<?xml version="1.0" encoding="UTF-8"?>
<!DOCTYPE root>
<article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:ali="http://www.niso.org/schemas/ali/1.0/" article-type="research-article" dtd-version="1.2" xml:lang="en"><front><journal-meta><journal-id journal-id-type="publisher-id">Environmental Dynamics and Global Climate Change</journal-id><journal-title-group><journal-title xml:lang="en">Environmental Dynamics and Global Climate Change</journal-title><trans-title-group xml:lang="ru"><trans-title>Динамика окружающей среды и глобальные изменения климата</trans-title></trans-title-group></journal-title-group><issn publication-format="print">2218-4422</issn><issn publication-format="electronic">2541-9307</issn><publisher><publisher-name xml:lang="en">Yugra State University</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="publisher-id">10534</article-id><article-id pub-id-type="doi">10.17816/edgcc10534</article-id><article-categories><subj-group subj-group-type="toc-heading" xml:lang="en"><subject>Theoretical works</subject></subj-group><subj-group subj-group-type="toc-heading" xml:lang="ru"><subject>Теоретические работы</subject></subj-group><subj-group subj-group-type="article-type"><subject>Research Article</subject></subj-group></article-categories><title-group><article-title xml:lang="en">Anaerobic methane oxidation by nitrate: kinetic isotope effect</article-title><trans-title-group xml:lang="ru"><trans-title>Anaerobic methane oxidation by nitrate: kinetic isotope effect</trans-title></trans-title-group></title-group><contrib-group><contrib contrib-type="author"><name-alternatives><name xml:lang="en"><surname>Vavilin</surname><given-names>Vasiliy A.</given-names></name><name xml:lang="ru"><surname>Vavilin</surname><given-names>Vasiliy А.</given-names></name></name-alternatives><address><country country="RU">Russian Federation</country></address><email>vavilin@iwp.ru</email><xref ref-type="aff" rid="aff1"/></contrib></contrib-group><aff id="aff1"><institution>Water problems institute of the Russian Academy of Sciences</institution></aff><pub-date date-type="pub" iso-8601-date="2019-01-01" publication-format="electronic"><day>01</day><month>01</month><year>2019</year></pub-date><volume>10</volume><issue>1</issue><issue-title xml:lang="en"/><issue-title xml:lang="ru"/><fpage>3</fpage><lpage>15</lpage><history><date date-type="received" iso-8601-date="2018-11-26"><day>26</day><month>11</month><year>2018</year></date></history><permissions><copyright-statement xml:lang="en">Copyright ©; 2019, Vavilin V.A.</copyright-statement><copyright-statement xml:lang="ru">Copyright ©; 2019, Вавилин В.А.</copyright-statement><copyright-year>2019</copyright-year><copyright-holder xml:lang="en">Vavilin V.A.</copyright-holder><copyright-holder xml:lang="ru">Вавилин В.А.</copyright-holder><ali:free_to_read xmlns:ali="http://www.niso.org/schemas/ali/1.0/"/><license><ali:license_ref xmlns:ali="http://www.niso.org/schemas/ali/1.0/">http://creativecommons.org/licenses/by-nd/4.0</ali:license_ref></license></permissions><self-uri xlink:href="https://edgccjournal.org/EDGCC/article/view/10534">https://edgccjournal.org/EDGCC/article/view/10534</self-uri><abstract xml:lang="en"><p><italic>The ratio of stable carbon isotopes (<sup>13</sup>C/<sup>12</sup>C) in different environments serves as a significant limitation in estimating the global balance of methane [Hornibrook et al., 2000]. In this case, the value of <sup>13</sup>C/<sup>12</sup>C largely depends on the kinetic isotope effect associated with the metabolism of microorganisms that produce and consume CH<sub>4</sub>. The article suggests a dynamic model of the processes of methane formation and its anaerobic oxidation with nitrate by methanotrophic denitrifying microorganisms (DAOM), which allowed estimating the fractionation factor of stable carbon isotopes. In the experiment with peat from the minerotrophic bog [Smemo, Yavitt, 2007], the dynamics of the amount of methane and </italic><italic>was measured. The dynamic model showed that the introduction of nitrate leads to a slow decrease in the partial pressure of methane. Since methane in the DAOM process is a substrate, methane is enriched with heavier carbon <sup>13</sup>C in the system under study. This leads to an increase in the value </italic><italic>. The carbon isotope fractionation factor during methane oxidation with nitrate was equal to 1.018 and comparable with the fraction of carbon isotope fractionation in the process of acetoclastic methanogenesis (1.01). Model calculations have shown that during incubation the apparent fractionation factor of carbon isotopes with the simultaneous formation of methane and DAOM slowly decreases. The ratio of <sup>13</sup>C/<sup>12</sup>C isotopes in dissolved and gaseous methane practically does not differ. The model showed that an increase in the initial concentration of nitrate increases the rate of DAOM, which leads to a decrease in the concentration of dissolved methane. In this case, the value of <sup>13</sup>C/<sup>12</sup>C increases. In field studies, Shi et al. (2017) showed that the presence of DAOM in peat bogs in which fertilizers penetrate can be controlled by the amount of nitrate used and the depth of penetration into the anoxic layer. Two MATLAB files describing DAOM are attached to the article.</italic></p></abstract><trans-abstract xml:lang="ru"><p><italic>The ratio of stable carbon isotopes (<sup>13</sup>C/<sup>12</sup>C) in different environments serves as a significant limitation in estimating the global balance of methane [Hornibrook et al., 2000]. In this case, the value of <sup>13</sup>C/<sup>12</sup>C largely depends on the kinetic isotope effect associated with the metabolism of microorganisms that produce and consume CH<sub>4</sub>. The article suggests a dynamic model of the processes of methane formation and its anaerobic oxidation with nitrate by methanotrophic denitrifying microorganisms (DAOM), which allowed estimating the fractionation factor of stable carbon isotopes. In the experiment with peat from the minerotrophic bog [Smemo, Yavitt, 2007], the dynamics of the amount of methane and was measured. The dynamic model showed that the introduction of nitrate leads to a slow decrease in the partial pressure of methane. Since methane in the DAOM process is a substrate, methane is enriched with heavier carbon <sup>13</sup>C in the system under study. This leads to an increase in the value . The carbon isotope fractionation factor during methane oxidation with nitrate was equal to 1.018 and comparable with the fraction of carbon isotope fractionation in the process of acetoclastic methanogenesis (1.01). Model calculations have shown that during incubation the apparent fractionation factor of carbon isotopes with the simultaneous formation of methane and DAOM slowly decreases. The ratio of <sup>13</sup>C/<sup>12</sup>C isotopes in dissolved and gaseous methane practically does not differ. The model showed that an increase in the initial concentration of nitrate increases the rate of DAOM, which leads to a decrease in the concentration of dissolved methane. In this case, the value of <sup>13</sup>C/<sup>12</sup>C increases. In field studies, Shi et al. (2017) showed that the presence of DAOM in peat bogs in which fertilizers penetrate can be controlled by the amount of nitrate used and the depth of penetration into the anoxic layer. Two MATLAB files describing DAOM are attached to the article.</italic></p> <p><italic>Отношение стабильных изотопов углерода (<sup>13</sup>C/<sup>12</sup>C) служит важным фактором при оценке глобального баланса метана [</italic><italic>Hornibrook</italic> <italic>et</italic> <italic>al</italic><italic>., 2000]</italic><italic>. При этом величина <sup>13</sup>C/<sup>12</sup>C в значительной степени зависит от кинетического изотопного эффекта, связанного с метаболизмом микроорганизмов, которые производят и потребляют CH<sub>4</sub>. В статье предлагается динамическая модель процессов образования метана и его анаэробного окисления нитратом метанотрофными денитрифицирующими микроорганизмами (</italic><italic>DAOM</italic><italic>), что позволило оценить коэффициент фракционирования стабильных изотопов углерода. В эксперименте с торфом из минеротрофного болота [</italic><italic>Smemo</italic><italic>, </italic><italic>Yavitt</italic><italic>, 2007],</italic><italic> измерялась динамика количества метана и величины . Предлагаемая нами модель показала, что введение нитрата приводит к медленному снижению парциального давления метана. Поскольку метан в процессе </italic><italic>DAOM</italic> <italic>является субстратом, в исследуемой системе происходит обогащение метана более тяжелым углеродом <sup>13</sup>С. Это приводит к возрастанию величины . Коэффициент фракционирования изотопов углерода в процессе окисления метана нитратом оказался равным 1.018 и сопоставимым с коэффициентом фракционирования изотопов углерода в процессе ацетокластического метаногенеза (1.01). Модельные расчеты показали, что к</italic><italic>ажущийся коэффициент фракционирования изотопов углерода</italic> <italic>при одновременном образовании метана и </italic><italic>DAOM</italic> <italic>в ходе инкубации медленно снижается. Отношение изотопов <sup>13</sup>C/<sup>12</sup>C в растворенном и газообразном метане практически не отличаются.</italic></p> <p><italic>Просим обратить внимание на тот факт, что текст статьи на русском языке представлен в приложении (см. пункт "Дополнительные файлы")</italic></p></trans-abstract><kwd-group xml:lang="en"><kwd>methane formation</kwd><kwd>anaerobic methane oxidation</kwd><kwd>microorganisms</kwd><kwd>nitrate</kwd><kwd>kinetic isotope effect</kwd></kwd-group><kwd-group xml:lang="ru"><kwd>образование метана</kwd><kwd>анаэробное окисление метана</kwd><kwd>микроорганизмы</kwd><kwd>нитрат</kwd><kwd>кинетический изотопный эффект</kwd></kwd-group><funding-group><funding-statement xml:lang="en">The work was carried out in under the scientific program of Water Problems Insititute of the Russian Academy of Sciences (State Registration number АААА-А18-118022090104-8).</funding-statement><funding-statement xml:lang="ru">Работа выполнена по плану НИР ИВП РАН АААА-А18-118022090104-8.</funding-statement></funding-group></article-meta></front><body></body><back><ref-list><ref id="B1"><label>1.</label><mixed-citation>Галимов ЭМ, 1973. Изотопы углерода в нефтегазовой геологии. Наука, Москва; 384 с. [Galimov EM, 1973. Izotopy Ugleroda v Neftegazovoy Geologii. Nauka, Moscow: 384 pp (In Russian)].</mixed-citation></ref><ref id="B2"><label>2.</label><mixed-citation>Batstone DJ, Keller J, Angelidaki I, 2002. Anaerobic Digestion Model No.1 (ADM1). Water Science &amp; Technology. 45:65–73.</mixed-citation></ref><ref id="B3"><label>3.</label><mixed-citation>Bridgham R, Cadillo-Quiroz H, Keller J, Zhuang Q, 2013. Methane emissions from wetlands: biogeochemical, microbial, and modeling perspectives from local to global scales. Glob. Change Biol. 19:1325–1346. doi: 10.1111/gcb.12131</mixed-citation></ref><ref id="B4"><label>4.</label><mixed-citation>Conrad R, 2005. Quantification of methanogenic pathways using stable carbon isotopic signatures: a review and a proposal. Organ. Geochem. 36:739–752. doi: 10.1016/j.orggeochem.2004.09.006</mixed-citation></ref><ref id="B5"><label>5.</label><mixed-citation>Craig H, 1957. Isotopic standards for carbon and oxygen and correction factors for mass-spectrometric analysis of carbon dioxide. Geochim. Cosmochim. Acta. 12:133–149. doi: 10.1016/0016-7037(57)90024-8</mixed-citation></ref><ref id="B6"><label>6.</label><mixed-citation>Ettwig K, Butler M, Le Paslier D, 2010. Nitrite-driven anaerobic methane oxidation by oxygenic bacteria. Nature. 464:543–550.</mixed-citation></ref><ref id="B7"><label>7.</label><mixed-citation>Hornibrook E, Longstaffe F, Fyfe W, 2000. Evolution of stable carbon isotope compositions for methane and carbon dioxide in freshwater wetlands and other anaerobic environments. Geochim. Cosmochim. Acta. 64:1013–1027. doi: 10.1016/s0016-7037(99)00321-x</mixed-citation></ref><ref id="B8"><label>8.</label><mixed-citation>Kallistova AY, Merkel AY, Pimenov NV, Tarnovetskii IY, 2017. Methane formation and oxidation by prokaryotes. Microbiology (Mikrobiologiya). 86:671–691. doi: 10.7868/S002636561706009X</mixed-citation></ref><ref id="B9"><label>9.</label><mixed-citation>Knox M, Quay P, Wilbur D, 1992. Kinetic isotopic fractionation during air-water gas transfer of O2, N2, CH4, and H2. Journal of Geophys. Res. 97:20335–20343. doi: 10.1029/92jc00949</mixed-citation></ref><ref id="B10"><label>10.</label><mixed-citation>Lynd LR, Weimer P, Zyl W van, Pretorius I, 2002. Microbial cellulose utilization: fundamentals and biotechnology. Microbiol. Molecul. Biol. Rev. 66:506–577. doi: 10.1128/mmbr.66.4.739.2002</mixed-citation></ref><ref id="B11"><label>11.</label><mixed-citation>MathWorks Inc., 1984. The MathWorks, Inc., Natick, Massachusetts, USA.</mixed-citation></ref><ref id="B12"><label>12.</label><mixed-citation>Penning H, Claus P, Casper P, Conrad R, 2006. Carbon isotope fractionation during acetoclastic methanogenesis by Methanosaeta concilii in culture and lake sediment. Appl. Environ. Microbiol. 72:5648–5652. doi: 10.1128/aem.00727-06</mixed-citation></ref><ref id="B13"><label>13.</label><mixed-citation>Rasigraf O, Vogt C, Richnow H, Jetten M, Ettwig K, 2012. Carbon and hydrogen isotope fractionation during nitrite-dependent anaerobic methane oxidation by Methylomirabilis oxyfera. Cosmochim. Acta. 89:256–264. doi: 10.1016/j.gca.2012.04.054</mixed-citation></ref><ref id="B14"><label>14.</label><mixed-citation>Rayleigh J, 1896. Theoretical consideration respecting the separation of gases by diffusion and similar processes. Philos. Mag. 42:493–498. doi: 10.1080/14786449608620944</mixed-citation></ref><ref id="B15"><label>15.</label><mixed-citation>Rittmann B, McCarty P, 2001. Environmental Biotechnology: Principles and Applications. McGraw-Hill, New York: 768 pp.</mixed-citation></ref><ref id="B16"><label>16.</label><mixed-citation>Shi Y, Wang Z, He C, Zhang X, Sheng L, Ren X, 2017. Using 13C isotopes to explore denitrification-dependent anaerobic methane oxidation in paddy-peatland. Nature Publ. Group. Sci. Rep. 7:40848. doi: 10.1038/srep40848. 10.1038/srep40848</mixed-citation></ref><ref id="B17"><label>17.</label><mixed-citation>Smemo K, Yavitt J, 2007. Evidence for anaerobic CH4 oxidation in freshwater peatlands. Geomicrobiol. J. 24:583–597. doi: 10.1080/01490450701672083</mixed-citation></ref><ref id="B18"><label>18.</label><mixed-citation>Smemo K, Yavitt J, 2011. Anaerobic oxidation of methane: an underappreciated aspect of methane cycling in peatland ecosystems? Biogeosciences. 8:779–793. doi: 10.5194/bg-8-779-2011</mixed-citation></ref><ref id="B19"><label>19.</label><mixed-citation>Vavilin V, Rytov S, 2015. Nitrate denitrification with nitrite or nitrous oxide as intermediate products: Stoichiometry, kinetics and dynamics of stable isotope signatures. Chemosphere. 134:417–426. doi: 10.1016/j.chemosphere.2015.04.091</mixed-citation></ref><ref id="B20"><label>20.</label><mixed-citation>Vavilin V, Rytov S, Lokshina L, 2018. Dynamic isotope equations for 13CH4 and 13CO2 describing methane formation with a focus on the effect of anaerobic respiration in sediments of some tropical lakes. Ecol. Modell. 386:59–70. doi: 10.1016/j.ecolmodel.2018.08.005</mixed-citation></ref><ref id="B21"><label>21.</label><mixed-citation>Vavilin V, Rytov S, Lokshina L, 2018. Modelling the specific pathway of CH4 and CO2 formation using carbon isotope fractionation: an example for a boreal mesotrophic fen. Isotope Env. Health Studies. 54:475–493. doi: 10.1080/10256016.2018.1478820</mixed-citation></ref><ref id="B22"><label>22.</label><mixed-citation>Vavilin VA, Rytov SV, 2016. Inhibition by nitrite ion in the process of methane anaerobic oxidation by microorganisms and fractionation dynamics of stable carbon and hydrogen isotopes. Water Resources 43:663–667. doi: 10.7868/S0321059616040167</mixed-citation></ref><ref id="B23"><label>23.</label><mixed-citation>Vavilin VA, Rytov SV, Conrad R. Modelling methane formation in sediments of tropical lakes focusing on syntrophic acetate oxidation: Dynamic and static isotope equations. Ecol. Modell. 2017;363:81-95. doi: 10.1016/j.ecolmodel.2017.08.024</mixed-citation></ref><ref id="B24"><label>24.</label><mixed-citation>Whiticar M, 1999. Carbon and hydrogen isotope systematics of bacterial formation and oxidation of methane. Chem. Geology. 161:291–314. doi: 10.1016/s0009-2541(99)00092-3</mixed-citation></ref><ref id="B25"><label>25.</label><mixed-citation>Zinder S, 1993. Physiological Ecology of Methanogens., p. 128–206 In: Ferry J (ed.), Methanogenesis, Ecology, Physiology, Biochemistry and Genetics., New York: Chapman &amp; Hall. doi: 10.1007/978-1-4615-2391-8_4</mixed-citation></ref></ref-list></back></article>
