ACS Earth and Space Chemistry最新文献

{"title":"Adsorption of REEs to Kaolinite via Ion Exchange and Surface Complexation as a Function of Water Chemistry","authors":"Elmira Ramazanova,&nbsp;Neha Sharma,&nbsp;Elaine D. Flynn,&nbsp;Olwen Stagg,&nbsp;Jeffrey G. Catalano and Daniel E. Giammar*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0038910.1021/acsearthspacechem.4c00389","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00389https://doi.org/10.1021/acsearthspacechem.4c00389","url":null,"abstract":"<p >Rare earth elements (REEs) are critical components of modern technology behind renewable energy, transportation, and electronics but have a limited current supply. A substantial portion of global REE production relies on ion adsorption deposits. A high abundance of kaolinite in REE enrichment zones within these deposits suggests that kaolinite controls the subsurface migration of REEs. This study aimed to improve the current understanding of REE binding to kaolinite under varying water chemistry conditions. We conducted batch experiments with kaolinite (KGa-2) and three REEs (Nd, Dy, and Yb) at varying pH, electrolyte concentration, dissolved inorganic carbon (DIC), low molecular weight organic acids (citric and oxalic acids), and total REE concentration conditions. Increasing electrolyte concentration inhibits REE adsorption at pH &lt; 7, suggesting that ion exchange contributes to adsorption at these pH values. DIC affects adsorption above pH 7–8 by forming strong aqueous complexes with heavy REEs. Citric acid decreases REE adsorption via aqueous complexation of REEs at pH &gt; 5 but does not affect adsorption at pH &lt; 5. The surface complexation model captures the main adsorption trends with two mechanisms: ion exchange on basal planes at pH &lt; ∼6 and inner-sphere surface complexation to edge sites at pH &gt; ∼6. Equilibrium constants for surface complexation increase in the order of Yb &gt; Dy &gt; Nd, indicating a higher strength of adsorption for heavy REEs. This study demonstrates how water chemistry conditions control the adsorption mechanisms that may determine the mobility of REEs in subsurface environments rich in kaolinite.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 6","pages":"1430–1442 1430–1442"},"PeriodicalIF":2.9,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312418","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 Characterization of Nascent and Aged Sea Spray Aerosol.","authors":"Dilini K Gamage, Elias Hasenecz, Glorianne P Dorcé, Kathryn J Mayer, Jon S Sauer, Christopher Lee, Kimberly A Prather, Elizabeth A Stone","doi":"10.1021/acsearthspacechem.4c00412","DOIUrl":"10.1021/acsearthspacechem.4c00412","url":null,"abstract":"<p><p>The chemical aging of sea spray aerosol (SSA) was examined in the Sea Spray Chemistry and Particle Evolution (SeaSCAPE) experiment in which nascent SSA particles were generated from seawater by breaking waves in a glass wave channel. Particles and gases in the air in the wave channel headspace were aged in an oxidative flow reactor. Nascent SSA (before reaction) and aged SSA (after reaction) particles were chemically analyzed for inorganic ions, organic carbon (OC), and select organic species, including organosulfates, fatty acids, and alkyl amines. Nascent SSA mass primarily consisted of inorganic ions associated with sea salt. On average, OC accounted for 52% of particle mass <0.25 μm and 0.2% of mass in both supermicron and submicron particles, with an increase in OC relative to Na⁺ with decreasing particle size. The aging process increased the sulfate, phosphate, nitrate, ammonium, and OC concentrations relative to sodium. The largest increases in the sulfate and OC to Na⁺ ratios (by factors of 7 and 5) in aged SSA were observed in particles with diameters <0.25 μm. Organosulfates, which accounted for approximately 1% of SSA OC mass in PM_1.0, were enhanced in aged SSA and indicated the formation of low-volatility secondary organic aerosol products associated with aging biological molecules such as unsaturated fatty acids, isoprene, and monoterpenes. For example, isoprene-derived organosulfates (e.g., 2-methyltetrol sulfate, C₅H₁₁SO₇ ^-; <i>m</i>/<i>z</i> 215.0225) increased by a factor of 40 in samples of aged SSA and marine volatile organic compounds. Among the strongest organosulfate signals in nascent and aged SSA were alkyl organosulfates, which are known to be anthropogenic surfactants in coastal waters. Homologous series of saturated and unsaturated fatty acids, fatty acid derivatives, and alkyl amines were also identified in nascent and aged SSA, with some species enhanced by aging (i.e., diethylamine) and others not. Together, these bulk and molecular analyses provide insight into molecular modifications that occur upon the chemical aging of nascent SSA.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 6","pages":"1453-1464"},"PeriodicalIF":2.9,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12183759/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144482513","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":"Rate Constants and Product Yields for the C + CH3CHO Reaction at Low Temperatures","authors":"Kevin M. Hickson*,&nbsp;Jean-Christophe Loison and Valentine Wakelam,&nbsp;","doi":"10.1021/acsearthspacechem.5c0011110.1021/acsearthspacechem.5c00111","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.5c00111https://doi.org/10.1021/acsearthspacechem.5c00111","url":null,"abstract":"<p >Reactions involving atomic carbon in its ground electronic state, C(³P), play an important role in astrochemistry due to high C atom abundance levels. Here we performed a kinetic investigation of the reaction between C(³P) and acetaldehyde, CH₃CHO, determining rate constants for this process over the 50–296 K range. Measurements of the formation of atomic hydrogen, H(²S), were also performed to provide insight into product formation. Experiments were conducted using a supersonic flow reactor coupled with pulsed laser photolysis for C atom generation and pulsed laser-induced fluorescence in the vacuum ultraviolet range for the detection of both C(³P) and H(²S) atoms. Quantum chemical calculations of the ground triplet state potential energy surface of C₃H₄O were also performed to provide theoretical support for the measurements. The rate constants were large and temperature independent with an average value of 4.0 × 10^–10 cm³ s^–1. This result is consistent with the theoretical results which predict either very low barriers or none at all on the underlying potential energy surface. Although experimental difficulties prevented the quantitative determination of H atom formation, qualitatively, H atom yields were very low with CH₃CH/C₂H₄ + CO as the major products based on the calculations. The influence of this reaction on interstellar chemistry was tested using a gas-grain model of dense interstellar clouds. These simulations predict that the C(³P) + CH₃CHO reaction decreases gas-phase CH₃CHO abundances by more than an order of magnitude at early and intermediate cloud ages, with a lower influence at typical dense cloud ages.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 6","pages":"1679–1690 1679–1690"},"PeriodicalIF":2.9,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312439","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 Characterization of Nascent and Aged Sea Spray Aerosol","authors":"Dilini K. Gamage,&nbsp;Elias Hasenecz,&nbsp;Glorianne P. Dorcé,&nbsp;Kathryn J. Mayer,&nbsp;Jon S. Sauer,&nbsp;Christopher Lee,&nbsp;Kimberly A. Prather and Elizabeth A. Stone*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0041210.1021/acsearthspacechem.4c00412","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00412https://doi.org/10.1021/acsearthspacechem.4c00412","url":null,"abstract":"<p >The chemical aging of sea spray aerosol (SSA) was examined in the Sea Spray Chemistry and Particle Evolution (SeaSCAPE) experiment in which nascent SSA particles were generated from seawater by breaking waves in a glass wave channel. Particles and gases in the air in the wave channel headspace were aged in an oxidative flow reactor. Nascent SSA (before reaction) and aged SSA (after reaction) particles were chemically analyzed for inorganic ions, organic carbon (OC), and select organic species, including organosulfates, fatty acids, and alkyl amines. Nascent SSA mass primarily consisted of inorganic ions associated with sea salt. On average, OC accounted for 52% of particle mass &lt;0.25 μm and 0.2% of mass in both supermicron and submicron particles, with an increase in OC relative to Na⁺ with decreasing particle size. The aging process increased the sulfate, phosphate, nitrate, ammonium, and OC concentrations relative to sodium. The largest increases in the sulfate and OC to Na⁺ ratios (by factors of 7 and 5) in aged SSA were observed in particles with diameters &lt;0.25 μm. Organosulfates, which accounted for approximately 1% of SSA OC mass in PM_1.0, were enhanced in aged SSA and indicated the formation of low-volatility secondary organic aerosol products associated with aging biological molecules such as unsaturated fatty acids, isoprene, and monoterpenes. For example, isoprene-derived organosulfates (e.g., 2-methyltetrol sulfate, C₅H₁₁SO₇^–; <i>m</i>/<i>z</i> 215.0225) increased by a factor of 40 in samples of aged SSA and marine volatile organic compounds. Among the strongest organosulfate signals in nascent and aged SSA were alkyl organosulfates, which are known to be anthropogenic surfactants in coastal waters. Homologous series of saturated and unsaturated fatty acids, fatty acid derivatives, and alkyl amines were also identified in nascent and aged SSA, with some species enhanced by aging (i.e., diethylamine) and others not. Together, these bulk and molecular analyses provide insight into molecular modifications that occur upon the chemical aging of nascent SSA.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 6","pages":"1453–1464 1453–1464"},"PeriodicalIF":2.9,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00412","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312417","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":"Carolyn Liu-Kang,&nbsp;Laura-Hélèna Rivellini,&nbsp;Xinke Wang and Jonathan P. D. Abbatt*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 5","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144443525","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":"Yudai Kobayashi,&nbsp; and ,&nbsp;Tomoko Ikeda-Fukazawa*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 5","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00006","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144443531","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":"Jayant Nirmalkar,&nbsp;Ji Yi Lee,&nbsp;Kwangyul Lee,&nbsp;Joonyoung Ahn and Mijung Song*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 5","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00039","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144443532","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":"Silvia Alessandrini*,&nbsp;Hexu Ye and Cristina Puzzarini*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 5","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsearthspacechem.5c00034","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144443534","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":"","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 5","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/spv009i005_1935490","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144362074","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":"Updated in-cloud secondary aerosol production in the Northern Hemisphere predicted by the Community Multiscale Air Quality modeling system.","authors":"Kathleen M Fahey, Neha Sareen, Annmarie G Carlton, William T Hutzell","doi":"10.1021/acsearthspacechem.4c00370","DOIUrl":"10.1021/acsearthspacechem.4c00370","url":null,"abstract":"<p><p>Clouds are important physicochemical processors of atmospheric pollutants. Major contributors to secondary sulfate, clouds also provide media for the production and processing of secondary organic aerosol (SOA). Sulfate and organic compounds often dominate particulate mass, and the accurate representation of their important production and loss pathways in models is necessary to effectively address the adverse health, ecosystem, and climate effects associated with elevated particulate concentrations. In this study we investigate the impacts of an extended cloud-chemistry scheme on predictions of particulate sulfur and low molecular weight organic acids in an annual hemispheric application of the Community Multiscale Air Quality (CMAQ) modeling system, version 5.3. Building upon the previously developed Kinetic Mass Transfer (KMT) framework¹, the AQCHEM-KMT version 2 (KMT2) cloud-chemistry scheme supplements CMAQ's default (AQCHEM) seven-reaction cloud-chemistry parameterization with additional inorganic and organic aqueous-phase chemistry, including additional S(IV) reactions and replacement of the default in-cloud SOA parameterization with an explicit representation of the aqueous oxidation of small carbonyl compounds. Modeled impacts vary seasonally and spatially, and results indicate that, compared with the default seven-reaction cloud-chemistry scheme, the extended aqueous-phase chemistry mechanism contributes to predicted inorganic and organic aerosol fractions and can lead to increases in seasonally averaged PM_2.5 predictions up to ~1 μg m^-3, with greater episodic impacts. While model performance for particulate sulfur species is mixed and, in fact, slightly degraded over CONUS on average for these simulations, a comparison with seasonal oxalate observations indicates that the updated cloud chemistry code may lead to improved model performance for organic aerosol, particularly in areas and seasons where there is limited influence from primary organic acid and/or biomass emissions. The work here suggests there may be a potential benefit realized from re-evaluating and updating the simple cloud chemistry parameterizations that are common in chemical transport models. Future efforts should continue improving representation of the most important aqueous-phase chemical pathways in air quality models while minimizing computational cost.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 5","pages":"1043-1059"},"PeriodicalIF":2.9,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12180745/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144367626","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}