ACS Earth and Space Chemistry最新文献

{"title":"Reactant Discovery with an Ab Initio Nanoreactor: Exploration of Astrophysical N-Heterocycle Precursors and Formation Pathways","authors":"Sommer L. Johansen,&nbsp;Heejune Park,&nbsp;Lee-Ping Wang* and Kyle N. Crabtree*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0012010.1021/acsearthspacechem.4c00120","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00120https://doi.org/10.1021/acsearthspacechem.4c00120","url":null,"abstract":"<p >The incorporation of nitrogen atoms into cyclic compounds is essential for terrestrial life; nitrogen-containing (N-)heterocycles make up DNA and RNA nucleobases, several amino acids, B vitamins, porphyrins, and other components of biomolecules. The discovery of these molecules on meteorites with non-terrestrial isotopic abundances supports the hypothesis of exogenous delivery of prebiotic material to early Earth; however, there has been no detection of these species in interstellar environments, indicating that there is a need for greater knowledge of their astrochemical formation and destruction pathways. Here, we present results of simulations of gas-phase pyrrole and pyridine formation from an <i>ab initio</i> nanoreactor, a first-principles molecular dynamics simulation method that accelerates reaction discovery by applying non-equilibrium forces that are agnostic to individual reaction coordinates. Using the nanoreactor in a retrosynthetic mode, starting with the N-heterocycle of interest and a radical leaving group, then considering the discovered reaction pathways in reverse, a rich landscape of N-heterocycle-forming reactivity can be found. Several of these reaction pathways, when mapped to their corresponding minimum energy paths, correspond to novel barrierless formation pathways for pyridine and pyrrole, starting from both detected and hypothesized astrochemical precursors. This study demonstrates how first-principles reaction discovery can build mechanistic knowledge in astrochemical environments as well as in early Earth models such as Titan’s atmosphere where N-heterocycles have been tentatively detected.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00120","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273712","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":"A Network Approach for the Accurate Characterization of Water Lines Observable in Astronomical Masers and Extragalactic Environments","authors":"Wim Ubachs*,&nbsp;Attila G. Császár,&nbsp;Meissa L. Diouf,&nbsp;Frank M. J. Cozijn and Roland Tóbiás*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0016110.1021/acsearthspacechem.4c00161","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00161https://doi.org/10.1021/acsearthspacechem.4c00161","url":null,"abstract":"<p >The water molecule, crucial to the chemical composition and dynamics of the universe, is typically identified in its gas phase via radio and submillimeter transitions, with frequencies up to a few THz. To understand the physicochemical behavior of astronomical objects, accurate transition frequencies are required for these lines. From a set of 26 new and 564 previous Lamb dip measurements, utilizing our ultrasensitive laser-based spectrometers in the near-infrared region, ultrahigh-precision spectroscopic networks were set up for H₂¹⁶O and H₂¹⁸O, augmented with 40 extremely accurate frequencies taken from the literature. Based on kHz-accuracy paths of these networks, considerably improved line-center frequencies have been obtained for 35 observed or predicted maser lines of H₂¹⁶O, as well as for 14 transitions of astronomical significance of H₂¹⁸O. These reference frequencies, attached with 5–25 kHz uncertainties, may help future studies in various fields of astrochemistry and astrophysics, in particular when precise information is demanded about Doppler-velocity components, including the gas flows of galactic cores, the kinematics of planetary nebulae, or the motion in exoplanetary atmospheres.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00161","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273713","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":"Vacuum Ultraviolet Photoionization of Methane-Water Clusters Leads to Methanol Formation","authors":"Nureshan Dias, Alexander K. Lemmens, Anna Wannenmacher, Musahid||Dias, Ahmed","doi":"10.1021/acsearthspacechem.4c00151","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00151","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141922776","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":"Unveiling the Nitrogen Chemistry of Titan with the Dragonfly Mass Spectrometer: Experimental Focus on Amines and Amides","authors":"C. Freissinet, V. Moulay, Xiang Li, C. Szopa, A. Buch, Antoine Palanca, Victoria Da Poian, Alex Abello, D. Boulesteix, Sandrine Vinatier, S. Teinturier, Jennifer C. Stern, W. Brinckerhoff, M. Trainer","doi":"10.1021/acsearthspacechem.4c00143","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00143","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141926192","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":"Unveiling the Nitrogen Chemistry of Titan with the Dragonfly Mass Spectrometer: Experimental Focus on Amines and Amides","authors":"Caroline Freissinet*,&nbsp;Valentin Moulay,&nbsp;Xiang Li,&nbsp;Cyril Szopa,&nbsp;Arnaud Buch,&nbsp;Antoine Palanca,&nbsp;Victoria Da Poian,&nbsp;Alex Abello,&nbsp;David Boulesteix,&nbsp;Sandrine Vinatier,&nbsp;Samuel Teinturier,&nbsp;Jennifer C. Stern,&nbsp;William B. Brinckerhoff and Melissa G. Trainer,&nbsp;","doi":"10.1021/acsearthspacechem.4c0014310.1021/acsearthspacechem.4c00143","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00143https://doi.org/10.1021/acsearthspacechem.4c00143","url":null,"abstract":"<p >The Dragonfly mission payload includes the Dragonfly Mass Spectrometer (DraMS) instrument, which operates in both gas chromatography–mass spectrometry (GCMS) and laser desorption mass spectrometry (LDMS) analysis modes. DraMS will investigate Titan chemistry at geologically diverse locations. Titan uniquely offers direct access to abundant, complex, carbon- and nitrogen-rich chemistry on the surface of a water-ice-dominated ocean world. Amino and amide functional groups, if both present, would be witnesses of redox conditions in the surface environment. An enantiomeric excess in those compounds could help discriminate the chemical or biological origins of these molecules. In this study, we first investigated a wide range of amines and amides (primary, secondary, tertiary, aliphatic, aromatic, branched, and linear moieties) using DraMS-like GCMS protocols, with sample volatilization via both pyrolysis and wet chemistry (derivatization with dimethylformamide dimethyl acetal─DMF-DMA). We determined the general patterns of this derivatization according to the chemical families: dimethylformamidination of the primary amines and amides; methylation, formylation, and dimethoxymethylation of the secondary amines; and lack of derivatization of the secondary amides. The minor coproducts were also identified for each chemical family, to help strict identification of molecules in a Titan GCMS spectrum. The limits of detection and quantification showed that N-species could be detected in the range of tens of fmol to hundreds of pmol. Out of the six chiral amines and amides investigated, five were enantiomerically resolved. We also performed LDMS measurements on a subset of compounds, amines─aliphatic and aromatic─and an amide, and their detection and identification demonstrated the complementarity of LDMS and GCMS modes. Altogether, our results demonstrate the application of DraMS to characterize the expected wide diversity of N-containing compounds of interest at Titan’s surface.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270015","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":"Advances in Reverse Weathering and Its Role in Clay Mineral Formation and the Carbon Dioxide Cycle","authors":"Kejun Zheng,&nbsp;Shangying Li,&nbsp;Yulong Gao,&nbsp;Wenzhe Meng and Hongfei Cheng*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0010510.1021/acsearthspacechem.4c00105","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00105https://doi.org/10.1021/acsearthspacechem.4c00105","url":null,"abstract":"<p >Reverse weathering plays a significant role in the cycle of atmospheric carbon dioxide (CO₂) and elements between oceanic and continental environments during the Earth’s evolution. Through summarizing various previous research on reverse weathering, this review found much evidence that suggested that reverse weathering commonly occurs in dynamic areas of element exchange and abundant material sources, such as river mouths, deltas, sedimentary basins, and deep-sea sediments, accompanied by the formation of authigenic clay minerals. These clay minerals, by incorporating elements including Si, K, Li, and Mg, are reburied and contribute to a crucial reverse weathering sink, resulting in maintaining an elemental balance between the ocean and land. Concurrently, the process of reverse weathering releases CO₂, which holds great significance in studying CO₂ anomalies in the paleoenvironment. The extensive formation of authigenic clay minerals during pre-Cambrian glaciations and the δ⁷Li shifts around the Permian–Triassic boundary and within the Cenozoic provide compelling evidence of the occurrence of reverse weathering. This evidence sheds light on explaining the prolonged high CO₂ concentrations during pre-Cambrian glaciations, dramatic CO₂ concentration changes near the Permian–Triassic boundary, and cooling of the Cenozoic climate. It also offers new perspectives for paleoenvironmental reconstructions and the study of carbon cycling. This review can help to deeply understand the significant role of reverse weathering concerning clay mineral formation and the CO₂ cycle during Earth’s evolution, providing a theoretical foundation for future research endeavors.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142269984","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":"Advances in Reverse Weathering and Its Role in Clay Mineral Formation and the Carbon Dioxide Cycle","authors":"Kejun Zheng, Shangying Li, Yulong Gao, Wenzhe Meng, Hongfei Cheng","doi":"10.1021/acsearthspacechem.4c00105","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00105","url":null,"abstract":"Reverse weathering plays a significant role in the cycle of atmospheric carbon dioxide (CO₂) and elements between oceanic and continental environments during the Earth’s evolution. Through summarizing various previous research on reverse weathering, this review found much evidence that suggested that reverse weathering commonly occurs in dynamic areas of element exchange and abundant material sources, such as river mouths, deltas, sedimentary basins, and deep-sea sediments, accompanied by the formation of authigenic clay minerals. These clay minerals, by incorporating elements including Si, K, Li, and Mg, are reburied and contribute to a crucial reverse weathering sink, resulting in maintaining an elemental balance between the ocean and land. Concurrently, the process of reverse weathering releases CO₂, which holds great significance in studying CO₂ anomalies in the paleoenvironment. The extensive formation of authigenic clay minerals during pre-Cambrian glaciations and the δ⁷Li shifts around the Permian–Triassic boundary and within the Cenozoic provide compelling evidence of the occurrence of reverse weathering. This evidence sheds light on explaining the prolonged high CO₂ concentrations during pre-Cambrian glaciations, dramatic CO₂ concentration changes near the Permian–Triassic boundary, and cooling of the Cenozoic climate. It also offers new perspectives for paleoenvironmental reconstructions and the study of carbon cycling. This review can help to deeply understand the significant role of reverse weathering concerning clay mineral formation and the CO₂ cycle during Earth’s evolution, providing a theoretical foundation for future research endeavors.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141944298","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":"Molecular Structure and Rotational Dynamics in the Acetonitrile:Acetylene (1:2) Plastic Co-crystal at Titan Conditions","authors":"Atul C. Thakur, Richard C. Remsing","doi":"10.1021/acsearthspacechem.4c00157","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00157","url":null,"abstract":"The surface of Saturn’s moon Titan is coated with small-molecule organic solids termed cryominerals. Cryominerals play an analogous role to minerals on Earth in Titan’s surface geology and geochemistry. To develop a predictive understanding of Titan’s surface geochemistry, we need to characterize the structure and dynamics of cryominerals at the molecular scale. We use <i>ab initio</i> molecular dynamics simulations to quantify the structure and dynamics of the acetonitrile:acetylene (1:2) co-crystal at Titan surface conditions. We suggest that acetonitrile:acetylene is in a plastic phase, in which acetonitrile molecules are dynamically disordered about the N–C–C axis on sub-picosecond timescales, and that this rotational, plastic disorder persists at least to temperatures of 30 K. We anticipate that many cryominerals may have plastic phases at or near Titan surface conditions, and understanding this disorder will be crucial to predicting chemistry on Titan’s surface.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141969241","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":"Sensitivity Analysis and Uncertainty Quantification of PFAS Fate and Transport in Heterogeneous Riparian Sediments","authors":"Pei Li*,&nbsp;Jeffery T. McGarr,&nbsp;Farzad Moeini,&nbsp;Zhenxue Dai and Mohamad Reza Soltanian*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0003710.1021/acsearthspacechem.4c00037","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00037https://doi.org/10.1021/acsearthspacechem.4c00037","url":null,"abstract":"<p >Per- and polyfluoroalkyl substances (PFAS) are surface-active contaminants, which are detected in groundwater globally, presenting serious health concerns. The vadose zone and surface water are recognized as primary sources of PFAS contamination. Previous studies have explored PFAS transport and retention mechanisms in the vadose zone, revealing that adsorption at interfaces and soil/sediment heterogeneity significantly influences PFAS retention. However, our understanding of how surface water–groundwater interactions along river corridors impact PFAS transport remains limited. To analyze PFAS transport during surface water–groundwater interactions, we performed saturated–unsaturated flow and reactive transport simulations in heterogeneous riparian sediments. Incorporating uncertainty quantification and sensitivity analysis, we identified key physical and geochemical sediment properties influencing PFAS transport. Our models considered aqueous-phase transport and adsorption both at the air–water interface (AWI) and the solid-phase surface. We tested different cases of heterogeneous sediments with varying volume proportions of higher permeability sediments, conducting 2000 simulations for each case, followed by global sensitivity and response surface analyses. Results indicate that sediment porosities, which are correlated to permeabilities, are crucial for PFAS transport in riparian sediments during river stage fluctuations. High-permeable sediment (e.g., sandy gravel, sand) is the preferential path for the PFAS transport, and low-permeable sediment (e.g., silt, clay) is where PFAS is retained. Additionally, the results show that adsorption at interfaces (AWI and solid phase) has a small impact on PFAS retention in riparian environments. This study offers insights into factors influencing PFAS transport in riparian sediments, potentially aiding the development of strategies to reduce the risk of PFAS contamination in groundwater from surface water.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141984444","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":"Sensitivity Analysis and Uncertainty Quantification of PFAS Fate and Transport in Heterogeneous Riparian Sediments","authors":"Pei Li, Jeffery T. McGarr, Farzad Moeini, Zhenxue Dai, Mohamad Reza Soltanian","doi":"10.1021/acsearthspacechem.4c00037","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00037","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are surface-active contaminants, which are detected in groundwater globally, presenting serious health concerns. The vadose zone and surface water are recognized as primary sources of PFAS contamination. Previous studies have explored PFAS transport and retention mechanisms in the vadose zone, revealing that adsorption at interfaces and soil/sediment heterogeneity significantly influences PFAS retention. However, our understanding of how surface water–groundwater interactions along river corridors impact PFAS transport remains limited. To analyze PFAS transport during surface water–groundwater interactions, we performed saturated–unsaturated flow and reactive transport simulations in heterogeneous riparian sediments. Incorporating uncertainty quantification and sensitivity analysis, we identified key physical and geochemical sediment properties influencing PFAS transport. Our models considered aqueous-phase transport and adsorption both at the air–water interface (AWI) and the solid-phase surface. We tested different cases of heterogeneous sediments with varying volume proportions of higher permeability sediments, conducting 2000 simulations for each case, followed by global sensitivity and response surface analyses. Results indicate that sediment porosities, which are correlated to permeabilities, are crucial for PFAS transport in riparian sediments during river stage fluctuations. High-permeable sediment (e.g., sandy gravel, sand) is the preferential path for the PFAS transport, and low-permeable sediment (e.g., silt, clay) is where PFAS is retained. Additionally, the results show that adsorption at interfaces (AWI and solid phase) has a small impact on PFAS retention in riparian environments. This study offers insights into factors influencing PFAS transport in riparian sediments, potentially aiding the development of strategies to reduce the risk of PFAS contamination in groundwater from surface water.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141944297","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}