ACS Earth and Space Chemistry最新文献

{"title":"Toward Accurate Characterization of the Puzzling NSO and SNO Moieties","authors":"Vincenzo Barone*,&nbsp;Lina Uribe*,&nbsp;Satyam Srivastav* and Amit Pathak*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0025610.1021/acsearthspacechem.4c00256","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00256https://doi.org/10.1021/acsearthspacechem.4c00256","url":null,"abstract":"<p >The structural and spectroscopic properties in the gas phase of prototypical compounds containing the NSO and SNO moieties have been analyzed by a general computational strategy based on recent Pisa composite schemes (PCS). In a first step, an accurate semiexperimental (SE) equilibrium structure has been derived for <i>cis</i>-HNSO and employed, together with the already available SE equilibrium structures of <i>cis</i>- and <i>trans</i>-HSNO, to validate the geometrical parameters delivered by different quantum chemical methods. The results confirm the accuracy of the proposed composite schemes, provided that the complementary auxiliary basis set correction is included for the Hartree–Fock component. However, perturbative inclusion of quadruple excitations is mandatory for obtaining a correct S–N bond length in the case of HSNO. In this way, it is possible to obtain accurate geometrical parameters and ground state rotational constants, employing in the latter case vibrational corrections obtained by methods rooted in density functional theory (DFT) in the framework of second-order vibrational perturbation theory. The results delivered by a much cheaper model based on DFT geometry optimizations and one-parameter bond corrections, while slightly less accurate, represent a remarkable improvement with respect to current methods of comparable cost. The nearly identical correction induced by quadruple excitations on the S–N bond length of HSNO and CH₃SNO paves the way toward the study of larger compounds of biochemical interest containing the NSO or SNO moieties.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2334–2344 2334–2344"},"PeriodicalIF":2.9,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691552","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 Effect of Salinity on the Dielectric Permittivity of Nanoconfined Geofluids","authors":"Alireza Chogani*,&nbsp;Helen E. King,&nbsp;Aleksandar Živković and Oliver Plümper,&nbsp;","doi":"10.1021/acsearthspacechem.4c0021010.1021/acsearthspacechem.4c00210","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00210https://doi.org/10.1021/acsearthspacechem.4c00210","url":null,"abstract":"<p >Nanoporosity is a characteristic feature of geological formations that provides potential pathways for geofluids to meander and interact with minerals. Confinement of water within nanopores leads to unique phenomena. The dielectric constant of water becomes anisotropic and adopts tensorial properties rather than remaining a scalar value. In such nanoconfinement, it has been found that the permittivity of water decreases perpendicularly and increases parallel to the interface. As geofluids are rarely pure water in nature, being a water–salt(−gas) mixture within the Earth, it becomes pivotal to examine how these additional constituents of water affect the permittivity of fluids confined within the nanopores of rocks. In this study, we present the calculation of the permittivity of saline water in calcite slit nanopores using molecular dynamics simulations under low-pressure–temperature conditions. The dielectric properties are weakly dependent on salinity for both the perpendicular and parallel dielectric permittivity components. We analyzed the atomic charge and polarization density of the fluid perpendicular to the nanochannel walls and the orientation of water molecules’ dipole inside the nanochannel. From our analysis, most of these factors were generally not altered significantly in the presence of salinity. These findings are significant because they enable us to use well-studied pure water properties under nanoconfinement to determine the geochemical behavior of fluids within natural nanoporous systems.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2284–2293 2284–2293"},"PeriodicalIF":2.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00210","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691312","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":"The Effect of Salinity on the Dielectric Permittivity of Nanoconfined Geofluids.","authors":"Alireza Chogani, Helen E King, Aleksandar Živković, Oliver Plümper","doi":"10.1021/acsearthspacechem.4c00210","DOIUrl":"10.1021/acsearthspacechem.4c00210","url":null,"abstract":"<p><p>Nanoporosity is a characteristic feature of geological formations that provides potential pathways for geofluids to meander and interact with minerals. Confinement of water within nanopores leads to unique phenomena. The dielectric constant of water becomes anisotropic and adopts tensorial properties rather than remaining a scalar value. In such nanoconfinement, it has been found that the permittivity of water decreases perpendicularly and increases parallel to the interface. As geofluids are rarely pure water in nature, being a water-salt(-gas) mixture within the Earth, it becomes pivotal to examine how these additional constituents of water affect the permittivity of fluids confined within the nanopores of rocks. In this study, we present the calculation of the permittivity of saline water in calcite slit nanopores using molecular dynamics simulations under low-pressure-temperature conditions. The dielectric properties are weakly dependent on salinity for both the perpendicular and parallel dielectric permittivity components. We analyzed the atomic charge and polarization density of the fluid perpendicular to the nanochannel walls and the orientation of water molecules' dipole inside the nanochannel. From our analysis, most of these factors were generally not altered significantly in the presence of salinity. These findings are significant because they enable us to use well-studied pure water properties under nanoconfinement to determine the geochemical behavior of fluids within natural nanoporous systems.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2284-2293"},"PeriodicalIF":2.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11587090/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142724449","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":"Understudied High-Pollution Band along Long Island’s South Coastline Caused by the Interaction of New York City Urban Plumes and a Stagnant Sea Breeze Front","authors":"Jie Zhang*,&nbsp;Margaret J. Schwab,&nbsp;Tianyu Zhu,&nbsp;Alexandra Catena and James J. Schwab*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0019310.1021/acsearthspacechem.4c00193","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00193https://doi.org/10.1021/acsearthspacechem.4c00193","url":null,"abstract":"<p >Recent observations have highlighted extreme ozone exceedances (exceeding 100 ppb) and significant surface ozone variability along Long Island’s south shore, driven by the interaction between New York City urban plumes and a stagnant sea breeze front. Despite this, detailed spatial distribution data and associated aerosol processing information have been lacking, reducing attention to this high-pollution phenomenon. In this study, mobile lab measurements captured three extreme high ozone events on August 21, September 4, and September 6, 2023. These events confirmed the presence of a high ozone band, extending from Jones Beach to Ponquogue Beach (80–90 km). High-resolution rapid refresh (HRRR) simulations indicate that the extreme ozone concentrations (near or exceeding 100 ppb) were confined to the shallow marine boundary layer with a height of about 20–40 m along the coastline, with notable increases in particle NH₄NO₃ levels. The three year temporary Heckscher State Park monitor site measurements on the south shore further suggest a possible increasing trend in high ozone conditions for the Long Island south shore. This polluted band poses significant health risks to local communities as well as beachgoers on hot, sunny days and presents an opportunity for research on marine-related aerosol processing. Our study underscores the need for expanded air quality monitoring and alert systems for Long Island’s south shore as well as further studies on the marine–urban interface based on this highly polluted band.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2110–2116 2110–2116"},"PeriodicalIF":2.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00193","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691425","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":"Profiling Phenotypic Heterogeneity of Circulating Tumor Cells through Spatially Resolved Immunocapture on Nanoporous Micropillar Arrays","authors":"Lianyu Lu,&nbsp;Yaohui Wang,&nbsp;Yue Ding,&nbsp;Yuqing Wang,&nbsp;Zhi Zhu,&nbsp;Jinsong Lu*,&nbsp;Liu Yang*,&nbsp;Peng Zhang* and Chaoyong Yang*,&nbsp;","doi":"10.1021/acsnano.4c0889310.1021/acsnano.4c08893","DOIUrl":"https://doi.org/10.1021/acsnano.4c08893https://doi.org/10.1021/acsnano.4c08893","url":null,"abstract":"<p >The phenotype of circulating tumor cells (CTCs) offers valuable insights into monitoring cancer metastasis and recurrence. While microfluidics presents a promising approach for capturing these rare cells in blood, the phenotypic profiling of CTCs remains technically challenging. Herein, we developed a nanoporous micropillar array chip enabling highly efficient capture and in situ phenotypic analysis of CTCs through enhanced and tunable on-chip immunoaffinity binding. The nanoporous micropillar array addresses the fundamental limits in fluidic mass transfer, surface stagnant flow boundary effect, and interface topographic and multivalent reactions simultaneously within a single device, resulting in a synergistic enhancement of CTC immunocapture efficiency. The CTC capture efficiency increased by approximately 40% for cancer cells with low surface marker expressing. By manipulating fluidic velocity (hydrodynamic drag force) on the chip, a cell adhesion gradient was generated in the capture chamber, enabling individual CTCs with varying expression levels of epithelial cellular adhesion molecules to be immunocaptured at the corresponding spatial locations where equilibrium drag force is provided. The clinical utility of the nanoporous micropillar array was demonstrated by accurately distinguishing early and advanced stages of breast cancer and further longitudinally monitoring treatment response. We envision that the nanoporous micropillar array chip will provide an in situ capture and molecular profiling approach for CTCs and enhance the clinical application of CTC liquid biopsy.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31135–31147 31135–31147"},"PeriodicalIF":15.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608356","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":"Gas-Phase and Model Ice-Surface Reactions of S(1D) with Water and Methanol: A Computational Investigation and Implications for Cosmochemistry/Astrochemistry","authors":"Andrea Giustini,&nbsp;Gabriella Di Genova,&nbsp;Dimitrios Skouteris,&nbsp;Cecilia Ceccarelli,&nbsp;Marzio Rosi and Nadia Balucani*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0022910.1021/acsearthspacechem.4c00229","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00229https://doi.org/10.1021/acsearthspacechem.4c00229","url":null,"abstract":"<p >Gas-phase reactions of atomic sulfur in its first electronically excited metastable state, S(¹D), with water and methanol have been theoretically investigated to characterize their potential energy surfaces, the reaction mechanisms, and the product branching fractions. According to our results, both reactions proceed with the formation of bound intermediates that, for the isolated systems, decompose into products because of the large energy content with which they are formed. The SO(a ¹Δ) + H₂ channel is the only open one for the S(¹D) + H₂O reaction, while many channels are open for the S(¹D) + CH₃OH reaction. For the latter case, statistical estimates of the product branching fractions indicate that the main channels are those leading to CH₂OH + SH, H₂CO + H₂S, H₂CS + H₂O, and CH₃ + HSO. The mechanism of the related O(¹D) + CH₃SH reaction has also been unveiled. Since the reaction intermediates can be stabilized by energy loss to surrounding species on ice or in liquid water, to gain some insights into the possible effects of water molecules, we have also analyzed how the two reactions behave when four additional water molecules are added. The conclusion is that the initial intermediates formed by the insertion or addition mechanism, namely, HOSH (hydrogen thioperoxide) and H₂OS for S(¹D) + H₂O and CH₂OHSH (mercaptomethanol), CH₄OS and CH₃OSH (methyl thioperoxide) for S(¹D) + CH₃OH, as well as CH₃SOH (methyl sulfenic acid) for O(¹D) + CH₃SH, will probably be stabilized by the interaction with the additional water molecules. Our results can help in understanding sulfur chemistry in space, especially in the case of comets. On the one hand, the S(¹D) + H₂O gas-phase reaction could account for the additional SO source necessary to explain the observed distribution of this species obtained by using the Plateau de Bure interferometer of Institut de Radioastronomie Millimétrique (IRAM) for the Hale Bopp comet. On the other hand, some of the S/O-containing molecules identified by ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) during the enhanced dust emission events of the 67/P comet (e.g., species with the gross formula HSO, H₂SO, and CH₄OS) could be the results of the chemistry occurring on ice that we have exposed in this work.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2318–2333 2318–2333"},"PeriodicalIF":2.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691245","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":"Lead Translocation and Isotopic Fractionation after Uptake by Brassica juncea (Brown Mustard)","authors":"Trent G. Stegink,&nbsp; and ,&nbsp;Shelby T. Rader*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0017410.1021/acsearthspacechem.4c00174","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00174https://doi.org/10.1021/acsearthspacechem.4c00174","url":null,"abstract":"<p >The behavior of lead (Pb) during plant uptake is poorly understood, particularly as it pertains to plant isotopic fractionation patterns and whether they can accurately reflect unique geogenic or anthropogenic sources of contamination. Here, we characterize concentrations and changes in plant Pb ratios during uptake to determine the feasibility of bioremediation and isotopic fingerprinting for Pb sourcing in <i>Brassica juncea</i> (<i>B. juncea</i>), a known Pb-tolerant species, which was grown in a controlled greenhouse environment. Twenty individuals were cultivated from three trials using substrates amended with Pb from different sources (natural ore, anthropogenic, and mixed) and a control with no Pb amendment. After maturation, plants were harvested, split into individual parts, and analyzed for both Pb concentrations and isotopic composition. Results demonstrate significant translocation of Pb from the roots to the leaves, showing an average leaf translocation factor of 3.6. Other above-ground parts’ translocation factors were consistently below 1 (TF = 0.4, on average). Results also show no preferential uptake of any given Pb isotope into the plants, resulting in similar isotopic compositions throughout. Above-ground plant part, ²⁰⁶Pb/²⁰⁷Pb (1.17–1.19) were within the range of initial substrate values (1.14–1.18), though the roots did show a significant increase in ²⁰⁶Pb/²⁰⁷Pb (1.21–1.22). We were unable to differentiate plants grown from each treated substrate, making them unreliable for isotopic fingerprinting of substrate Pb sources. This confirms the limitations of <i>B. juncea</i> as a potential biomonitoring apparatus but demonstrates a greater than expected ability to translocate Pb to its above-ground parts, which may indicate some useful and significant phytoextraction potential during phytostabilization projects and subsequent health concerns for those consuming the plant when grown in low [Pb] soils.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2187–2197 2187–2197"},"PeriodicalIF":2.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691244","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":"Triggered Cascade-Activation Nanoplatform to Alleviate Hypoxia for Effective Tumor Immunotherapy Guided by NIR-II Imaging","authors":"Yu Ji,&nbsp;Suchen Qu,&nbsp;Gaoyu Shi,&nbsp;Liansheng Fan,&nbsp;Jing Qian,&nbsp;Zhaorui Sun*,&nbsp;Feng Lu* and Xin Han*,&nbsp;","doi":"10.1021/acsnano.4c1133410.1021/acsnano.4c11334","DOIUrl":"https://doi.org/10.1021/acsnano.4c11334https://doi.org/10.1021/acsnano.4c11334","url":null,"abstract":"<p >Hypoxia is one of the most typical features among various types of solid tumors, which creates an immunosuppressive tumor microenvironment (TME) and limits the efficacy of cancer treatment. Alleviating hypoxia becomes a key strategy to reshape hypoxic TME which improves cancer immunotherapy. However, it remains challenging to perform tumor precision therapy with controllable switches through hypoxia-activated gene editing and prodrugs to alleviate hypoxia. In this study, silica-coated second near-infrared window (NIR-II) emitting silver sulfide quantum dots are used as the carrier to load the Clustered Regularly Interspaced Short Palindromic Repeats/Cas9 (CRISPR/Cas9) system to target hypoxia-inducible factor-1 (HIF-1α) and guide tumor-targeted imaging. To reduce the off-target effects in nontumor cells and better control safety risks, a TME-triggered cascade-activation nanodiagnostic and therapeutic platform (AA@Cas-H@HTS) is designed, which achieves the hypoxia activation of prodrug tirapazamine (TPZ) and spatiotemporal release of CRISPR/Cas9 ribonucleoprotein. Tumor hypoxia is greatly alleviated by the synergistic function of HIF-1α depletion by gene editing and TPZ activation. Importantly, targeting HIF-1α disrupts the programmed cell death 1/programmed cell death ligand 1 (PD-1/PD-L1) signaling pathway, which effectively reshapes the immune-suppressive TME and activates T cell-mediated antitumor immunity. Taken together, we have provided a TME-triggered cascade-activation nanoplatform to alleviate hypoxia for improved cancer immunotherapy.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31421–31434 31421–31434"},"PeriodicalIF":15.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608542","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":"Ozone Oxidation of the Flame Retardant BDE-209: Kinetics and Molecular-Level Analysis of the Gas-Phase Product Compounds","authors":"Siyu Liu,&nbsp;Jinli Xu,&nbsp;Yingxin Xie,&nbsp;Bowen He,&nbsp;Qingxin Deng,&nbsp;Yanan Hu,&nbsp;Jiangping Liu,&nbsp;Davide Vione,&nbsp;Xue Li* and Sasho Gligorovski*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0016210.1021/acsearthspacechem.4c00162","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00162https://doi.org/10.1021/acsearthspacechem.4c00162","url":null,"abstract":"<p >Polybrominated diphenyl ether (PBDE) flame retardants are persistent organic pollutants that are ubiquitous in both indoor and outdoor environments and exhibit adverse health effects. Among all of the PBDEs, decabromodiphenyl ether (BDE-209) is the most abundant due to the increased production of electronic devices. Here we evaluate the uptake coefficients of ozone (O₃) on glass plates coated with BDE-209 at different relative humidities (RH) over a range of temperatures. The uptake of O₃ slightly increased with the increase of RH from 1.2 × 10^–5 at 30% RH to 2.2 × 10^–5 at 90% RH, but was independent of the temperature change. Real-time measurements of the gas-phase product compounds formed by the reaction of O₃ with BDE-209 were performed with a high-resolution Q Exactive hybrid quadrupole Orbitrap mass spectrometer (UHR-MS) in both positive and negative ionization modes. Interestingly, the molecular-level analysis revealed that the observed gas-phase product compounds in the presence of water vapor did not contain Br atoms and, in most cases, had fewer than 12 C atoms, indicating that both debromination and aromatic ring fragmentation occurred. The developed reaction mechanism suggests that the formation of most CHO compounds occurs by the combination of reductive debromination triggered by HO₂ with ring and open-chain fragmentation induced by O₃. The molecular-level understanding of the volatile product compounds produced by the ozonolysis of glass coated with BDE-209 provides valuable insights into the reaction mechanism, enabling more accurate characterization in atmospheric model studies.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2166–2175 2166–2175"},"PeriodicalIF":2.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691235","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":"Dominant Production of Dissolved Inorganic Carbon by Organic Matter Degradation in a Coastal Lagoon: Evidence from Carbon Isotopes","authors":"Mohd Danish,&nbsp; and ,&nbsp;Gyana Ranjan Tripathy*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0014810.1021/acsearthspacechem.4c00148","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00148https://doi.org/10.1021/acsearthspacechem.4c00148","url":null,"abstract":"<p >Coastal oceanic settings are biogeochemically active zones and play a dominant role in the global carbon cycle. In this contribution, we have investigated the spatial distribution of dissolved inorganic carbon (DIC) and δ¹³C_DIC along the salinity gradient of a large tropical coastal lagoon (Chilika, India) and major source waters (river, groundwater) to the lagoon for three different (pre-monsoon, monsoon, and post-monsoon) seasons. These data were used to constrain internal cycling and DIC fluxes to the Bay of Bengal. The average [DIC] and δ¹³C_DIC values of the Chilika, although they exhibit significant variation within a season, are found comparable for the pre-monsoon (1.8 ± 0.6 mM; −5 ± 3 ‰), monsoon (1.7 ± 0.4 mM; −4 ± 2 ‰), and post-monsoon (1.9 ± 0.3 mM; −4 ± 3‰) samples. Co-variation between DIC (and δ¹³C_DIC) and salinity during all three seasons deviates from the theoretical mixing line (TML) between river and seawater, indicating nonconservative behavior of DIC in the lagoon. The magnitude of the DIC and δ¹³C_DIC deviations from their corresponding TML points to dominancy of organic matter degradation in causing this nonconservative trend. Additionally, the pre-monsoon samples also show a minor effect of calcite precipitation on the [DIC]. The LOICZ model estimates that the DIC flux from this lagoon to the ocean is higher than that reported for several peninsular Indian rivers, despite their high (378 km³/yr) freshwater influxes to the Bay of Bengal. This disproportionally higher DIC flux is linked to remineralization of organic matter, underscoring its importance in regulating the inorganic carbon cycle of this highly productive coastal system.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2155–2165 2155–2165"},"PeriodicalIF":2.9,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691630","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}