ACS Earth and Space ChemistryPub Date : 2024-07-11DOI: 10.1021/acsearthspacechem.4c0015910.1021/acsearthspacechem.4c00159
Zhaoyan Zhang, Xiangyu Zang, Yingqi Zhao, Ya Zhao, Hua Xie, Gang Li*, Ling Jiang* and Xueming Yang,
{"title":"Assessing the Difference in the Effects of NOx on the Photooxidation Mechanisms of Isomeric Compounds of α-Pinene and Δ3-Carene","authors":"Zhaoyan Zhang, Xiangyu Zang, Yingqi Zhao, Ya Zhao, Hua Xie, Gang Li*, Ling Jiang* and Xueming Yang, ","doi":"10.1021/acsearthspacechem.4c0015910.1021/acsearthspacechem.4c00159","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00159https://doi.org/10.1021/acsearthspacechem.4c00159","url":null,"abstract":"<p >Elucidating the difference between the photooxidation mechanisms of isomeric volatile organic compounds (VOCs) by anthropogenic pollutants helps to unravel the structural dependence of VOCs on the formation of secondary organic aerosols (SOAs). Herein, the effects of NO<sub><i>x</i></sub> (NO and NO<sub>2</sub>) on the SOA formation from the photooxidation of isomeric monoterpenes of α-pinene and Δ<sup>3</sup>-carene were compared by a series of experimental and theoretical studies. For both the α-pinene and the Δ<sup>3</sup>-carene systems, the increase of NO and NO<sub>2</sub> concentration ([NO] and [NO<sub>2</sub>]) first enhances and then suppresses the particle number concentration but enhances the particle size growth (except for the photooxidation of Δ<sup>3</sup>-carene with NO). The increase of [NO<sub><i>x</i></sub>] first promotes and then suppresses the SOA yields of α-pinene. In particular, the increase of [NO] suppresses the SOA yields of Δ<sup>3</sup>-carene, whereas the increase of [NO<sub>2</sub>] promotes the SOA yields of Δ<sup>3</sup>-carene. These findings imply that the “rate effect” (a faster oxidation rate leads to a higher SOA yield) of photooxidation for Δ<sup>3</sup>-carene with NO<sub>2</sub> may be more pronounced than that of α-pinene. The number of SOA components with higher O/C in the Δ<sup>3</sup>-carene system is larger than that in the α-pinene system, which could be rationalized that the bond tension of the three-membered ring structure of Δ<sup>3</sup>-carene is larger than that of the four-membered ring of α-pinene. The present findings serve as a model for clarifying the effects of NO<sub><i>x</i></sub> on the SOA formation of VOCs with the same chemical formula and stimulate systematic studies on a broad class of isomeric VOCs toward the improvement of SOA models.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141984362","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 : 2024-07-11DOI: 10.1021/acsearthspacechem.4c0013410.1021/acsearthspacechem.4c00134
Mingrui Sun, and , Geoffrey D. Smith*,
{"title":"Photolytic Mass Loss of Humic Substances Measured with a Quartz Crystal Microbalance","authors":"Mingrui Sun, and , Geoffrey D. Smith*, ","doi":"10.1021/acsearthspacechem.4c0013410.1021/acsearthspacechem.4c00134","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00134https://doi.org/10.1021/acsearthspacechem.4c00134","url":null,"abstract":"<p >Laboratory studies have shown that photolytic mass loss can be a significant sink for secondary organic aerosol (SOA). Here, we use a quartz crystal microbalance to measure mass loss of Suwannee River Humic Acid (SRHA) and Suwannee River Fulvic Acid (SRFA), surrogates for SOA, exposed to 254, 300, and 405 nm radiation over the course of 24 h. We find that the photolytic mass loss rates of these materials are comparable to those for laboratory-generated limonene and toluene SOA material from the study of Baboomian et al, <i>ACS Earth Space Chem</i>. <b>2020,</b> <i>4,</i> 1078. Scaling our results to ambient conditions, we estimate that humic substances in aerosols can lose as much as 8% by mass in the first day of exposure in the atmosphere, equivalent to 0.025% of <i>J</i><sub>NO<sub>2</sub></sub>, the photolysis rate of nitrogen dioxide. By using zero air instead of nitrogen, we also find that the presence of oxygen accelerates the photolytic mass loss rate by a factor of 2 to 4 at all wavelengths suggesting a potential role for reactive oxygen species. UV photolysis of an aqueous SRFA solution demonstrated both photobleaching at UV wavelengths and photoenhancement at visible wavelengths. Ultrahigh-resolution mass spectrometric analysis showed that condensed-phase SRFA photolysis led to decreased intensity in the 100–300 <i>m</i>/<i>z</i> range while aqueous SRFA photolysis resulted in an increase in intensity in the same range. This work reaffirms that photolytic mass loss is a potentially significant sink for SOA, but only on the time scale of a day or two and demonstrates that SRHA and SRFA are suitable surrogates for atmospheric SOA with respect to photolytic mass loss.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00134","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141984363","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}
Zhaoyan Zhang, Xiangyu Zang, Yingqi Zhao, Ya Zhao, Hua Xie, Gang Li, Ling Jiang, Xueming Yang
{"title":"Assessing the Difference in the Effects of NOx on the Photooxidation Mechanisms of Isomeric Compounds of α-Pinene and Δ3-Carene","authors":"Zhaoyan Zhang, Xiangyu Zang, Yingqi Zhao, Ya Zhao, Hua Xie, Gang Li, Ling Jiang, Xueming Yang","doi":"10.1021/acsearthspacechem.4c00159","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00159","url":null,"abstract":"Elucidating the difference between the photooxidation mechanisms of isomeric volatile organic compounds (VOCs) by anthropogenic pollutants helps to unravel the structural dependence of VOCs on the formation of secondary organic aerosols (SOAs). Herein, the effects of NO<sub><i>x</i></sub> (NO and NO<sub>2</sub>) on the SOA formation from the photooxidation of isomeric monoterpenes of α-pinene and Δ<sup>3</sup>-carene were compared by a series of experimental and theoretical studies. For both the α-pinene and the Δ<sup>3</sup>-carene systems, the increase of NO and NO<sub>2</sub> concentration ([NO] and [NO<sub>2</sub>]) first enhances and then suppresses the particle number concentration but enhances the particle size growth (except for the photooxidation of Δ<sup>3</sup>-carene with NO). The increase of [NO<sub><i>x</i></sub>] first promotes and then suppresses the SOA yields of α-pinene. In particular, the increase of [NO] suppresses the SOA yields of Δ<sup>3</sup>-carene, whereas the increase of [NO<sub>2</sub>] promotes the SOA yields of Δ<sup>3</sup>-carene. These findings imply that the “rate effect” (a faster oxidation rate leads to a higher SOA yield) of photooxidation for Δ<sup>3</sup>-carene with NO<sub>2</sub> may be more pronounced than that of α-pinene. The number of SOA components with higher O/C in the Δ<sup>3</sup>-carene system is larger than that in the α-pinene system, which could be rationalized that the bond tension of the three-membered ring structure of Δ<sup>3</sup>-carene is larger than that of the four-membered ring of α-pinene. The present findings serve as a model for clarifying the effects of NO<sub><i>x</i></sub> on the SOA formation of VOCs with the same chemical formula and stimulate systematic studies on a broad class of isomeric VOCs toward the improvement of SOA models.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141610682","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":"Photolytic Mass Loss of Humic Substances Measured with a Quartz Crystal Microbalance","authors":"Mingrui Sun, Geoffrey D. Smith","doi":"10.1021/acsearthspacechem.4c00134","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00134","url":null,"abstract":"Laboratory studies have shown that photolytic mass loss can be a significant sink for secondary organic aerosol (SOA). Here, we use a quartz crystal microbalance to measure mass loss of Suwannee River Humic Acid (SRHA) and Suwannee River Fulvic Acid (SRFA), surrogates for SOA, exposed to 254, 300, and 405 nm radiation over the course of 24 h. We find that the photolytic mass loss rates of these materials are comparable to those for laboratory-generated limonene and toluene SOA material from the study of Baboomian et al, <i>ACS Earth Space Chem</i>. <b>2020,</b> <i>4,</i> 1078. Scaling our results to ambient conditions, we estimate that humic substances in aerosols can lose as much as 8% by mass in the first day of exposure in the atmosphere, equivalent to 0.025% of <i>J</i><sub>NO<sub>2</sub></sub>, the photolysis rate of nitrogen dioxide. By using zero air instead of nitrogen, we also find that the presence of oxygen accelerates the photolytic mass loss rate by a factor of 2 to 4 at all wavelengths suggesting a potential role for reactive oxygen species. UV photolysis of an aqueous SRFA solution demonstrated both photobleaching at UV wavelengths and photoenhancement at visible wavelengths. Ultrahigh-resolution mass spectrometric analysis showed that condensed-phase SRFA photolysis led to decreased intensity in the 100–300 <i>m</i>/<i>z</i> range while aqueous SRFA photolysis resulted in an increase in intensity in the same range. This work reaffirms that photolytic mass loss is a potentially significant sink for SOA, but only on the time scale of a day or two and demonstrates that SRHA and SRFA are suitable surrogates for atmospheric SOA with respect to photolytic mass loss.","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141610680","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}
Andrey A. Zolotarev, Margarita S. Avdontceva, Sergey V. Krivovichev*, Ella V. Sokol, Elena S. Zhitova, Jianhua Chen, Yuqiong Li, Anatoly A. Zolotarev, Natalia S. Vlasenko and Mikhail A. Rassomakhin,
{"title":"Burned Coal Dumps as a Source of New Compounds: The Novel Mixed-Valent Iron Oxysulfide Ca4Fe2+3Fe3+2O6S4 from the Chelyabinsk Coal Basin, South Ural","authors":"Andrey A. Zolotarev, Margarita S. Avdontceva, Sergey V. Krivovichev*, Ella V. Sokol, Elena S. Zhitova, Jianhua Chen, Yuqiong Li, Anatoly A. Zolotarev, Natalia S. Vlasenko and Mikhail A. Rassomakhin, ","doi":"10.1021/acsearthspacechem.4c00058","DOIUrl":"10.1021/acsearthspacechem.4c00058","url":null,"abstract":"<p >“Ovchinnikovite”, a unique iron oxysulfide from the burned dumps of the Chelyabinsk coal basin (Ural, Russia), is a product of high-temperature (1000–1200 °C) alteration of xenoliths of siderite and ankerite rocks by the sulfide-rich gases emanating from the interior of the dumps. According to chemical and crystal-structure analysis, the compound is orthorhombic, with the chemical formula Ca<sub>4</sub>Fe<sup>2+</sup><sub>3</sub>Fe<sup>3+</sup><sub>2</sub>O<sub>6</sub>S<sub>4</sub> (<i>Z</i> = 8). Among five Fe positions with octahedral coordination, two Fe<sup>3+</sup> sites are bonded to four O and two S atoms each, while three Fe sites occupied by Fe<sup>2+</sup> are bonded to two O and four S atoms each. The structure is based upon a three-dimensional framework of Fe-centered octahedra, with two types of layers alternating along the <i>a</i> axis. One layer type is built from corner-sharing Fe<sup>3+</sup>O<sub>4</sub>S<sub>2</sub> octahedra (connected through O atoms). In the second layer, Fe<sup>2+</sup>O<sub>2</sub>S<sub>4</sub> octahedra share faces and corners. S atoms connect the adjacent layers, and Ca atoms with 9-fold coordination are in between the layers. Density functional theory calculations indicate that Fe<sub>40</sub>Ca<sub>32</sub>O<sub>48</sub>S<sub>32</sub> (i.e., Fe<sub>2.5</sub>Ca<sub>2</sub>O<sub>3</sub>S<sub>2</sub>) is a magnetic semimetal material. Other physical characteristics (spin magnetic moment; band structure; optical and dielectric properties) are presented. Crystal chemical relationships with synthetic Ca–Fe oxysulfides are discussed. Conditions of formation of “ovchinnikovite” are compared to those of rare oxysulfides in natural combustion metamorphic rocks as well as in metallurgical processes. The study of “ovchinnikovite” shows that man-made geochemical environments such as those occurring in burned coal dumps serve as another source of novel crystal chemistries almost unprecedented among synthetic systems.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141610683","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}
Xia Li, Kaiming Liu, Hai Zhang, Xinyi Dong, Li Bai, Xiaolong Liu*, Jun Li and Mingguo Wang,
{"title":"Production Mechanism and Emissions of CO2 in Water Networks of an Agricultural Watershed during Drainage Period","authors":"Xia Li, Kaiming Liu, Hai Zhang, Xinyi Dong, Li Bai, Xiaolong Liu*, Jun Li and Mingguo Wang, ","doi":"10.1021/acsearthspacechem.4c00077","DOIUrl":"10.1021/acsearthspacechem.4c00077","url":null,"abstract":"<p >Growing evidence shows that water networks in agricultural watersheds, including rivers, paddy fields (PFs), and ditches (DCs), are hotspots of aquatic greenhouse gas emissions globally. However, the knowledge of the role of natural processes and anthropogenic activities, including agricultural practices, in promoting CO<sub>2</sub> production and emissions still remains unclear. In this study, sampling and analysis of different surface waters during the agricultural drainage period were conducted to clarify the production mechanism and emission of CO<sub>2</sub>. The results showed that all of the surface waters in the Nongjiang River (NJR) watershed acted as sources with respect to atmospheric CO<sub>2</sub>, while a few in the Honghe Wetland and the estuary acted as CO<sub>2</sub> sinks. Longitudinal variations of CO<sub>2</sub> in mainstreams of the NJR indicated that fertilizer application, manure, and sewage discharges stimulated the CO<sub>2</sub> production, while those in the Yalu River (YLR) were mainly affected by the natural wetlands. The accumulation of carbon and nitrogen in waters of PF and DC have enhanced CO<sub>2</sub> emissions during drainage periods. The high ratio of ΔCO<sub>2</sub>/ΔO<sub>2</sub> revealed the important role of the extensive respiration in CO<sub>2</sub> production in the NJR. Furthermore, the correlation between dissolved oxygen and CO<sub>2</sub> demonstrated that respiration and photosynthesis dominated CO<sub>2</sub> production and consumption in all types of water bodies. This study implied that agricultural water networks might be vague sources for aquatic systems, and effort is still urgently needed to quantitatively assess the CO<sub>2</sub> emissions in the context of wetland–farmland shifts regionally and worldwide.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141587474","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}
Gabriela Silva-Vera, Giulia M. Bovolenta, Namrata Rani, Sebastian Vera and Stefan Vogt-Geisse*,
{"title":"Pathways to Interstellar Amides via Carbamoyl (NH2CO) Isomers by Radical-Neutral Reactions on Ice Grain Mantles","authors":"Gabriela Silva-Vera, Giulia M. Bovolenta, Namrata Rani, Sebastian Vera and Stefan Vogt-Geisse*, ","doi":"10.1021/acsearthspacechem.4c00106","DOIUrl":"10.1021/acsearthspacechem.4c00106","url":null,"abstract":"<p >Explaining the formation pathways of amides on ice-grain mantels is crucial to understanding the prebiotic chemistry in an interstellar medium. In this computational study, we explore different radical-neutral formation pathways for some of the observed amides (formamide, acetamide, urea, and <i>N</i>-methylformamide) via intermediate carbamoyl (NH<sub>2</sub>CO) radical precursors and their isomers. We assess the relative energy of four NH<sub>2</sub>CO isomers in the gas phase and evaluate their binding energy on small water clusters to discern the affinity that the isomers present to an ice model. We consider three possible reaction pathways for the formation of the carbamoyl radicals, namely, the OH + HCN, CN + H<sub>2</sub>O, and NH<sub>2</sub> + CO reaction channels. We computed the binding energy distribution for the HCN and CH<sub>3</sub>CN precursors on an ice model consisting of a set of clusters of 22 water molecules each to serve as a starting point for the reactivity study on the ice surface. The computations revealed that the lowest barrier to the formation of an NH<sub>2</sub>CO isomer corresponds to the NH<sub>2</sub> + CO reaction (12.6 kJ mol<sup>–1</sup>). The OH + HCN reaction pathway results in the exothermic formation of the N-radical form of carbamoyl HN(C═O)H with a reaction barrier of 26.7 kJ mol<sup>–1</sup>. We found that the CN + H<sub>2</sub>O reaction displays a high energy barrier of 70.6 kJ mol<sup>–1</sup>. Finally, we also probed the direct formation of the acetamide radical precursor via the OH + CH<sub>3</sub>CN reaction and found that the most probable outcome on interstellar ices is the H-abstraction reaction to yield CH<sub>2</sub>CN and H<sub>2</sub>O. Based on these results, we believe that including alternative reaction pathways, leading to the formation of amides via the N-radical form of carbamoyl, would provide an improvement in the prediction of the amide abundances in astrochemical models, especially regarding the chemistry of star-forming regions.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530718","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}
Laura N. Olive, Alexandra D. Heide, Justin M. Turney and Henry F. Schaefer III*,
{"title":"Ethynyl Radical Hydrogen Abstraction Energetics and Kinetics Utilizing High-Level Theory","authors":"Laura N. Olive, Alexandra D. Heide, Justin M. Turney and Henry F. Schaefer III*, ","doi":"10.1021/acsearthspacechem.4c00040","DOIUrl":"10.1021/acsearthspacechem.4c00040","url":null,"abstract":"<p >The ethynyl radical, C<sub>2</sub>H, is found in a variety of different environments ranging from interstellar space and planetary atmospheres to playing an important role in the combustion of various alkynes under fuel-rich conditions. Hydrogen-atom abstraction reactions are common for the ethynyl radical in these contrasting environments. In this study, the C<sub>2</sub>H + HX → C<sub>2</sub>H<sub>2</sub> + X, where HX = HNCO, <i>trans</i>-HONO, <i>cis</i>-HONO, C<sub>2</sub>H<sub>4</sub>, and CH<sub>3</sub>OH, reactions have been investigated at rigorously high levels of theory, including CCSD(T)-F12a/cc-pVTZ-F12. For the stationary points thus located, much higher levels of theory have been used, with basis sets as large as aug-cc-pV5Z and methods up to CCSDT(Q), and core correlation was also included. These molecules were chosen because they can be found in either interstellar or combustion environments. Various additive energy corrections have been included to converge the relative enthalpies of the stationary points to subchemical accuracy (≤0.5 kcal mol<sup>–1</sup>). Barriers predicted here (2.19 kcal mol<sup>–1</sup> for the HNCO reaction and 0.47 kcal mol<sup>–1</sup> for C<sub>2</sub>H<sub>4</sub>) are significantly lower than previous predictions. Reliable kinetics were acquired over a wide range of temperatures (50–5000 K), which may be useful for future experimental studies of these reactions.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00040","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515257","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}
Qing Ma*, Yaoqi Zhou*, Aubrey Zerkle and Mengchun Cao,
{"title":"Seawater Redox Conditions in the Late Paleoproterozoic: Insight from the North China Craton","authors":"Qing Ma*, Yaoqi Zhou*, Aubrey Zerkle and Mengchun Cao, ","doi":"10.1021/acsearthspacechem.4c00061","DOIUrl":"10.1021/acsearthspacechem.4c00061","url":null,"abstract":"<p >The “Boring Billion” (BB, ∼1800–800 Ma) is characterized by the perceived stasis of carbon isotopes within the geological record of that time. However, geochemical data obtained from global Paleo-Mesoproterozoic strata indicate heterogeneity and complexity of oxygen contents in the oceans, which hinder paleoenvironmental reconstructions from this period. Furthermore, there has been a dearth of studies focused on the Paleoproterozoic strata in the western and southern parts of the North China Craton (NCC). In this paper, we report elemental abundances and Fe speciation data from the Huangqikou Formation in the Ordos Basin, western NCC, and the Dagushi, Bingmagou, Baicaoping, and Puyu Formations in the Xiong’er Basin, southern NCC. Our latest findings, integrated with prior research, indicate that sedimentary environments in these parts of the NCC in the late Paleoproterozoic were uniformly anoxic and ferruginous. During a marine transgression, we see limited evidence of oxic surface waters entering the sedimentary water and resulting in intermittent oxygenation events in the Ordos Basin. However, microbial respiration of oxygen and/or limited oxygen replenishment under sluggish circulation in the basin might have caused the consistently anoxic conditions in the Xiong’er Basin during the late Paleoproterozoic.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504617","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}
Audrey Laberge-Carignan, Martin Pilote, Dominic Larivière, Florence Mercier, Diogo Folhas and Raoul-Marie Couture*,
{"title":"Seasonal Contrasts in Dissolved Selenium Dynamics in Subarctic Thaw Lakes","authors":"Audrey Laberge-Carignan, Martin Pilote, Dominic Larivière, Florence Mercier, Diogo Folhas and Raoul-Marie Couture*, ","doi":"10.1021/acsearthspacechem.4c00041","DOIUrl":"10.1021/acsearthspacechem.4c00041","url":null,"abstract":"<p >Thermokarst ponds (thaw lakes) are ubiquitous in northern landscapes. They are hotspots for the biogeochemical processing of elements, such as carbon (C), nitrogen (N), sulfur (S), iron (Fe) and manganese (Mn). In turn, those elementary cycles may control the mobility of selenium (Se), an essential micronutrient. To unravel these coupled biogeochemical cycles and identify processes controlling Se mobility, we studied four thermokarst ponds in a subarctic peatland valley influenced by permafrost thaw. The data set comprises of water column and sediment porewater concentration profiles collected during both summer and winter. Physicochemical parameters and dissolved concentrations of major elements, nutrients, and Se were measured and used to model fluxes at the sediment–water interface and to calculate Se speciation. The results suggest that the proximity of the pond from the permafrost structures influenced their biogeochemical dynamics. In the ponds close to permafrost, Se concentrations are 2-fold higher in winter compared to summer, accompanied by an increase in sediment fluxes from 13 to 149 pmol cm<sup>–2</sup> yr<sup>–1</sup> between summer and winter. The combination of comparatively older dissolved organic matter and of oxygenated conditions explain the seasonal variation in Se concentrations. In the ponds further from the permafrost, Se concentrations are higher, remain unchanged in the water column across seasons, and are linearly correlated with both DOC (<i>R</i><sup>2</sup> = 0.64, <i>p</i> < 0.01, <i>n</i> = 50) and Fe (<i>R</i><sup>2</sup> = 0.60) concentrations. Thermodynamic calculations show that Se(IV) dominates Se speciation in the porewater at all sites, while the water column reaches saturation with respect to elemental zerovalent Se, suggesting that precipitation of elemental Se could mediate dissolved Se concentrations. Collectively, our results point to the strong control that redox conditions exert on Se mobility, via DOC and Fe, and to the linkages between landscape features, pond physicochemistry, and Se dynamics.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141515261","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}