ACS Earth and Space ChemistryPub Date : 2024-08-30DOI: 10.1021/acsearthspacechem.4c0004610.1021/acsearthspacechem.4c00046
Gregory W. Vandergrift, Sheryl L. Bell, Shannon E. Schrader, Sonja M. Jensen, Jon H. Wahl, Jerry D. Tagestad, Swarup China* and Kirsten S. Hofmockel*,
{"title":"Harvest Initiated Volatile Organic Compound Emissions from In-Field Tall Wheatgrass","authors":"Gregory W. Vandergrift, Sheryl L. Bell, Shannon E. Schrader, Sonja M. Jensen, Jon H. Wahl, Jerry D. Tagestad, Swarup China* and Kirsten S. Hofmockel*, ","doi":"10.1021/acsearthspacechem.4c0004610.1021/acsearthspacechem.4c00046","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00046https://doi.org/10.1021/acsearthspacechem.4c00046","url":null,"abstract":"<p >While crop and grassland usage continues to increase, the full diversity of plant-specific volatile organic compounds (VOCs) emitted from these ecosystems, including their implications for atmospheric chemistry and carbon cycling, remains poorly understood. It is particularly important to investigate VOCs in the context of potential biofuels: aside from the implications of large-scale land use, harvest may shift both the flux and speciation of emitted VOCs. To this point, we evaluate the diversity of VOCs emitted both pre and postharvest from “Alkar” tall wheatgrass (<i>Thinopyrum ponticum</i>), a candidate biofuel that exhibits greater tolerance to frost and saline land compared to other grass varieties. Mature plants grown under field conditions (<i>n</i> = 6) were sampled for VOCs both pre- and postharvest (October 2022). Via hierarchical clustering of emitted VOCs from each plant, we observe distinct “volatilomes” (diversity of VOCs) specific to the pre- and postharvest conditions despite plant-to-plant variability. In total, 50 VOCs were found to be unique to the postharvest tall wheatgrass volatilome, and these unique VOCs constituted a significant portion (26%) of total postharvest signal. While green leaf volatiles (GLVs) dominate the speciation of postharvest emissions (e.g., 54% of unique postharvest VOC signal was due to 1-penten-3-ol), we demonstrate novel postharvest VOCs from tall wheatgrass that are under characterized in the context of carbon cycling and atmospheric chemistry (e.g., 3-octanone). Continuing evaluations will quantitatively investigate tall wheatgrass VOC fluxes, better informing the feasibility and environmental impact of tall wheatgrass as a biofuel.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Earth and Space ChemistryPub Date : 2024-08-29DOI: 10.1021/acsearthspacechem.4c0011110.1021/acsearthspacechem.4c00111
Malak Rizk-Bigourd*, Cyril Szopa, David Coscia, Jean-Pierre Pineau, Vincent Guerrini, Frederic Ferreira, Fabrice Bertrand, Arnaud Philippart, Audrey Boco, Guillaume Rioland, Valérie Peulon-Agasse, Arnaud Buch and Pascal Cardinael,
{"title":"Development and Integration of an Ultraminiaturized Gas Chromatograph Prototype Based on Lab-on-a-Chip Microelectromechanical Systems for Space Exploration Missions","authors":"Malak Rizk-Bigourd*, Cyril Szopa, David Coscia, Jean-Pierre Pineau, Vincent Guerrini, Frederic Ferreira, Fabrice Bertrand, Arnaud Philippart, Audrey Boco, Guillaume Rioland, Valérie Peulon-Agasse, Arnaud Buch and Pascal Cardinael, ","doi":"10.1021/acsearthspacechem.4c0011110.1021/acsearthspacechem.4c00111","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00111https://doi.org/10.1021/acsearthspacechem.4c00111","url":null,"abstract":"<p >We developed, integrated, and tested an ultraminiaturized gas chromatograph prototype for space applications based on microelectromechanical system (MEMS) preconcentrator, column, and detector subunits. The fluidic interface, the mechanical design, and the electronic system were all designed to be easily transposable to space instrumentation. The response linearity, reproducibility as well as the preconcentrator, column, and detector performances were demonstrated using a mixture of <i>n</i>-pentane, <i>n</i>-hexane, benzene, and toluene. Using the column, the response linearity of the nano-gravimetric detector (NGD) was observed over 1 to 2 orders of magnitude with a high <i>R</i><sup>2</sup> value of 0.99. The retention time reproducibility was evaluated with a variation lower than 0.2%. The column separation performances were also qualified in terms of number of theoretical plates (<i>N</i>) and height equivalent to a theoretical plate (HETP) with 8275 ± 45 plates (equivalent to 1655 ± 9 plates per meter) and 0.6 mm on average, respectively. The preconcentrator performance for trapping and desorption was also validated. The NGD showed high sensitivity, and the limit of detection was evaluated to be about 3.1 pmol for toluene, which is very suitable for space exploration. The analytical performance of the first μGC-MEMS prototype was already satisfying and adapted for space studies. Nevertheless, some ways of optimization were identified (like back-flush injection for the preconcentrator or the use of valves more suited to space applications) to improve both performances and instrument robustness, and they will be tested in the future with a second version of our prototype.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270210","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Development and Integration of an Ultraminiaturized Gas Chromatograph Prototype Based on Lab-on-a-Chip Microelectromechanical Systems for Space Exploration Missions","authors":"Malak Rizk-Bigourd, Cyril Szopa, David Coscia, Jean-Pierre Pineau, Vincent Guerrini, Frederic Ferreira, Fabrice Bertrand, Arnaud Philippart, Audrey Boco, Guillaume Rioland, Valérie Peulon-Agasse, Arnaud Buch, Pascal Cardinael","doi":"10.1021/acsearthspacechem.4c00111","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00111","url":null,"abstract":"We developed, integrated, and tested an ultraminiaturized gas chromatograph prototype for space applications based on microelectromechanical system (MEMS) preconcentrator, column, and detector subunits. The fluidic interface, the mechanical design, and the electronic system were all designed to be easily transposable to space instrumentation. The response linearity, reproducibility as well as the preconcentrator, column, and detector performances were demonstrated using a mixture of <i>n</i>-pentane, <i>n</i>-hexane, benzene, and toluene. Using the column, the response linearity of the nano-gravimetric detector (NGD) was observed over 1 to 2 orders of magnitude with a high <i>R</i><sup>2</sup> value of 0.99. The retention time reproducibility was evaluated with a variation lower than 0.2%. The column separation performances were also qualified in terms of number of theoretical plates (<i>N</i>) and height equivalent to a theoretical plate (HETP) with 8275 ± 45 plates (equivalent to 1655 ± 9 plates per meter) and 0.6 mm on average, respectively. The preconcentrator performance for trapping and desorption was also validated. The NGD showed high sensitivity, and the limit of detection was evaluated to be about 3.1 pmol for toluene, which is very suitable for space exploration. The analytical performance of the first μGC-MEMS prototype was already satisfying and adapted for space studies. Nevertheless, some ways of optimization were identified (like back-flush injection for the preconcentrator or the use of valves more suited to space applications) to improve both performances and instrument robustness, and they will be tested in the future with a second version of our prototype.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142179688","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Stephanie R. Schneider, Douglas B. Collins, Matthew Boyer, Rachel Y.-W. Chang, Michel Gosselin, Victoria E. Irish, Lisa A. Miller, Jonathan P. D. Abbatt
{"title":"Abiotic Emission of Volatile Organic Compounds from the Ocean Surface: Relationship to Seawater Composition","authors":"Stephanie R. Schneider, Douglas B. Collins, Matthew Boyer, Rachel Y.-W. Chang, Michel Gosselin, Victoria E. Irish, Lisa A. Miller, Jonathan P. D. Abbatt","doi":"10.1021/acsearthspacechem.4c00163","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00163","url":null,"abstract":"An important goal in marine atmospheric chemistry is to determine the impact of the surface ocean on the overlying marine boundary layer in terms of the ocean’s potential to release volatile organic compounds (VOCs) that may impact atmospheric oxidizing capacity and aerosol growth. In addition to direct biogenic production of VOCs that are eventually emitted to the atmosphere, abiotic mechanisms that produce VOCs include direct or sensitized photochemistry and oxidation reactions initiated by gas phase oxidants. In this laboratory study, we use proton-transfer-reaction mass spectrometry to measure the emission fluxes resulting from both UV irradiation and ozone oxidation of Arctic surface microlayer water and the underlying bulk seawater. Under our experimental conditions, both mechanisms lead to comparable VOC emission fluxes, which scale closely with the total and dissolved organic carbon content of the sample. However, the composition of the seawater sample can strongly affect the emission fluxes of specific molecules. For example, nonanal fluxes from oxidation correlate closely with the phytoplankton abundance in the samples, indicating that unsaturated lipids may be the substrate. Conversely, the best predictor for the nitrogenated VOC flux under irradiation conditions is photosynthetic prokaryotes (i.e., cyanobacteria) abundance. Similar studies in a wider range of environments, ideally conducted in the field, will better constrain the importance of these abiotic processes to global ocean-to-atmosphere fluxes.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142223771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Earth and Space ChemistryPub Date : 2024-08-26DOI: 10.1021/acsearthspacechem.4c0016310.1021/acsearthspacechem.4c00163
Stephanie R. Schneider*, Douglas B. Collins, Matthew Boyer, Rachel Y.-W. Chang, Michel Gosselin, Victoria E. Irish, Lisa A. Miller and Jonathan P. D. Abbatt,
{"title":"Abiotic Emission of Volatile Organic Compounds from the Ocean Surface: Relationship to Seawater Composition","authors":"Stephanie R. Schneider*, Douglas B. Collins, Matthew Boyer, Rachel Y.-W. Chang, Michel Gosselin, Victoria E. Irish, Lisa A. Miller and Jonathan P. D. Abbatt, ","doi":"10.1021/acsearthspacechem.4c0016310.1021/acsearthspacechem.4c00163","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00163https://doi.org/10.1021/acsearthspacechem.4c00163","url":null,"abstract":"<p >An important goal in marine atmospheric chemistry is to determine the impact of the surface ocean on the overlying marine boundary layer in terms of the ocean’s potential to release volatile organic compounds (VOCs) that may impact atmospheric oxidizing capacity and aerosol growth. In addition to direct biogenic production of VOCs that are eventually emitted to the atmosphere, abiotic mechanisms that produce VOCs include direct or sensitized photochemistry and oxidation reactions initiated by gas phase oxidants. In this laboratory study, we use proton-transfer-reaction mass spectrometry to measure the emission fluxes resulting from both UV irradiation and ozone oxidation of Arctic surface microlayer water and the underlying bulk seawater. Under our experimental conditions, both mechanisms lead to comparable VOC emission fluxes, which scale closely with the total and dissolved organic carbon content of the sample. However, the composition of the seawater sample can strongly affect the emission fluxes of specific molecules. For example, nonanal fluxes from oxidation correlate closely with the phytoplankton abundance in the samples, indicating that unsaturated lipids may be the substrate. Conversely, the best predictor for the nitrogenated VOC flux under irradiation conditions is photosynthetic prokaryotes (i.e., cyanobacteria) abundance. Similar studies in a wider range of environments, ideally conducted in the field, will better constrain the importance of these abiotic processes to global ocean-to-atmosphere fluxes.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Earth and Space ChemistryPub Date : 2024-08-25DOI: 10.1021/acsearthspacechem.4c0018910.1021/acsearthspacechem.4c00189
Kunpeng Chen*, Yuqing Sha, Hengjia Ou and Jun Zhao,
{"title":"HOSO2 Released from Mineral Dust: A Novel Channel of Heterogeneous Oxidation of Sulfur Dioxide during Dust Storms","authors":"Kunpeng Chen*, Yuqing Sha, Hengjia Ou and Jun Zhao, ","doi":"10.1021/acsearthspacechem.4c0018910.1021/acsearthspacechem.4c00189","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00189https://doi.org/10.1021/acsearthspacechem.4c00189","url":null,"abstract":"<p >Mineral dust has been recognized as an emerging source of radicals that may significantly influence the fate of environmental pollutants. While the production of hydroxyl (OH) radicals from an aqueous dust surface has been recently clarified, other radical-produced channels have been little understood. Here, we propose a novel channel of hydroxysulfonyl (HOSO<sub>2</sub>) radical production from the aqueous surface of α-Fe<sub>2</sub>O<sub>3</sub>, a ubiquitous iron mineral, during the heterogeneous oxidation of sulfur dioxide (SO<sub>2</sub>). The reactive force field molecular dynamic (ReaxFF-MD) simulations and the density functional theory (DFT) calculations disclosed that the OH groups bound to the α-Fe<sub>2</sub>O<sub>3</sub> surface can oxidize the adsorbed SO<sub>2</sub> into HOSO<sub>2</sub> radicals in the presence of the surface water layer. The HOSO<sub>2</sub> radical can be released from the dust surface and subsequently contribute to the gaseous sulfuric acid (H<sub>2</sub>SO<sub>4</sub>) formation. Our kinetic modeling revealed that, despite most SO<sub>2</sub> converting to interfacial sulfate through competing reactions on the aqueous dust surface, the abundant surface-bound OH groups and high dust particle concentration during dust storms may enable substantial gaseous H<sub>2</sub>SO<sub>4</sub> production. The level of gaseous H<sub>2</sub>SO<sub>4</sub> production from the HOSO<sub>2</sub>-released channel is likely comparable to that from the traditional gas-phase OH oxidation pathway. This study demonstrates that mineral-produced radicals may play a critical role in transforming atmospheric pollutants and hence modulate the impacts of mineral dust on local and regional air quality.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00189","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273833","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"HOSO2 Released from Mineral Dust: A Novel Channel of Heterogeneous Oxidation of Sulfur Dioxide during Dust Storms","authors":"Kunpeng Chen, Yuqing Sha, Hengjia Ou, Jun Zhao","doi":"10.1021/acsearthspacechem.4c00189","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00189","url":null,"abstract":"Mineral dust has been recognized as an emerging source of radicals that may significantly influence the fate of environmental pollutants. While the production of hydroxyl (OH) radicals from an aqueous dust surface has been recently clarified, other radical-produced channels have been little understood. Here, we propose a novel channel of hydroxysulfonyl (HOSO<sub>2</sub>) radical production from the aqueous surface of α-Fe<sub>2</sub>O<sub>3</sub>, a ubiquitous iron mineral, during the heterogeneous oxidation of sulfur dioxide (SO<sub>2</sub>). The reactive force field molecular dynamic (ReaxFF-MD) simulations and the density functional theory (DFT) calculations disclosed that the OH groups bound to the α-Fe<sub>2</sub>O<sub>3</sub> surface can oxidize the adsorbed SO<sub>2</sub> into HOSO<sub>2</sub> radicals in the presence of the surface water layer. The HOSO<sub>2</sub> radical can be released from the dust surface and subsequently contribute to the gaseous sulfuric acid (H<sub>2</sub>SO<sub>4</sub>) formation. Our kinetic modeling revealed that, despite most SO<sub>2</sub> converting to interfacial sulfate through competing reactions on the aqueous dust surface, the abundant surface-bound OH groups and high dust particle concentration during dust storms may enable substantial gaseous H<sub>2</sub>SO<sub>4</sub> production. The level of gaseous H<sub>2</sub>SO<sub>4</sub> production from the HOSO<sub>2</sub>-released channel is likely comparable to that from the traditional gas-phase OH oxidation pathway. This study demonstrates that mineral-produced radicals may play a critical role in transforming atmospheric pollutants and hence modulate the impacts of mineral dust on local and regional air quality.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142179689","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Non-Hydroxyl Radical Species Production during Dark Air Oxidation of Alluvial Soils","authors":"Elora Bourbon, Frédéric Averseng, Pierre Le Pape, Thierry Allard, Fulvia Baratelli, Fabrice Alliot, Alexandre Gélabert, Valentine Rollot, Elodie Guigon, Jessica Brest, Sylvie Nélieu, Guillaume Morin","doi":"10.1021/acsearthspacechem.4c00113","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00113","url":null,"abstract":"Natural environments subjected to hydrologically driven redox fluctuations are regarded as propitious to contaminant degradation since they favor the cyclic oxygenation of Fe(II) minerals, which produces oxygen reactive species (ROS), such as the hydroxyl radical, OH<sup>•</sup>. However, the identity of these reactive species may vary as a function of physicochemical conditions and remains a matter of research. Here, using spin-trapping electron paramagnetic resonance (EPR) with 5,5-dimethyl-1-pyrroline <i>N</i>-oxide (DMPO) as a spin trap, we show that a non-hydroxyl reactive species is produced in significant amounts upon air-oxidation of alluvial soil suspensions (Seine River Basin, France). Indeed, among the DMPO–OH<sup>•</sup>, DMPO–CO<sub>2</sub><sup>•–</sup>, and DMPO–alkyl<sup>•</sup> adducts observed, the latter dramatically increases with the addition of ethanol or, to a lesser extent, <i>tert</i>-butanol, especially with phosphate buffer. This result reveals a dominant non-hydroxyl species, which we interpret as Fe(IV) since it is known to oxidize alcohols to alkyl<sup>•</sup> radicals and is favored by phosphate ligands. With phosphate buffer and ethanol, the DMPO–alkyl<sup>•</sup> production correlates with the initial reduced-state iron pool in the samples, as determined using Fe K-edge X-ray absorption spectroscopy (XAS). Fe(II) phyllosilicates, Fe(0) in one soil core and, to a lesser extent, vivianite, are found to be the most significantly oxidized iron phases upon soil oxygenation, and pyrite appears less reactive. Hence, we show that a significant reactive species, differing from OH<sup>•</sup>, forms upon oxygenation of soil Fe(II) minerals, especially in the presence of soil-sourced phosphate. Our results may therefore call to further directly identify this putative Fe(IV) species and to investigate its ability to degrade organic contaminants in natural environments.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142223772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Earth and Space ChemistryPub Date : 2024-08-24DOI: 10.1021/acsearthspacechem.4c0011310.1021/acsearthspacechem.4c00113
Elora Bourbon, Frédéric Averseng, Pierre Le Pape, Thierry Allard, Fulvia Baratelli, Fabrice Alliot, Alexandre Gélabert, Valentine Rollot, Elodie Guigon, Jessica Brest, Sylvie Nélieu and Guillaume Morin*,
{"title":"Non-Hydroxyl Radical Species Production during Dark Air Oxidation of Alluvial Soils","authors":"Elora Bourbon, Frédéric Averseng, Pierre Le Pape, Thierry Allard, Fulvia Baratelli, Fabrice Alliot, Alexandre Gélabert, Valentine Rollot, Elodie Guigon, Jessica Brest, Sylvie Nélieu and Guillaume Morin*, ","doi":"10.1021/acsearthspacechem.4c0011310.1021/acsearthspacechem.4c00113","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00113https://doi.org/10.1021/acsearthspacechem.4c00113","url":null,"abstract":"<p >Natural environments subjected to hydrologically driven redox fluctuations are regarded as propitious to contaminant degradation since they favor the cyclic oxygenation of Fe(II) minerals, which produces oxygen reactive species (ROS), such as the hydroxyl radical, OH<sup>•</sup>. However, the identity of these reactive species may vary as a function of physicochemical conditions and remains a matter of research. Here, using spin-trapping electron paramagnetic resonance (EPR) with 5,5-dimethyl-1-pyrroline <i>N</i>-oxide (DMPO) as a spin trap, we show that a non-hydroxyl reactive species is produced in significant amounts upon air-oxidation of alluvial soil suspensions (Seine River Basin, France). Indeed, among the DMPO–OH<sup>•</sup>, DMPO–CO<sub>2</sub><sup>•–</sup>, and DMPO–alkyl<sup>•</sup> adducts observed, the latter dramatically increases with the addition of ethanol or, to a lesser extent, <i>tert</i>-butanol, especially with phosphate buffer. This result reveals a dominant non-hydroxyl species, which we interpret as Fe(IV) since it is known to oxidize alcohols to alkyl<sup>•</sup> radicals and is favored by phosphate ligands. With phosphate buffer and ethanol, the DMPO–alkyl<sup>•</sup> production correlates with the initial reduced-state iron pool in the samples, as determined using Fe K-edge X-ray absorption spectroscopy (XAS). Fe(II) phyllosilicates, Fe(0) in one soil core and, to a lesser extent, vivianite, are found to be the most significantly oxidized iron phases upon soil oxygenation, and pyrite appears less reactive. Hence, we show that a significant reactive species, differing from OH<sup>•</sup>, forms upon oxygenation of soil Fe(II) minerals, especially in the presence of soil-sourced phosphate. Our results may therefore call to further directly identify this putative Fe(IV) species and to investigate its ability to degrade organic contaminants in natural environments.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Earth and Space ChemistryPub Date : 2024-08-23DOI: 10.1021/acsearthspacechem.4c0020210.1021/acsearthspacechem.4c00202
Rebecca M. Blake, Nicholas D. Stapleton, Isabelle M. Jones, James R. Brookes, Gemma F. Turner, Stephanie A. Bird, Alan Riboldi-Tunnicliffe, Rachel M. Williamson, Rosemary Young, Helen E. Maynard-Casely, Dino Spagnoli* and Stephen A. Moggach*,
{"title":"Structural Evolution of Trimethylacetonitrile under Pressure: A Combined X-ray Diffraction and Computational Study","authors":"Rebecca M. Blake, Nicholas D. Stapleton, Isabelle M. Jones, James R. Brookes, Gemma F. Turner, Stephanie A. Bird, Alan Riboldi-Tunnicliffe, Rachel M. Williamson, Rosemary Young, Helen E. Maynard-Casely, Dino Spagnoli* and Stephen A. Moggach*, ","doi":"10.1021/acsearthspacechem.4c0020210.1021/acsearthspacechem.4c00202","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00202https://doi.org/10.1021/acsearthspacechem.4c00202","url":null,"abstract":"<p >Three high-pressure phases of trimethylacetonitrile, a compound of potential interest in the context of Titan’s atmospheric chemistry, have been investigated using single-crystal X-ray diffraction, periodic density functional theory, and CrystalExplorer intermolecular energy calculations. A disordered tetragonal <i>P</i>4/<i>nmm</i> phase is formed between 0.07 and 0.29 GPa (denoted hp-I). Compression to 0.43 GPa forms an ordered orthorhombic <i>Pnma</i> phase (hp-II), which transforms to a monoclinic <i>P</i>2<sub>1</sub>/<i>m</i> phase (hp-III) at 1.52 GPa. The hp-III phase persists to at least 3.34 GPa. Phase transitions are driven by densification of the crystal and facilitated by rearrangement of the supramolecular hydrogen-bonding network, with 180° reorientation of half the molecules. Compression of each phase is associated with slight shortening of the intermolecular hydrogen bonds, with gradual destabilization of the cohesive energy to 3.34 GPa.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}