41598-021-02840-9 |
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