ACS Earth and Space Chemistry最新文献

{"title":"","authors":"Xu Ma, Mengyi Zi, Xiaoming Zhao*, Yuyin Ma, Dan Zhao*, Meiling Shi and Jinru Lin, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 7","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.9,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00060","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144640916","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":"","authors":"Daniel R. Crocker*, Kevin M. Sutherland, Benjamin Freudenberg, Kimberly Alonso, Ann Pearson, Collin P. Ward and David T. Johnston*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 7","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.9,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00057","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144640930","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":"","authors":"Patricia B. C. Forbes*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 7","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.9,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00184","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144640935","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":"Can Boronyl-Bearing Carbon Chains Serve as Gas-Phase Molecular Carriers of Interstellar Boron?","authors":"Cinthya K. Prieto-García,&nbsp;Heidy M. Quitián-Lara,&nbsp;Josep M. Masqué,&nbsp;Felipe Fantuzzi* and J. Oscar C. Jiménez-Halla*,&nbsp;","doi":"10.1021/acsearthspacechem.5c00089","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.5c00089","url":null,"abstract":"<p >Boron is an exotic element in space. However, although no boron-bearing molecules have yet been identified in the interstellar medium (ISM), its unique chemical properties suggest that it could play a pivotal role in astrobiology and the origins of life. Given the isoelectronic relationship between the cyano (CN) and boronyl (BO) groups and the widespread detection of HC_<i>n</i>CN carbon chains in the ISM, we herein computationally investigate the potential of analogous BO-bearing chains (HC_<i>n</i>BO, <i>n</i> = 1–12) as viable gas-phase carriers of interstellar boron. Our calculations indicate that HC_<i>n</i>BO species exhibit lower enthalpies of formation and higher dipole moments than their CN-bearing counterparts, suggesting enhanced intrinsic stability and potential for detection via rotational spectroscopy. However, analysis of their formation and destruction pathways reveals that BO-bearing chains are susceptible to exergonic decomposition through reactions with CN radicals and H^– anions, which may significantly affect their abundances in the ISM. These findings underscore that, while HC_<i>n</i>BO systems emerge as theoretically attractive interstellar boron carriers, competitive decomposition and the element’s low cosmic abundance pose substantial challenges to their astrophysical detection.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 8","pages":"2045–2055"},"PeriodicalIF":2.9,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00089","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144878064","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":"VUV Processing of Nitrile Ice: Direct Comparison of Branching in Ice and TPD Spectra","authors":"Travis J. Hager,&nbsp;Bailey M. Moore,&nbsp;Quentin D. Borengasser,&nbsp;Kyle T. Renshaw,&nbsp;Rachel Johnson,&nbsp;Anudha C. Kanaherarachchi and Bernadette M. Broderick*,&nbsp;","doi":"10.1021/acsearthspacechem.5c00133","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.5c00133","url":null,"abstract":"<p >The interplay between radiation chemistry and sublimation dynamics of condensed organic compounds on cold grains is fundamental to describe observed gas- and ice-phase molecular abundances in the interstellar medium (ISM). Infrared measurements are generally used to identify molecules synthesized in irradiated ices in laboratory experiments, while mass spectrometric techniques have been used to monitor the products following temperature-programmed desorption (TPD). The IR measurements are often used quantitatively to monitor the chemical transformation of ices during the course of irradiation, but the gas-phase methods applied with TPD generally do not permit quantitative branching determination. Here, we combine reflection–absorption infrared spectroscopy (RAIRS) of ices with broadband rotational spectroscopy of the sublimed products to study the branching of photoproducts produced by the VUV (120–160 nm) irradiation of condensed CH₃CN (methyl cyanide) and CH₃CH₂CN (ethyl cyanide) ices. This permits direct comparison between the ice-phase and gas-phase branching following temperature-programmed desorption (TPD). This comparison is analogous to astronomical observations of ices in protostellar disks, such as by the James Webb Space Telescope employed in conjunction with ALMA observations in the corresponding warm-up regions of the same objects. In the condensed CH₃CN VUV-processed ices, we quantified the HCN, CH₃NC (methyl isocyanide), H₂CCNH (ketenimine), CH₃NH₂ (methylamine), and CH₄ (methane) abundances. The CH₃CH₂CN ices also readily produced the corresponding isocyanide and HCN in addition to a significant yield of CH₂CHCN (vinyl cyanide). The ethyl cyanide ice produced (CH₃)HCCNH (methyl ketenimine) rather than CH₃NH₂, and no CH₄ formation was observed. In the gas phase, we detected the isocyanides, HCN, and CH₂CHCN. The relative abundances of photoproducts are normalized to the abundance of the isocyanide formed in both ices. Following irradiation of CH₃CN, the HCN:CH₃NC ratio was found to be 0.5 ± 0.1 and 1.5 ± 0.1 in the ice and gas phase, respectively. The HCN:CH₃CH₂NC ratios were 1.7 ± 0.2 in the ice phase and 5.7 ± 0.4 in the gas phase for CH₃CH₂CN. The CH₂CHCN:CH₃CH₂NC ratio for ice and gas phases was found to be 0.9 ± 0.1 and 2.5 ± 0.5, respectively. The ice- and gas-phase relative abundances could all be brought into agreement if the unknown IR band strength of the isocyanide C–N stretch is assumed to be ∼3 times larger than that of the cyanides.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 8","pages":"2137–2147"},"PeriodicalIF":2.9,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144878065","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":"Long-Lived Isomers of C11H9+: New Experimental Insights from the PIRENEA Setup","authors":"Ana I. Lozano,&nbsp;Anthony Bonnamy,&nbsp;Aude Simon and Christine Joblin*,&nbsp;","doi":"10.1021/acsearthspacechem.5c00071","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.5c00071","url":null,"abstract":"<p >The dehydrogenated cation of methylated benzene is known to exist in two isomeric forms: benzylium and tropylium. Structurally similar forms have been proposed for the –H cations of methylated polycyclic aromatic hydrocarbons, but their spectroscopic characterization remains limited, and their photophysical properties are still poorly understood. Previous studies identified 2-naphthylmethylium and benzyltropylium as specific long-lived isomers of the –H fragment of methylnaphthalene cations. Here, we investigate the photodissociation spectroscopy and photoprocessing of gas-phase C₁₁H₉⁺ ions in the visible range. Experiments are conducted using the versatile laboratory astrophysics setup PIRENEA, which enables studies over long timescales (∼1000 s) and allows photoprocessing to be combined with ion–molecule reaction experiments. We confirm the presence of 2-naphthylmethylium and benzyltropylium and additionally identify 1-naphthylmethylium, previously undetected in experiments. Moreover, we present the first complete quantitative analysis of the relative abundances of these isomers and provide clear evidence of interconversion among the three long-lived species. These isomerization processes occur below the dissociation threshold, a finding supported by molecular dynamics simulations. The photophysical properties of C₁₁H₉⁺ isomers─including isomerization and fluorescence─make them intriguing candidates for consideration in astrophysical environments exposed to mild UV irradiation (<i>h</i>ν &lt; 7 eV). Moreover, their detection via rotational spectroscopy in such regions is facilitated by their closed-shell electronic structure.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 8","pages":"2017–2032"},"PeriodicalIF":2.9,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144878149","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":"The Monomolecular-Layer Selective Adsorption of Amino Acids on Microbial Proto-Dolomite Induced by the Cyanobacterium Leptolyngbya Boryana","authors":"Yanyang Zhao,&nbsp;Yishui Han,&nbsp;Xiao Gao,&nbsp;Xiangyu Wei,&nbsp;Chao Han,&nbsp;Zhaopeng Wang,&nbsp;Karim Benzerara,&nbsp;Maurice E. Tucker and Zuozhen Han*,&nbsp;","doi":"10.1021/acsearthspacechem.5c00142","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.5c00142","url":null,"abstract":"<p >Microbially mediated mineralization is widely recognized as a key pathway for proto-dolomite formation, with extracellular polymeric substances (EPS), especially amino acids, considered important mediators. Yet, the surface interactions between amino acids and proto-dolomite remain insufficiently characterized. In this study, we examined the adsorption behavior of four representative amino acids─aspartic acid (Asp), arginine (Arg), glycine (Gly), and proline (Pro)─on organic-free proto-dolomite (Cpdol) synthesized by the cyanobacterium <i>Leptolyngbya boryana</i>. Experiments were conducted across a range of pH and salinity conditions, and amino acid concentrations were measured using high-performance liquid chromatography. The adsorption data were well described by Langmuir isotherms, indicating a monomolecular-layer selective adsorption model. Adsorption capacity varied among amino acids (Asp &gt; Gly &gt; Pro &gt; Arg) and showed a positive correlation with pH and a negative correlation with salinity. Based on density functional theory (DFT) calculations, the adsorption energies of the four amino acids were evaluated on seven crystal surfaces of proto-dolomite. The results indicate that surface complexation between carboxyl groups and surface metal ions is the primary mechanism driving adsorption. Under higher pH conditions, the deprotonated amino group can further enhance adsorption by lowering the adsorption energy. These findings suggest that, beyond acidic amino acids, surface complexation of various environmentally responsive amino acids may play an important role in regulating the early-stage formation of proto-dolomite in microbial environments.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 7","pages":"1946–1957"},"PeriodicalIF":2.9,"publicationDate":"2025-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807843","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":"The Role of Wind Velocity in Saline Water Evaporation from Porous Media and Surface Salt Crystallization Dynamics","authors":"Sahar Jannesarahmadi*,&nbsp;Milad Aminzadeh*,&nbsp;Rainer Helmig,&nbsp;Dani Or,&nbsp;Bastian Oesterle and Nima Shokri*,&nbsp;","doi":"10.1021/acsearthspacechem.5c00130","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.5c00130","url":null,"abstract":"<p >This study systematically investigates the effect of wind flow on evaporation dynamics and salt crystallization patterns in porous media. Well-controlled experiments were conducted in a laboratory wind tunnel, where the surface of sand columns saturated with freshwater and NaCl solutions at concentrations of 10%, 15%, and 20% were subjected to wind flows of 0.5 and 5 m/s, corresponding to laminar and turbulent flow regimes, respectively. Mass loss measurements from the samples, combined with optical imaging of their surfaces, revealed distinct evaporation dynamics and crystallization patterns. We observed that the interaction between intermittent turbulent airflow and evolving salt crystals on the surface resulted in a relatively uniform crystallization pattern. In contrast, under laminar airflow conditions, salt crystal nucleation and formation primarily occurred at the leading edge of the sample, particularly at lower salt concentrations. We further investigated the impact of enhanced evaporative mass loss in the presence of wind on crystallization dynamics by quantifying the crystal coverage and its lateral extent on the surface. Under turbulent flow conditions, we observed that full coverage of the surface with salt crystals requires 2 to 3 times higher evaporative losses in 10% NaCl sample relative to the 15% and 20% samples, respectively. These findings highlight the complex interplay between evaporation and crystallization processes under varying airflow conditions, thus offering valuable insight for improving hydrological and climatological modeling.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 7","pages":"1938–1945"},"PeriodicalIF":2.9,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00130","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807715","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":"Geochemical Settings at an Alkaline Hydrothermal Vent Stabilized Ribose: Evidence from Chemical Garden and Other Simulation Experiments","authors":"Raksha Umesh,&nbsp; and ,&nbsp;Nanishankar V. Harohally*,&nbsp;","doi":"10.1021/acsearthspacechem.5c00095","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.5c00095","url":null,"abstract":"<p >The origin of life is an unsolved mystery. The discovery of a hydrothermal vent starting from black smoke to a lost city has sparked a spotlight on a hydrothermal vent as the place of origin of life having all the prerequisite settings including a proton gradient, thermal energy, mineral catalysts, and simple constituent molecules for the emergence of life. On the other hand, the RNA world hypothesis, which is an offshoot of the primordial soup theory, presupposes ribose availability and its stability as the primary milestone for abiotic synthesis of RNA. We demonstrate through chemical garden and other simulation experiments stabilization of ribose under a geochemical setting of deep ocean hydrothermal vents occurring via acidic ocean water interaction with brucite and calcite chimneys. The early Earth scenario, wherein boric acid-containing seawater interacts with hydrothermal vent materials such as CaCO₃, Mg(OH)₂, and Ca(OH)₂ along with ribose, has been modeled utilizing chemical garden and prebiotic simulation experiments (NMR scale as well as synthetic scale). The performed experiments reveal formation of metal borate, and its subsequent role in stabilization of ribose is demonstrated via concrete evidence consisting of FT-IR, ¹H NMR, and ¹¹B NMR spectra.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 7","pages":"1871–1880"},"PeriodicalIF":2.9,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807834","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":"Sampling and Purification Methods for Dating by Atom Trap Trace Analysis in Various Environmental Applications","authors":"Yannis Arck*,&nbsp;Florian Meienburg,&nbsp;David Wachs,&nbsp;Stefan Beyersdorfer,&nbsp;Arne Kersting,&nbsp;Maximilian Schmidt,&nbsp;Markus Oberthaler and Werner Aeschbach,&nbsp;","doi":"10.1021/acsearthspacechem.5c00128","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.5c00128","url":null,"abstract":"<p >Atom Trap Trace Analysis (ATTA) has enabled new applications of the noble gas radioisotopes ³⁹Ar, ⁸¹Kr, and ⁸⁵Kr for dating environmental processes in a broad range of environmental systems on time scales of years to about 1 Myr. Compared to low-level counting of ³⁹Ar and ⁸⁵Kr, ATTA has reduced sample size requirements from over 1000 to a few liters of water. The scope of possible applications has widened from groundwater systems to the global ocean, stratified lakes, alpine glaciers, and ice deposits, or even nonhydrological systems like permafrost and rocks. New applications and sample types require appropriate sampling and preparation procedures, presented herein with a focus on ³⁹Ar applications in ocean water, lake water, and glacier ice. Water (or gas) samples with volumes around 10 L can be collected, transported, and stored in commercial propane gas bottles. Blocks or drill cores of ice must be transported frozen, transferred into suitable vacuum containers, evacuated, and then melted to release trapped gases. A dedicated sample preparation line extracts all gases from the sample containers. After removing water vapor the remaining gases are collected on a cooled activated charcoal trap. Thereafter, the gas mixture passes two titanium sponge getters at different temperatures to absorb all reactive gases, leaving only the purified inert noble gases with a dominating argon fraction. An additional gas-chromatographic separation of krypton from argon is possible if required. The presence of vast amounts of gases may necessitate sophisticated sampling methods and modifications to the preparation process to remove the undesired bulk gases before the standardized purification to protect the getters. Important purification parameters of selected samples from field campaigns are presented as examples for different environmental compartments, including groundwater, ocean water, extremely gas-rich lake water, and glacier ice.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 7","pages":"1927–1937"},"PeriodicalIF":2.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144806732","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}